Ambiental - Quimica Ambiental - Colin Baird - Inglês

Periodic Table
1 18
1 2
H He
1.00797 2 13 14 15 16 17 4.003
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
6.941 9.012 10.81 12.011 14.007 15.9994 19.00 20.179
11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
22.990 24.31 3 4 5 6 7 8 9 10 11 12 26.98 28.09 30.974 32.064 35.453 39.948
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.102 40.08 44.96 47.88 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.38 69.72 75.59 74.92 78.96 79.90 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 88.906 91.22 92.91 95.94 (98) 101.1 102.905 106.4 107.870 112.41 114.82 118.69 121.75 127.60 126.90 131.29
55 56 57–71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba Rare Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.905 137.33 Earths 178.49 180.95 183.85 186.2 190.2 192.2 195.09 196.97 200.59 204.37 207.19 208.98 (210) (210) (222)
87 88 89–103 104 105 106 107 108 109 110 111 112
Fr Ra Actinides Rf Du Sg Bh Hs Mt — — —
(223) (226) (261) (260) (263) (262) (265) (266) (273) (?) (277)
57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
Rare Earths La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
(Lanthanides) 138.91 140.12 140.91 144.24 (147) 150.36 152.0 157.25 158.92 162.50 164.93 167.26 168.93 173.04 174.97
89 90 91 92 93 94 95 96 97 98 99 100 101 102 103

Actinides Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
227.03 232.04 231.04 238.03 237.05 (244) (243) (247) (247) (251) (252) (257) (258) (259) (260)
The 1–18 group designation has been recommended by the International Union of Pure and Applied Chemistry (IUPAC).
E N V I R O N M E N TA L C H E M I S T R Y
ENVIRONMENTAL
CHEMISTRY FOURTH
EDITION
 COLIN BAIRD
University of Western Ontario
 MICHAEL CANN
University of Scranton
W. H. FREEMAN AND COMPANY

New York
Publisher: Clancy Marshall
Senior Acquisitions Editor: Jessica Fiorillo
Marketing Manager: Anthony Palmiotto
Media and Supplements Editor: Samantha Calamari
Assistant Editor: Kathryn Treadway
Photo Editor: Ted Szczepanski
Cover and Text Designer: Blake Logan
Project Editor: Vivien Weiss
Illustrations: ICC Macmillan Inc.
Senior Illustration Coordinator: Bill Page
Production Coordinator: Paul W. Rohloff
Composition: ICC Macmillan Inc.
Printing and Binding: RR Donnelley
Library of Congress Preassigned Control Number: 2007939344

ISBN-13: 978-1-4292-0146-0
ISBN-10: 1-4292-0146-0
© 2008 by W. H. Freeman and Company.

All rights reserved
Printed in the United States of America
First printing
W. H. Freeman and Company

41 Madison Avenue
New York, NY 10010
Houndmills, Basingstoke RG21 6XS, England
www.whfreeman.com
BRIEF CONTENTS
Preface xv
Environmental Chemistry 1
Scientific American Feature Article: Little Green Molecules 14
PART I ATMOSPHERIC CHEMISTRY

AND AIR POLLUTION 25
CHAPTER 1 Stratospheric Chemistry: The Ozone Layer 27
CHAPTER 2 The Ozone Holes 59
CHAPTER 3 The Chemistry of Ground-Level
Air Pollution 91
CHAPTER 4 The Environmental and Health Consequences
of Polluted Air—Outdoors and Indoors 145
CHAPTER 5 The Detailed Chemistry of the Atmosphere 175
Environmental Instrumental Analysis I: Instrumental
Determination of NOX via Chemiluminescence 199
PART II ENERGY AND CLIMATE

CHANGE 203
CHAPTER 6 The Greenhouse Effect 205
CHAPTER 7 Fossil-Fuel Energy, CO2 Emissions,
and Global Warming 261
CHAPTER 8 Renewable Energy, Alternative Fuels,
and the Hydrogen Economy 311
CHAPTER 9 Radioactivity, Radon, and Nuclear Energy 367
Environmental Instrumental Analysis II: Instrumental
Determination of Atmospheric Methane 398
Scientific American Feature Article: A Plan to Keep Carbon
in Check 402
v
vi Brief Contents
PART III TOXIC ORGANIC

COMPOUNDS 413
CHAPTER 10 Pesticides 415
CHAPTER 11 Dioxins, Furans, and PCBs 469
CHAPTER 12 Other Toxic Organic Compounds
of Environmental Concern 507
Environmental Instrumental Analysis III: Electron Capture
Detection of Pesticides 537
Environmental Instrumental Analysis IV: Gas Chromatography/
Mass Spectrometry (GC/MS) 540
Scientific American Feature Article: Tackling Malaria 544
PART IV WATER CHEMISTRY AND

WATER POLLUTION 555
CHAPTER 13 The Chemistry of Natural Waters 557
CHAPTER 14 The Pollution and Purification of Water 601
Environmental Instrumental Analysis V: Ion Chromatography
of Environmentally Significant Anions 657
PART V METALS, SOILS,

SEDIMENTS, AND
WASTE DISPOSAL 661
CHAPTER 15 Toxic Heavy Metals 663
CHAPTER 16 Wastes, Soils, and Sediments 713
Environmental Instrumental Analysis VI: Inductively Coupled
Plasma Determination of Lead 770
Scientific American Feature Article: Mapping Mercury 775
Appendix: Background Organic Chemistry AP-1

Answers to Selected Odd-Numbered Problems AN-1
Index I-1
CONTENTS
Preface xv
Environmental Chemistry 1
Introduction 1
A Brief History of Environmental Regulation 3
Green Chemistry 4
The 12 Principles of Green Chemistry 5
Presidential Green Chemistry Challenge Awards 7
Real-World Examples of Green Chemistry 7
Further Readings 12
Websites of Interest 12
Scientific American Feature Article: Little Green Molecules 14
PART I ATMOSPHERIC CHEMISTRY

AND AIR POLLUTION 25
CHAPTER 1 Stratospheric Chemistry: The Ozone Layer 27
Introduction 27
The Physics and Chemistry of the Ozone Layer 30
Box 1-1: The Steady-State Analysis of Atmospheric Reactions 44
Catalytic Processes of Ozone Destruction 47
Box 1-2: The Rates of Free-Radical Reactions 49
Review Questions 56
Additional Problems 56
Further Readings 58
CHAPTER 2 The Ozone Holes 59

Introduction 59
The Ozone Hole and Other Sites of Ozone Depletion 63
Box 2-1: The Chemistry Behind Mid-Latitude Decreases
in Stratospheric Ozone 75
vii
viii Contents
The Chemicals That Cause Ozone Destruction 77

Green Chemistry: The Replacement of CFC and Hydrocarbon
Blowing Agents with Carbon Dioxide in Producing Foam
Polystyrene 79
Green Chemistry: Harpin Technology—Eliciting Nature’s
Own Defenses Against Diseases 86
Review Questions 87
Green Chemistry Questions 87
Further Readings 89
CHAPTER 3 The Chemistry of Ground-Level

Air Pollution 91
Introduction 91
Box 3-1: The Interconversion of Gas Concentrations 93
Urban Ozone: The Photochemical Smog Process 97
Technological Control of Emissions 109
Green Chemistry: The Replacement of Organic Solvents
with Supercritical and Liquid Carbon Dioxide; Development
of Surfactants for This Compound 119
Green Chemistry: Using Ionic Liquids to Replace Organic
Solvents; Cellulose, a Naturally Occurring Polymer
Replacement for Petroleum-Derived Polymers 120
Particulates in Air Pollution 132
Air Quality Indices and Size Characteristics for Particulate Matter 137
Box 3-2: Distribution of Particle Sizes in an Urban Air Sample 139
Review Questions 141
Further Readings 143
CHAPTER 4 The Environmental and Health

Consequences of Polluted Air—
Outdoors and Indoors 145
Introduction 145
Acid Rain 147
The Human Health Effects of Outdoor Air Pollutants 155
Indoor Air Pollution 163
Contents ix
CHAPTER 5 The Detailed Chemistry of the Atmosphere 175

Introduction 175
Box 5-1: Lewis Structures of Simple Free Radicals 176
Tropospheric Chemistry 177
Systematics of Stratospheric Chemistry 194
Environmental Instrumental Analysis I: Instrumental
Determination of NOX via Chemiluminescence 199
PART II ENERGY AND CLIMATE

CHANGE 203
CHAPTER 6 The Greenhouse Effect 205
Introduction 205
The Mechanism of the Greenhouse Effect 206
Box 6-1: A Simple Model of the Greenhouse Effect 213
Molecular Vibrations: Energy Absorption by Greenhouse Gases 214
The Major Greenhouse Gases 217
Green Chemistry: Supercritical Carbon Dioxide in the Production
of Computer Chips 225
Box 6-2: Supercritical Carbon Dioxide 228
Atmospheric Residence Time 231
Other Greenhouse Gases 234
Box 6-3: Determining the Emissions of “Old Carbon”
Sources of Methane 238
The Climate-Modifying Effects of Aerosols 246
Box 6-4: Cooling over China from Haze 250
Global Warming to Date 251
CHAPTER 7 Fossil-Fuel Energy, CO2 Emissions,
and Global Warming 261
Introduction 261
Energy Reserves and Usage 262
Fossil Fuels 270
Box 7-1: Petroleum Refining: Fractional Distillation 276
x Contents
Energy and Carbon Dioxide Emissions in the Future 292

Green Chemistry: Polylactic Acid—The Production
of Biodegradable Polymers from Renewable Resources;
Reducing the Need for Petroleum and the Impact on
the Environment 295
The Extent and Potential Consequences of Future
Global Warming 297
CHAPTER 8 Renewable Energy, Alternative Fuels,
and the Hydrogen Economy 311
Introduction 312
Renewable Energy 312
Alternative Fuels: Alcohols, Ethers, and Esters 333
Green Chemistry: Valuable Chemical Feedstocks from Glycerin,
a Waste By-Product in the Production of Biodiesel 348
Hydrogen—Fuel of the Future? 350
CHAPTER 9 Radioactivity, Radon, and Nuclear Energy 367
Introduction 367
Radioactivity and Radon Gas 368
Box 9-1: Steady-State Analysis of the Radioactive
Decay Series 373
Nuclear Energy 378
Box 9-2: Radioactive Contamination by
Plutonium Production 390
Environmental Instrumental Analysis II: Instrumental
Determination of Atmospheric Methane 398
Scientific American Feature Article: A Plan to Keep Carbon
in Check 402
Contents xi
PART III TOXIC ORGANIC

COMPOUNDS 413
CHAPTER 10 Pesticides 415
Introduction 415
DDT 421
The Accumulation of Organochlorines in Biological Systems 425
Other Organochlorine Insecticides 430
Box 10-1: The Controversial Insecticide Endosulfan 433
Principles of Toxicology 434
Organophosphate and Carbamate Insecticides 441
Natural and Green Insecticides, and Integrated Pest Management 447
Green Chemistry: Insecticides That Target Only
Certain Insects 449
Green Chemistry: A New Method for Controlling
Termites 450
Herbicides 452
Box 10-2: Genetically Engineered Plants 457
Summary 461
Box 10-3: The Environmental Distribution of Pollutants 462
CHAPTER 11 Dioxins, Furans, and PCBs 469

Introduction 469
Dioxins 469
Box 11-1: Deducing the Probable Chlorophenolic Origins
of a Dioxin 475
PCBs 477
Box 11-2: Predicting the Furans That Will Form from
a Given PCB 486
Other Sources of Dioxins and Furans 487
Green Chemistry: H2O2, an Environmentally Benign
Bleaching Agent for the Production of Paper 489
The Health Effects of Dioxins, Furans, and PCBs 493
xii Contents
CHAPTER 12 Other Toxic Organic Compounds

of Environmental Concern 507
Introduction 507
Polynuclear Aromatic Hydrocarbons (PAHs) 508
Box 12-1: More on the Mechanism of PAH Carcinogenesis 515
Environmental Estrogens 517
The Long-Range Transport of Atmospheric Pollutants 525
Brominated Fire Retardants 528
Perfluorinated Sulfonates 533
Environmental Instrumental Analysis III: Electron Capture Detection
of Pesticides 537
Environmental Instrumental Analysis IV: Gas Chromatography/Mass
Spectrometry (GC/MS) 540
Scientific American Feature Article: Tackling Malaria 544
PART IV WATER CHEMISTRY AND

WATER POLLUTION 555
CHAPTER 13 The Chemistry of Natural Waters 557
Introduction 557
Oxidation–Reduction Chemistry in Natural Waters 559
Box 13-1: Redox Equation Balancing Reviewed 560
Green Chemistry: Enzymatic Preparation of Cotton Textiles 565
Acid–Base Chemistry in Natural Waters: The Carbonate System 578
Box 13-2: Derivation of the Equations for Species Diagram Curves 580
Ion Concentrations in Natural Waters and Drinking Water 589
CHAPTER 14 The Pollution and Purification of Water 601

Introduction 601
Water Disinfection 602
Box 14-1: Activated Carbon 603
Box 14-2: The Desalination of Salty Water 608
Box 14-3: The Mechanism of Chloroform Production
in Drinking Water 614
Contents xiii
Groundwater: Its Supply, Chemical Contamination, and Remediation 618

The Chemical Contamination and Treatment of Wastewater
and Sewage 636
Box 14-4: Time Dependence of Concentrations in the Two-Step
Oxidation of Ammonia 639
Green Chemistry: Sodium Iminodisuccinate—A Biodegradable
Chelating Agent 642
Modern Wastewater and Air Purification Techniques 648
Environmental Instrumental Analysis V: Ion Chromatography
of Environmentally Significant Anions 657
PART V METALS, SOILS,

SEDIMENTS, AND
WASTE DISPOSAL 661
CHAPTER 15 Toxic Heavy Metals 663
Introduction 663
Mercury 666
Lead 679
Green Chemistry: Replacement of Lead in Electrodeposition
Coatings 684
Cadmium 692
Arsenic 694
Box 15-1: Organotin Compounds 697
Chromium 705
Green Chemistry: Removing the Arsenic and Chromium
from Pressure-Treated Wood 707
CHAPTER 16 Wastes, Soils, and Sediments 713

Introduction 713
Domestic and Commercial Garbage: Its Disposal and Minimization 714
Green Chemistry: Polyaspartate—A Biodegradable Antiscalant
and Dispersing Agent 721
xiv Contents
The Recycling of Household and Commercial Waste 723

Green Chemistry: Development of Recyclable Carpeting 732
Soils and Sediments 735
Box 16-1: The Superfund Program 748
Hazardous Wastes 758
Environmental Instrumental Analysis VI: Inductively
Coupled Plasma Determination of Lead 770
Scientific American Feature Article: Mapping Mercury 775
Appendix: Background Organic Chemistry AP-1

Index I-1
PREFACE
To the Student
There are many definitions of environmental chemistry. To some, it is solely
the chemistry of Earth’s natural processes in air, water, and soil. More com-
monly, as in this book, it is concerned principally with the chemical aspects
of problems that humankind has created in the natural environment. Part of
this infringement on the natural chemistry of our planet has resulted from
the activities of our everyday lives. In addition, chemists, through the products
they create and the processes used to create them, have also had a significant
impact on the chemistry of the environment.
Chemistry has played a major role in the advancement of society and in
making our lives longer, healthier, more comfortable, and more enjoyable.
The effects of human-made chemicals are ubiquitous and in many instances
quite positive. Without chemistry there would be no pharmaceutical drugs,
no computers, no automobiles, no TVs, no DVDs, no lights, no synthetic
fibers. However, along with all the positive advances that result from chem-
istry, copious amounts of toxic and corrosive chemicals have also been pro-
duced and dispersed into the environment. Historically, chemists as a group
have not always paid enough attention to the environmental consequences
of their activities.
But it is not just the chemical industry, or even industry as a whole, that has
emitted troublesome substances into the air, water, and soil. The fantastic
increase in population and affluence since the Industrial Revolution has over-
loaded our atmosphere with carbon dioxide and toxic air pollutants, our waters
with sewage, and our soil with garbage. We are exceeding the planet’s natural
capacity to cope with waste, and, in many cases, we do not know the conse-
quences of these actions. As a character in Margaret Atwood’s recent novel Oryx
and Crake, stated, “The whole world is now one vast uncontrolled experiment.”
During your journey through the chapters in this text, you will see that
scientists do have a good handle on many environmental chemistry problems
and have suggested ways—although sometimes very expensive ones—to keep
us from inheriting the whirlwind of uncontrolled experiments on the planet.
Chemists have also become more aware of the contributions of their own
profession and industry in creating pollution and have created the concept of
green chemistry to help minimize their environmental footprint in the future.
xv
xvi Preface
To illustrate these efforts, case studies of their initiatives have been included
in the book. However, as a prelude to these studies, in the Introduction we
discuss some of the history of environmental regulations—especially in the
United States—as well as the principles and an illustrative application of the
green chemistry movement that has developed.
Although the science underlying environmental problems is often mad-
deningly complex, its central aspects can usually be understood and appreciated
with only introductory chemistry as background preparation. However, stu-
dents who have not had some introduction to organic chemistry are encour-
aged to work through the Appendix on Background Organic Chemistry,
particularly before tackling Chapters 10 to 12. Furthermore, the listing of gen-
eral chemistry concepts that will be used in each chapter should assist in iden-
tifying topics from earlier courses that are worth reviewing.
To the Instructor
Environmental Chemistry, Fourth Edition, has been revised and updated in
line with comments and suggestions from various users and reviewers of the
third edition. In particular, where possible, we have fulfilled the request that
larger chapters be split so that they can be covered in a week or two. In sev-
eral places, some of the more advanced material has been placed in boxes that
have been reordered to appear at the end of a series of related chapters.
Some instructors prefer to cover chapters in a different order than we
have used, so the list of concepts that opens each chapter, describing mater-
ial covered elsewhere in the book, should help facilitate restructuring.
As in previous editions, the background required to solve both in-text
and end-of-chapter problems is either developed in the book or would have
been covered previously in a general chemistry course—as listed at the begin-
ning of each chapter. Where appropriate, hints are given to start students
on the solution. The Solutions Manual to the text includes worked solutions
to all problems (except for Review Questions, which are designed to direct
students back to descriptive material within each chapter).
New to This Edition

• All chapters now start with an outline of the concepts and methods from
introductory chemistry and from previous chapters of the text that will be
used in the chapter. This will give students a better idea of what background
material to review, and it will give instructors a better idea of what is assumed
in the material.
• Detailed applications of several of the newsworthy topics in the text have
been formulated as Case Studies and are available on the website for this text
(www.whfreeman.com/envchem4).
Preface xvii
• Much of the detail concerning CFCs (Chapter 2) has been cut, as it is

now largely irrelevant since CFCs have been banned. However, the back-
ground and politics of the controversy about the remaining ozone-depleting
substance have been documented in the new web-based Case Study
Strawberry Fields—The Banning of Methyl Bromide.
• Material on converters and traps for diesel engines and lawn mowers, as
well as the problems of two-stroke engines, together with the initiatives to
produce low-sulfur gasoline and diesel fuel, have been added to Chapter 3.
• The relatively advanced material on the distribution of particle sizes in
tropospheric air has been rewritten, with a new and more informative illus-
tration, and placed in Box 3-2.
• A new green chemistry case concerning the use of ionic liquids has been
added to Chapter 3.
• The information concerning the aqueous-phase oxidation of atmospheric
SO2 has been moved to a more relevant position in Chapter 3.
• Material concerning particulates in air as a health risk has been updated
and reformulated as the web-based Case Study The Effect of Urban Air
Particulates on Human Mortality, associated with Chapter 4.
• Material on the acid rain problem in China has been added and the con-
cept of critical load introduced (Chapter 4).
• The Indoor Air Pollution section on benzene has been expanded to
introduce the term air toxics and to discuss methylated benzenes as well as the
parent compound (Chapter 4).
• The term albedo is now introduced early in Chapter 6, and sunlight reflec-
tion is further discussed.
• Material introducing the greenhouse effect and the discussion of Earth’s
energy balance, previously split between these two areas, has logically been
combined and expanded by introducing a simple physical model for green-
house warming in Chapter 6. A more sophisticated model of the greenhouse
effect has been added as Box 6-1.
• A phase diagram for CO2, showing the supercritical region, has been
included to illustrate the green chemistry case in Box 6-2.
• The section on methane has been rewritten and updated, with new
graphs provided, especially with regard to its current concentration plateau
(Chapter 6).
• Updates on climate change based on the IPCC Fourth Assessment
Report are included in Chapter 6.
xviii Preface
• Chapter 7 now begins with a more extensive discussion of energy usage

and CO2 emissions by country, with an analysis of the factors that affect
them globally and with particular reference to the United States and
China.
• A separate Box 7-1, on fractional distillation of petroleum, has been
added.
• Material on carbon sequestration—particularly on the chemistry
involved—has been expanded and updated, given the growing importance of
this technique (Chapter 7).
• Material in Chapter 8 concerning renewable energy sources—wind,
hydroelectricity, biofuels, and geothermals—has been added, along with the
web-based Case Study Mercury Pollution and the James Bay Hydroelectric
Project (Canada).
• A new green chemistry case concerning the production of biodiesel has
been added to Chapter 8.
• The chapter Radioactivity, Radon, and Nuclear Energy (now Chapter 9)
has been repositioned into Part II, Energy and Climate Change.
• In the discussions about radioactivity (Chapter 9), definitions of the
bequerel and the curie are now provided. The controversial hormesis theory is
also introduced, and the debate about the existence of a threshold for health
damage from radioactivity has been expanded. The material on the repro-
cessing of nuclear waste has been developed into a fuller discussion of the
chemistry involved.
• The history of DDT, and an expanded discussion about banning it, have
been incorporated into the web-based Case Study To Ban or Not to Ban DDT?
Its History and Future, associated with Chapter 10.
• The term lethal concentration has been introduced in Chapter 10.
• The Chapter 10 material on organophosphate insecticides has been reor-
ganized so that a description of their molecular structure now precedes expla-
nation of their uses, etc. Pesticide toxicities are now discussed in terms of
World Health Organization (WHO) categories.
• An extended treatment of the controversial insecticide endosulfan has
been developed in the new Box 10-1.
• At the suggestion of several reviewers, a short discussion of the degrada-
tion of pesticides is now incorporated in Chapter 10.
• Chapter 11 now includes additional help for students in solving problems
that involve the production of dioxins from chlorophenols.
Preface xix
• The section concerning PBDEs (Chapter 12) now incorporates a descrip-

tion of the chemical mechanism by which brominated fire retardants operate,
and it has been extensively updated with new information concerning the
uses and regulatory status of PBDEs.
• Following the suggestion of several reviewers, a new Environmental
Instrumentation Analysis box on the widespread use of GC/MS for pesticide
analysis has been added at the end of Part III.
• The new Box 13-1 reviews the assignment of oxidation numbers and the
balancing of redox equations.
• The sections on sulfur compounds and acid mine drainage have been
revised and repositioned (Chapter 13) so that the pE concept need not be
covered as background to them.
• At reviewer request, the species diagram for the CO2–carbonate system
and its derivation have been added (Chapter 13).
• A new web-based Case Study, Mercury Emissions from Power Plants, a
topic of considerable current interest, has been added (Chapter 15).
• The information concerning the arsenic-contaminated drinking water in
Asia has been updated, and more information has been added concerning the
ways As can be removed from water (Chapter 15).
Scientific American Feature Articles

We are proud to feature several Scientific American articles in this edition.
The topics discussed in these articles are highly relevant to topics covered
in the book and allow students access to the most current thinking about
contemporary environmental issues by active researchers.
Supplements
The Solutions Manual (1-4292-1005-2) includes worked solutions to virtually
all problems (except for Review Questions, which are designed to direct stu-
dents back to the appropriate material within each chapter).
Students and instructors interested in pursuing specific topics in more
detail should consult the Further Readings section at the end of each chapter,
as well as the Websites of Interest that are given for each chapter on the
website, www.whfreeman.com/envchem4.
To All Readers of the Text

The authors are happy to receive comments and suggestions about the
content of this book from instructors and students via e-mail: Colin Baird at
[email protected] and Michael Cann at [email protected].
xx Preface
Acknowledgments
The authors wish to express their gratitude and appreciation to a number of
people who in various ways have contributed to this edition of the book:
To Professor Thomas Chasteen of Sam Houston State University for
masterfully writing the Environmental Instrumental Analysis boxes, which
shed light on the perspective of scientists working in this discipline and add
much to the book.
To Professor Brian D. Wagner of the University of Prince Edward Island,
for supplying some of the Additional Problems included in the book.
To the students and instructors who have used previous editions of the
text and who, via their reviews and e-mails, have pointed out subsections and
problems that needed clarifying or expanding.
To W. H. Freeman and Company Senior Acquisitions Editor for the third
and fourth editions, Jessica Fiorillo; Project Editor Vivien Weiss; and
Assistant Editor Kathryn Treadway—for their encouragement, ideas, insight-
ful suggestions, patience, and organizational abilities. To Margaret Comaskey
for her careful copyediting and suggestions again in this edition, to Ted
Szczepanski for finding the photographs, to Nancy Walker for obtaining per-
missions for figures and photographs, to Blake Logan for design, and to Paul
Rohloff for coordinating production.
Colin Baird wishes to express his thanks . . .

To Ron Martin and Martin Stillman, his colleagues at the University of
Western Ontario who used the first two editions and have made valuable sug-
gestions for improvement, and to his colleagues at Western and elsewhere
who supplied information or answered queries on various subjects: Myra
Gordon, Duncan Hunter, Roland Haines, Edgar Warnhoff, Marguerite Kane,
Currie Palmer, Rob Lipson, Dave Shoesmith, Felix Lee, Peter Guthrie, Geoff
Rayner-Canham, and Chris Willis.
To his secretaries through the years—Sandy McCaw, Clara Fernandez,
Darlene McDonald, Diana Timmermans, Elizabeth Moreau, Shannon
Woodhouse, Wendy Smith, and Judy Purves—for their brave attempts to
decipher his writing and for dealing with the always-urgent problems that
authors seem to have.
To his daughter Jenny—and others of her generation, and those follow-
ing them—for whom this subject matter really matters.
Mike Cann wishes to express his thanks . . .

To his students (especially Marc Connelly and Tom Umile) and fellow
faculty at the University of Scranton, who have made valuable suggestions
and contributions to his understanding of green chemistry and environmen-
tal chemistry.
To Joe Breen, who was one of the pioneers of green chemistry and one of
the founders of the Green Chemistry Institute.
Preface xxi
To Paul Anastas (Center for Green Chemistry and Green Engineering

at Yale) and Tracy Williamson (U.S. Environmental Protection Agency),
whose boundless energy and enthusiasm for green chemistry are contagious.
To Debra Jennings, who for over 30 years as the chemistry department
secretary has, to his amazement, managed to decode his handwriting and sim-
ply put up with him, always in good spirit.
To his loving wife, Cynthia, who has graciously and enthusiastically
endured countless discussions of green chemistry and environmental chemistry.
To his children, Holly and Geoffrey, and his grandchildren, McKenna,
Alexia, Alan Joshua, Samantha, and Arik, who, along with future genera-
tions, will reap the rewards of sustainable chemistry.
Both authors wish to express thanks to the reviewers of the fourth edition
of the text for their helpful comments and suggestions:
Ann Marie Anderssohn, University of Portland

D. Neal Boehnke, Jacksonville University
Nathan W. Bower, Colorado College
Michael Brabec, Eastern Michigan University
Patrick J. Castle, U.S. Air Force Academy
Jihong Cole-Dai, South Dakota State University
Arlene R. Courtney, Western Oregon University
James Donaldson, University of Toronto-Scarborough
Jennifer DuBois, University of Notre Dame
Robert Haines, University of Prince Edward Island
Yelda Hangun-Balkir, California University of Pennsylvania
Michael Ketterer, Northern Arizona University
John J. Manock, University of North Carolina-Wilmington
Steven Mylon, Lafayette College
Myrna Simpson, University of Toronto
Chuck Smithhart, Delta State University
Barbara Stallman, Lourdes College
Steven Sylvester, Washington State University, Vancouver
Brian Wagner, University of Prince Edward Island
Feiyue Wang, University of Manitoba
Z. Diane Xie, University of Utah
Chunlong (Carl) Zhang, University of Houston-Clear Lake
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ENVIRONMENTAL
CHEMISTRY
Introduction If mankind is to survive, we
shall require a substantially
In this book you will study the chemistry of the air, water, and soil, and new manner of thinking.
the effects of anthropogenic activities on the chemistry of the Earth. In
Albert Einstein
addition, you will learn about green chemistry, which aims to design
technologies that lessen the ecological footprint of our activities.
Environmental chemistry deals with the reactions, fates, movements,
and sources of chemicals in the air, water, and soil. In the absence of humans,
the discussion would be limited to naturally occurring chemicals. Today, with
the burgeoning population of the Earth, coupled with continually advancing
technology, human activities have an ever-increasing influence on the chem-
istry of the environment. To the earliest humans, and even until less than a
century ago, humans must have thought of the Earth as so vast that human
activity could scarcely have any more than local effects on the soil, water, and
air. Today we realize that our activities can have not only local and regional
but also global consequences.
There are now many indications that we have exceeded the carrying
capacity of the Earth, i.e., the ability of the planet to convert our wastes back
into resources (often called nature’s interest) as quickly as we consume its nat-
ural resources and produce waste. Some say that we are living beyond the
“interest” that nature provides us and dipping into nature’s capital. In short,
many of our activities are not sustainable.
As we write these introductory remarks, we are reminded of the environ-
mental consequences of human activities that impact the areas where we live
and beyond. Colin spends his summers on a small island just off the North
Atlantic coast in Nova Scotia, while Mike spends a few weeks each winter on
the west coast of southern Florida a few kilometers from the Gulf of Mexico.
Although these locations are a great distance apart, if predictions are correct,
both may be permanently submerged by the end of this century as a result of
rising sea levels brought about by enhanced global warming (see Chapters 6
and 7). The public footbridge that links Colin’s island to the mainland is
treated with creosote, and the local residents no longer harvest mussels from
the beds below for fear they may be contaminated with PAHs (Chapter 12).
Colin’s well on this island was tested for arsenic, a common pollutant in that
1
2 Environmental Chemistry
area of abandoned gold mines (Chapter 15). To the north, the once robust
cod fishing industry of Newfoundland has collapsed due to overfishing. Mike
lives in northeastern Pennsylvania on a lake where the wood in his dock is
preserved with the heavy metals arsenic, chromium, and copper (Chapter 15).
Within a short distance are two landfills (Chapter 16), which take in an
excess of 8000 tonnes of garbage per day (from municipalities as far as
150 kilometers away), two Superfund sites (Chapter 16), and a nuclear power
plant that generates plutonium and other radioactive wastes for which there
is no working disposal plan in the United States (Chapter 9). Colin’s home
in London, Ontario, is within an hour’s drive of Lake Erie, famous for nearly
having “died” of phosphate pollution (Chapter 14), and nuclear power plants
on Lake Huron. Nearby farmers grow corn to supply to a new factory that
produces ethanol for use as an alternative fuel (Chapter 8); in Ottawa, a
Canadian company has built the first demonstration plant to convert the
cellulose from agricultural residue to ethanol (Chapter 8).
On sunny days we apply extra sunscreen because of the thinning of the
ozone layer (Chapters 1 and 2). Three of the best salmon rivers in North
America in Nova Scotia must be stocked each season because the salmon no
longer migrate up the acidified waters. Many of the lakes and streams of the
beautiful Adirondack region of upstate New York are a deceptively beautiful
crystal clear, only because they are virtually devoid of plant and animal life,
again because of acidified waters (Chapters 3 and 4).
Environmental issues like these probably have parallels with those that
exist where you live; learning more about them may convince you that environ-
mental chemistry is not just a topic of academic interest, but one that touches
your life every day in very practical ways. Many of these environmental threats
are a consequence of anthropogenic activities over the last 50 to 100 years.
In 1983 the United Nations charged a special commission with develop-
ing a plan for long-term sustainable development. In 1987 the report titled
“Our Common Future” was issued. In this report (more commonly known
as the The Brundtland Report), the following definition of sustainable
development is found:
Sustainable development is development that meets the needs of the present
without compromising the ability of future generations to meet their own
needs.
Although there are many definitions of sustainable development (or sus-
tainability), this is the most widely used. The three intersecting areas of
sustainability are focused on society, the economy, and the environment.
Together they are known as the triple bottom line. In all three areas,
consumption (particularly of natural resources) and the concomitant pro-
duction of waste are central issues.
The concept of an “ecological footprint” is an attempt to measure the
amount of biologically productive space that is needed to support a particular
human lifestyle. Currently there are about 4.5 acres of biologically productive
A Brief History of Environmental Regulation 3
space for each person on the Earth. This land provides us with the resources
that we need to support our lifestyles and to receive the waste that we gener-
ate and convert it back into resources. If the entire population of 6.5 billion
people lived like Colin and Mike (rather typical North Americans), the total
ecological footprint would require five planet Earths. Obviously, everyone on
the planet can’t live in as large and inefficient a house, drive as many kilome-
ters in such an inefficient vehicle, consume as much food (particularly meat)
and energy, create as much waste, etc., as those living in the most developed
regions. As countries such as China and India, the two most populous coun-
tries in the world (with a combined total of over 2.3 billion people) and two
of the fastest growing economies in the world, continue to develop, they look
to the lifestyles of the 1 billion people on the planet who live in already devel-
oped countries. Factor in the expected increase in population to 9 billion by
2050, and clearly this is not sustainable development.
The people of the world (in particular, those in developed countries)
must strive to lead a lifestyle that is sustainable. This does not necessarily
mean a lower standard of living for those in the developed world, but it does
mean finding ways (more efficient technologies along with conservation) to
reduce our consumption of natural resouces and the concomitant produc-
tion of waste. A widespread movement toward the development and imple-
mentation of sustainable technologies or green technologies currently seeks
to reduce energy and resource consumption, to use and develop renewable
resources, and to reduce the production of waste. In chemistry, these devel-
opments are known as green chemistry, which is described later in this
Introduction and which we will see as a theme throughout this text.
A Brief History of Environmental Regulation

In the United States, many environmental disasters came to a head in the
1960s and 1970s. In 1962, the deleterious effects of the insecticide DDT were
brought to the forefront by Rachel Carson in her seminal book, Silent Spring.
In 1969, the Cayahoga River, which runs through Cleveland, Ohio, was so
polluted with industrial waste that it caught fire. The Love Canal neighbor-
hood in Niagara Falls, New York, was built on the site of a chemical dump; in
the mid-1970s, during an especially rainy season, toxic waste began to ooze
into the basements of area homes, and drums of waste surfaced. The U.S. gov-
ernment purchased the land and cordoned off the entire Love Canal neigh-
borhood. These distressing events were brought into the homes of Americans
on the nightly news and, along with other environmental disasters, became
rallying points for environmental reform.
This era saw the creation of the U.S. Environmental Protection Agency
(EPA) in 1970, the celebration of the first Earth Day, also in 1970, and a
mushrooming number of environmental laws. Before 1960, there were
approximately 20 environmental laws in the United States; now there are
over 120. Most of the earliest of these were focused on conservation, or
setting aside land from development. The focus of environmental laws

changed dramatically, starting in the 1960s. Some of the most familiar U.S.
environmental legislation includes the Clean Air Act (1970) and the Clean
Water Act (originally known as the Federal Water Pollution Control Act
Amendments of 1972). One of the major provisions of these acts was to set
up pollution control programs. In effect, these programs attempted to control
the release of toxic and other harmful chemicals into the environment. The
Comprehensive Environmental Response, Compensation and Liability Act
(also known as the Superfund Act) set up a procedure and provided funds for
cleaning up toxic waste sites. These acts thus focused on dealing with pollu-
tants after they were produced and are known as “end-of-the-pipe solutions”
and “command and control laws.”
The risk due to a hazardous substance is a function of the exposure to and
the hazard level of the substance:
risk f (exposure hazard)
The end-of-the-pipe laws attempt to control risk by preventing our exposure
to these substances. However, exposure controls inevitably fail, which points
out the weakness of these laws. The Pollution Prevention Act of 1990 is the
only U.S. environmental act that focuses on the paradigm of prevention of
pollution at the source: If hazardous substances are not used or produced,
then their risk is eliminated. There is also no need to worry about controlling
exposure, controlling dispersion into the environment, or cleaning up
hazardous chemicals.
Green Chemistry
The U.S. Pollution Prevention Act of 1990 set the stage for green chemistry.
Green chemistry became a formal focus of the U.S. EPA in 1991 and became
part of a new direction set by the EPA, by which the agency worked with
and encouraged companies to voluntarily find ways to reduce the environ-
mental consequences of their activities. Paul Anastas and John Warner
defined green chemistry as the design of chemical products and processes that
reduce or eliminate the use and generation of hazardous substances. Moreover,
green chemistry seeks to
• reduce waste (especially toxic waste),
• reduce the consumption of resources and ideally use renewable resources,
and
• reduce energy consumption.
Anastas and Warner also formulated the 12 principles of green chemistry. These
principles provide guidelines for chemists in assessing the environmental
impact of their work.
The 12 Principles of Green Chemistry 5
The 12 Principles of Green Chemistry

1. It is better to prevent waste than to treat or clean up waste after it is
formed.
2. Synthetic methods should be designed to maximize the incorporation of
all materials used in the process into the final product.
3. Wherever practicable, synthetic methodologies should be designed to
use and generate substances that possess little or no toxicity to human
health and the environment.
4. Chemical products should be designed to preserve efficacy of function
while reducing toxicity.
5. The use of auxiliary substances (solvents, separation agents, etc.)
should be made unnecessary whenever possible and innocuous
when used.
6. Energy requirements should be recognized for their environmental
and economic impacts and should be minimized. Synthetic methods
should be conducted at ambient temperature and pressure.
7. A raw material feedstock should be renewable rather than depleting
whenever technically and economically practical.
8. Unnecessary derivatization (blocking group, protection/deprotection,
temporary modification of physical/chemical processes) should be avoided
whenever possible.
9. Catalytic reagents (as selective as possible) are superior to stoichiometric
reagents.
10. Chemical products should be designed so that at the end of their
function they do not persist in the environment and ultimately break
down into innocuous degradation products.
11. Analytical methodologies need to be further developed to allow for
real-time in-process monitoring and control prior to the formation of
hazardous substances.
12. Substances and the form of a substance used in a chemical process
should be chosen so as to minimize the potential for chemical accidents,
including releases, explosions, and fires.
In many of the chapters that follow, real-world examples of green chem-

istry are discussed. During these discussions, you should keep in mind the
12 principles of green chemistry and decide which of them are met by the par-
ticular example. Although we won’t consider all of the principles at this
point, a brief discussion of some of them is beneficial.
• Principle 1 is the heart of green chemistry and places the emphasis on the
prevention of pollution at the source rather than cleaning up waste after it
has formed.
• Principles 2–5, 7–10, and 12 focus on the materials that are used in the
production of chemicals and the products that are formed.
° In a chemical synthesis, unwanted by-products are often formed in
addition to the desired product(s); these compounds are usually dis-
carded as waste. Principle 2 encourages chemists to look for synthetic
routes that maximize the production of the desired product(s) and
at the same time minimize the production of unwanted by-products
(see the synthesis of ibuprofen discussed later).
° Principles 3 and 4 stress that the toxicity of materials and products
should be kept to a minimum. As we will see in later discussions of
green chemistry, Principle 4 is often met when new pesticides are
designed with reduced toxicity to nontarget organisms.
° During the course of a synthesis, chemists employ not only com-
pounds that are actually involved in the reaction (reactants) but also
auxiliary substances such as solvents (to dissolve the reactants and to
purify the products) and agents that are used to separate and dry the
products. These materials are usually used in much larger quantities
than the reactants, and they contribute a great deal to the waste
produced during a chemical synthesis. When chemists are designing a
synthesis, Principle 5 reminds them to consider ways to minimize the
use of these auxiliary substances.
° Many organic chemicals are produced from petroleum, which is a non-
renewable resource. Principle 7 urges chemists to consider ways to produce
chemicals from renewable resources such as plant material (biomass).
° As we will see in Chapter 10, DDT is an effective pesticide. How-
ever, a major environmental problem is its stability in the natural envi-
ronment. DDT degrades slowly. Although it has been banned in most
developed countries since the 1970s (in the United States since 1972),
it can still be found in the environment, particularly in the fatty tissues
of animals. Principle 10 stresses the need to consider the lifetimes of
chemicals in the environment and the need to focus on materials (such
as pesticides) that degrade rapidly in the environment to harmless
substances.
• Many chemical reactions require heating or cooling and/or a pressure
higher or lower than atmospheric pressure. Performing reactions at other
than ambient temperature and pressure requires energy; Principle 6 reminds
chemists of these considerations when designing a synthesis.
Presidential Green Chemistry Challenge Awards

To recognize outstanding examples of green chemistry, the Presidential
Green Chemistry Challenge Awards were established in 1996 by the U.S.
EPA. Generally five awards are given each year at a ceremony held at the
National Academy of Sciences in Washington, D.C. The awards are given in
the following three categories.
1. The use of alternative synthetic pathways for green chemistry, such as:
• catalysis/biocatalysis,
• natural processes, such as photochemistry and biomimetic synthe-
sis, and
• alternative feedstocks that are more innocuous and renewable
(e.g., biomass).
2. The use of alternative reaction conditions for green chemistry, such as:
• solvents that have a reduced impact on human health and the
environment and
• increased selectivity and reduced wastes and emissions.
3. The design of safer chemicals that are, for example:
• less toxic than current alternatives and
• inherently safer with regard to accident potential.
Real-World Examples of Green Chemistry

To introduce you to the important and exciting world of green chemistry, we
provide you with real-world cases of green chemistry throughout this book.
These examples are winners of Presidential Green Chemistry Challenge
Awards. As you explore these examples, it will become apparent that green
chemistry is very important in lowering the ecological footprint of chemical
products and processes in the air, water, and soil.
We begin our journey into this important topic by briefly exploring how
green chemistry can be applied to the synthesis of ibuprofen, an important
everyday drug. We will see how the redesign of a chemical synthesis can elim-
inate a great deal of waste/pollution and reduce the amount of resources
required.
Before discussing the synthesis of ibuprofen, we must first take a brief
look at the concept of atom economy. This concept was developed by Barry
Trost of Stanford University and won a Presidential Green Chemistry Chal-
lenge Award in 1998. Atom economy focuses our attention on Green Chem-
istry Principle 2 by asking the question: How many of the atoms of the reactants
are incorporated into the final desired product and how many are wasted? As we
will see in our discussion of the synthesis of ibuprofen, when chemists synthe-
size a compound, not all the atoms of the reactants are utilized in the desired
product. Many of these atoms may end up in unwanted products (by-products),
which are in many instances considered waste. These waste by-products may
be toxic and can cause considerable environmental damage if not disposed of
properly. In the past, waste products from chemical and other processes have
not been disposed of properly, and environmental disasters such as the Love
Canal have resulted.
Before we take on the synthesis of ibuprofen, let us look at a simple
illustration of the concept of atom economy using the production of
the desired compound, 1-bromobutane (compound 4) from 1-butanol
(compound 1).
H3C ¬ CH2 ¬ CH2 ¬ CH2 ¬ OH + Na ¬ Br + H2SO4 ¬:

1 2 3
H3C ¬ CH2 ¬ CH2 ¬ CH2 ¬ Br + NaHSO4 + H2O

4 5 6
If we inspect this reaction, we find that not only is the desired product
formed, but so are the unwanted by-products sodium hydrogen sulfate and
water (compounds 5 and 6). On the left side of this reaction, all the atoms of
the reactants that are utilized in the desired product are printed in green and
the remainder of the atoms (which become part of our waste by-products) in
black. If we add up all of the green atoms on the left side of the reaction, we
get 4 C, 9 H, and 1 Br (reflecting the molecular formula of the desired product,
1-bromobutane). The molar mass of these atoms collectively is 137 g/mol, the
molar mass of 1-bromobutane. Adding up all the atoms of the reactants gives
4 C, 12 H, 5 O, 1 Br, 1 Na, and 1 S, and the total molar mass of all these atoms
is 275 g/mol. If we take the molar mass of the atoms that are utilized, divide
by the molar mass of all the atoms, and multiply by 100, we obtain the
% atom economy, here 50%. Thus we see that half of the molar mass of all
the atoms of the reactants is wasted and only half is actually incorporated
into the desired product.
% atom economy (molar mass of atoms utilized/molar mass of

all reactants) 100
(137兾275) 100 50%
This is one method of accessing the efficiency of a reaction. Armed

with this information, a chemist may want to explore other methods of
producing 1-bromobutane that have a greater % atom economy. We will
now see how the concept of atom economy can be applied to the prepara-
tion of ibuprofen.
Ibuprofen is a common analgesic and anti-inflammatory drug found in

such brand name products as Advil, Motrin, and Medipren. The first commer-
cial synthesis of ibuprofen was by the Boots Company PLC of Nottingham,
England. This synthesis, which has been used since the 1960s, is shown in
Figure In-1. Although a detailed discussion of the chemistry of this synthesis
CH3 H
O
H3C H3C Step 1
O
AlCl3 H3C
O
O
CH3 CH3
H3C
H
s
Step 2
s
Cl 9999 COOC2H5 NaOC2H5
s
H H3C O
H
CH3
CH3
CO2C2H5
CH3 COOH H3C
Step 3
H3C H3O

CH3
ibuprofen O
CH3
H3C
H H
O9H O9H
Step 6 NH2OH
Step 4
CH3 CH3
N
CH3 C#N CH3 OH
H3C H3C
Step 5
FIGURE In-1 The Boots Company synthesis of ibuprofen. [Source: M. C. Cann and M. E. Connelly,
Real-World Cases in Green Chemistry (Washington, D.C.: American Chemical Society, 2000).]
is beyond the scope of this book, we can calculate its atom economy and
obtain some idea of the waste produced. In Figure In-1, the atoms printed in
green are those that are incorporated into the final desired product, ibupro-
fen, while those in black end up in waste by-products. By inspecting the
structures of each of the reactants, we determine that the total of all the
atoms in the reactants is 20 C, 42 H, 1 N, 10 O, 1 Cl, and 1 Na. The molar
mass of all these atoms totals 514.5 g/mol. We also determine that the num-
ber of atoms of the reactants that are utilized in the ibuprofen (the atoms
printed in green) is 13 C, 18 H, and 2 O (the molecular formula of ibupro-
fen). These atoms have a molar mass of 206.0 g/mol (the molar mass of the
ibuprofen). The ratio of the molar mass of the utilized atoms to the molar
mass of all the reactant atoms, multiplied by 100, gives an atom economy
of 40%:

all reactants) 100
(206.0兾514.5) 100 40%
Only 40% of the molar mass of all the atoms of the reactants in this synthe-
sis ends up in the ibuprofen; 60% is wasted. Because more than 30 million
pounds of ibuprofen are produced each year, if we produced all the ibuprofen
by this synthesis, there would be over 35 million pounds of unwanted waste
produced just from the poor atom economy of this synthesis.
A new synthesis (Figure In-2) of ibuprofen was developed by the
BHC Company (a joint venture of the Boots Company PLC and Hoechst
Celanese Corporation), which won a Presidential Green Chemistry Chal-
lenge Award in 1997. This synthesis has only three steps as opposed to the
six-step Boots synthesis and is less wasteful in many ways. One of the most
obvious improvements is the increased atom economy. The molar mass of all
the atoms of the reactants in this synthesis is 266.0 g/mol (13 C, 22 H, 4 O;
note that the HF, Raney nickel, and the Pd in this synthesis are used only in
catalytic amounts and thus do not contribute to the atom economy), while
the utilized atoms (printed in green) again weigh 206.0 g/mol. This yields a
% atom economy of 77%.

all reactants) 100
(206.0兾266.0) 100 77%
A by-product from the acetic anhydride (reactant 2) used in step 1 is acetic

acid. The acetic acid is isolated and utilized, which increases the atom
economy of this synthesis to more than 99%. Additional environmental
advantages of the BHC synthesis include the elimination of auxiliary mate-
rials (Principle 5), such as solvents and the aluminum chloride promoter
CH3 H
H3C 1
O
H3C
Step 1 O HF
H3C
O
2
O
CH3 CH3
H3C 3
H2
Step 2 Raney nickel
4
OH
CH3 CH3
5
H3C
CO
6
Step 3 Pd
CH3 FIGURE In-2 The BHC

Company synthesis of
CH3 COOH ibuprofen. [Source: M. C.
Cann and M. E. Connelly,
7 Real-World Cases in Green
H3C Chemistry (Washington, D.C.:
ibuprofen American Chemical Society,
2000).]
(replaced with the catalyst HF, Principle 9), and higher yields. Thus the
green chemistry of the BHC Company synthesis lowers the environmental
impact for the synthesis of ibuprofen by lowering the consumption of reac-
tants and auxiliary substances while simultaneously reducing the waste.
Other improved syntheses that are winners of Presidential Green Chem-
istry Challenge Awards include the pesticide Roundup, the antiviral agent
Cytovene, and the active ingredient in the antidepressant Zoloft.
Green chemistry provides a paradigm for reducing both the consumption

of resources and the production of waste, thus moving toward sustainability.
One of the primary considerations in the manufacture of chemicals must be
the environmental impact of the chemical and the process by which it is pro-
duced. Sustainable chemistry must become part of the psyche of not only
chemists and scientists, but also business leaders and policymakers. With this
in mind, real-world examples of green chemistry have been incorporated
throughout this text to expose you (our future scientists, business leaders, and
policymakers) to sustainable chemistry.
Further Readings
1. P. T. Anastas and J. C. Warner, Green Chemistry 6. M. A. Ryan and M. Tinnesand, eds.,
Theory and Practice (New York: Oxford University Introduction to Green Chemistry (Washington,
Press, 1998). D.C.: American Chemical Society, 2002).
2. M. C. Cann and M. E. Connelly, Real-World 7. M. Kirchhoff and M. A Ryan, eds., Greener
Cases in Green Chemistry (Washington, D.C.: Approaches to Undergraduate Chemistry Experiments
American Chemical Society, 2000). (Washington, D.C.: American Chemical
Society, 2002).
3. M. C. Cann and T. P. Umile, Real-World Cases
in Green Chemistry, vol. 2 (Washington, D.C.: 8. World Commission on Environment and
American Chemical Society, 2008). Development, Our Common Future [The
Bruntland Report] (New York: Oxford
4. M. C. Cann, “Bringing State of the Art,
University Press, 1987).
Applied, Novel, Green Chemistry to the
Classroom, by Employing the Presidential 9. M. Wackernagel and W. Rees, Our Ecological
Green Chemistry Challenge Awards,” Journal Footprint: Reducing Human Impact on the Earth
of Chemical Education 76 (1999): 1639–1641. (Gabriola Island, BC: New Society Publishers,
1996).
5. M. C. Cann, “Greening the Chemistry
Curriculum at the University of Scranton,”
Green Chemistry 3 (2001): G23–G25.
Websites of Interest
1. EPA “Green Chemistry”: http://www.epa.gov/greenchemistry/index.html
2. The Green Chemistry Institute of the American Chemical Society
website: http://www.chemistry.org/portal/a/c/s/1/acsdisplay.html?DOC
greenchemistryinstitute\index.html
3. University of Scranton “Green Chemistry”: http://academic.scranton.edu/

faculty/CANNM1/greenchemistry.html
4. American Chemical Society Green Chemistry Educational Activities:
http://www.chemistry.org/portal/a/c/s/1/acsdisplay.html?DOCeducation\
greenchem\index.html
5. Our Common Future (Report of the World Commission on Environment and
Development): http://ringofpeace.org/environment/brundtland.html
6. Ecological Footprint: http://www.myfootprint.org/
L ITTLE G REEN
MOLECULES By Terrence J. Collins and Chip Walter
POLLUTION CONTROL: Catalysts called TAMLs

work with hydrogen peroxide to break down
chlorophenols, which contaminate the wastewater
from many industrial sources.
Terrence J. Collins and Chip Walter, “Little Green

Molecules,” Scientific American, March 2006,
82–90.
Chemists have invented a new class of catalysts that can destroy some of the
worst pollutants before they get into the environment
16 Little Green Molecules
ics and even birth-control hor- American Chemical Society, the
T
he fish that live in the
Anacostia River, which mones [see illustration on oppo- first principle of this community is:
flows through the heart site page]. The amounts are “It is better to prevent waste than to
of Washington, D.C., are not often infinitesimal, measured in treat or clean up waste after it has
enjoying its waters very much. parts per billion or trillion (a been created.” As part of this
The Anacostia is contaminated part per billion is roughly equiv- effort, however, researchers have
with the molecular remnants of alent to one grain of salt dis- also made discoveries that promise
dyes, plastics, asphalt and pesti- solved in a swimming pool), but cost-effective methods for purging
cides. Recent tests have shown scientists suspect that even tiny many persistent pollutants from
that up to 68 percent of the quantities of some pollutants can wastewater.
river’s brown bullhead catfish disrupt the developmental bio- In one example of this work,
suffer from liver cancer. Wildlife chemistry that determines human investigators at Carnegie Mellon
officials recommend that anyone behavior, intelligence, immunity University’s Institute for Green
who catches the river’s fish toss and reproduction. Oxidation Chemistry (one of us,
them back uneaten, and swim- Fortunately, help is on the way. Collins, is the institute’s director)
ming has been banned. Over the past decade researchers in have developed a group of designer
catalyst molecules
called TAML—tetra-
Green chemistry can lessen some of the amido macrocyclic
ligand—activators
environmental damage caused by traditional chemistry. that work with hydro-
gen peroxide and
The Anacostia is just one of the emerging field of green chem- other oxidants to break down a
dozens of severely polluted rivers istry have begun to design the haz- wide variety of stubborn pollu-
in the U.S. The textile industry ards out of chemical products and tants. TAMLs accomplish this
alone discharges 53 billion gallons processes. These scientists have task by mimicking the enzymes in
of wastewater—loaded with formulated safer substitutes for our bodies that have evolved over
reactive dyes and other haz- harmful paints and plastics and time to combat toxic com-
ardous chemicals—into America’s devised new manufacturing tech- pounds. In laboratory and real-
rivers and streams every year. New niques that reduce the introduc- world trials, TAMLs have proved
classes of pollutants are turning up tion of pollutants into the envi- they can destroy dangerous pesti-
in the nation’s drinking water: ronment. As outlined by the cides, dyes and other contaminants,
traces of drugs, pesticides, cosmet- Green Chemistry Institute of the greatly decrease the smells and color
from the wastewater dis-
Overview/Catalysts for Cleaning charged by paper mills, and
kill bacterial spores similar
■ Many pollutants released into waterways, such as dyes and pesticides,
to those of the deadly
have become so omnipresent that they pose a serious threat to human health. JEAN-FRANCOIS PODEVIN (preceding pages)
■ Chemists have recently created enzymelike catalysts called tetra-amido
anthrax strain. If broadly
macrocyclic ligand activators (TAMLs, for short) that can destroy stubborn adopted, TAMLs could
pollutants by accelerating cleansing reactions with hydrogen peroxide. save millions of dollars in
■ When applied to the wastewater from pulp mills, TAMLs have reduced staining
cleanup costs. Moreover,
and hazardous chemicals. The catalysts may also someday be used to this research demon-
disinfect drinking water and clean up contamination from bioterror attacks. strates that green chem-
istry can lessen some of
TEXTILE MILL PULP MILL
Dyes Colored lignin fragments,
organochlorines
FARM
Herbicides,
insecticides,
animal waste
and medicines
WATER POLLUTION comes from many sources, but the newly invented TAML catalysts
may be able to destroy some of the worst contaminants before they enter rivers and
lakes. For example, applying TAMLs to the wastewater from textile and pulp mills could break
down dyes, organochlorines and other hazardous chemicals. TAMLs could also be used to treat
SEWER
Dyes, cosmetics, the runoff from agricultural waste lagoons as well as residential sewage, which contains dyes from
drugs washing machines and traces of harmful pharmaceuticals that are excreted in human urine.
the environmental damage caused and iron—to create everything children, even at minuscule
by traditional chemistry. from paramecia to redwoods, doses, it is severely toxic. The
clown fish to humans. Our indus- same can be said for arsenic, cad-
tries, in contrast, gather elements mium, mercury, uranium and
The Need to Be Green from nearly every corner of the plutonium. These elements are
A FUNDAMENTAL CAUSE of our planet and distribute them in persistent pollutants—they do
escalating environmental plight is ways natural processes never not degrade in animal bodies or
that people perform chemistry in could. Lead, for example, used to in the surrounding environ-
different ways than Mother be found mostly in deposits so iso- ment—so there is a pressing need
Nature does. For eons, biochemi- lated and remote that nature to find safer alternatives.
cal processes have evolved by never folded it into living organ- Some of the new synthetic
drawing primarily on elements isms. But now lead is everywhere, molecules in medicines, plastics
that are abundant and close at primarily because our paints, cars and pesticides are so different
DON FOLEY
hand—such as carbon, hydrogen, and computers have spread it from the products of natural
oxygen, nitrogen, sulfur, calcium around. When it finds its way into chemistry that it is as though they
dropped in from an alien world. facturing processes with more receptor system that regulates the
Many of these molecules do not environment-friendly alternatives production of critical proteins.
degrade easily, and even some [see box on page 21]. The work of Rather than relying on chlo-
biodegradable compounds have Collins’s team at Carnegie Mellon rine, we wondered if we could put
become omnipresent because we traces its origins back to the nature’s own cleansing agents—
use them so copiously. Recent 1980s, when public health con- hydrogen peroxide and oxy-
research indicates that some of cerns about chlorine were intensi- gen—to the work of purifying
these substances can interfere fying. Chlorine was then, and still water and reducing industrial
with the normal expression of is, often used for large-scale clean- waste. These cleansers can safely
genes involved in the development ing and disinfection in manufac- and powerfully obliterate many
of the male reproductive system. turing, as well as for the treatment pollutants, but in nature the
Scientists have known for several of drinking water. Although chlo- process usually requires an
years that prenatal exposure to rine treatment is inexpensive and enzyme—a biochemical catalyst
phthalates, compounds used in effective, it can create some ugly that vastly increases the rate of
plastics and beauty products, can pollutants. The bleaching of wood the reaction. Whether natural or
alter the reproductive tract of pulp with elemental chlorine in man-made, catalysts act as old-
newborn male rodents; in 2005 paper mills had been a major fashioned matchmakers, except
Shanna H. Swan of the University source of cancer-causing dioxins that rather than bringing two
of Rochester School of Medicine until the Environmental Protection people together they unite spe-
and Dentistry reported similar Agency banned the process in cific molecules, enabling and
accelerating the
chemistry among
Whether natural or man-made, catalysts act as them. Some nat-
ural catalysts can
old-fashioned matchmakers. boost chemical
reaction rates a
billionfold. If not
effects in male infants. Another 2001. (Most mills now bleach for an enzyme called ptyalin,
study headed by Swan found that wood pulp with chlorine dioxide, found in our saliva, it would take
men with low sperm counts living which reduces the production of several weeks for our bodies to
in a rural farming area of dioxins but does not eliminate break down pasta into its con-
Missouri had elevated levels of it.) By-products created by the stituent sugars. Without enzymes,
herbicides (such as alachlor and chlorination of drinking water biochemistry would move at a
atrazine) in their urine. Starting have also been linked to certain numbingly slow pace, and life as we
from our factories, farms and cancers. Chlorine in its common know it would not exist.
sewers, persistent pollutants can natural form—chloride ions or In nature, enzymes called
journey intact by air, water and salts dissolved in water—is not peroxidases catalyze reactions
up the food chain, often right toxic, but when elemental chlo- involving hydrogen peroxide,
back to us. rine reacts with other molecules the familiar household chemi-
To confront this challenge, it can generate compounds that cal used to bleach hair and
green chemists at universities and can warp the biochemistry of liv- remove carpet stains. In
companies are investigating the ing animals. Dioxins, for forests, fungi on rotting trees
feasibility of replacing some of the instance, disrupt cellular devel- use peroxidases to marshal
most toxic products and manu- opment by interfering with a hydrogen peroxide to break
Little Green Molecules 19
down the lignin polymers in could not achieve our goal of survive the liquid fire that would
the wood, splitting the large reducing pollution unless we result from the activation of
molecules into smaller ones found a way to mimic this mol- hydrogen peroxide.
that the fungi can eat. Another ecular dance. Borrowing further from
family of enzymes, the cytochrome nature’s design, we eventually
p450s, catalyzes reactions involv- solved this problem by creating a
ing oxygen (also called oxida- Catalytic Converters catalyst in which four nitrogen
tion reactions). Cytochrome CREATING SYNTHETIC enzymes atoms are placed in a square with
p450s in our livers, for example, also meant assembling molecules a single iron atom anchored in the
use oxygen to efficiently destroy that would be robust enough to middle [see box on next page].
many toxic molecules we inhale resist the destructive reactions The nitrogen atoms are connected
or ingest. they were catalyzing. Any chem- to the much larger iron atom by
For decades, chemists have istry involving oxygen can be covalent bonds, meaning that they
been struggling to build small destructive because the bonds it share pairs of electrons; in this
synthetic molecules that could makes with other elements (espe- kind of structure, the smaller
emulate these enormous cially hydrogen) are so strong. atoms and attached groups sur-
enzymes. If scientists could cre- And because each molecule of rounding the central metal atom
ate designer molecules with hydrogen peroxide (H2O2) is are called ligands. Next we linked
such strong catalytic abilities, halfway between water (H2O) the ligands to form a big outer
they could replace the chlorine- and molecular oxygen (O2), this ring called a macrocycle. Over
and metal-based oxidation compound is also strongly oxi- time we learned how to make the
technologies that produce so dizing. In water, hydrogen perox- ligands and linking systems tough
many pollutants. In the early ide often produces a kind of liq- enough to endure the violent reac-
1980s, however, no one was uid fire that demolishes the tions that the TAMLs trigger. In
having much luck developing organic (carbon-containing) mol- effect, the ligands we invented
test-tube versions of the ecules around it. A lesson from became a kind of firewall that
enzymes. Over billions of years the enzymes was that a working resisted the liquid fire. The longer
of evolution, nature had chore- catalyst would probably need to it resisted, the more useful the cat-
ographed some wonderfully have an iron atom placed inside alyst. Of course, we did not want
elegant and extremely complex a molecular matrix of organic to create an indestructible cata-
catalytic dances, making our groups. So we had to toughen lyst, which could end up in efflu-
efforts in the laboratory look the molecular architecture of ent streams and perhaps produce
clunky. Yet we knew that we such groups to ensure they could a pollution problem of its own.
All our existing Fe-TAML cata-
lysts (TAMLs with iron as the
TERRENCE J. COLLINS and CHIP WALTER have worked together to educate central metal atom) decompose
the public about the challenges and possibilities of green chemistry. on timescales ranging from min-
THE AUTHORS
Collins is Thomas Lord Professor of Chemistry at Carnegie Mellon utes to hours.

University, where he directs the Institute for Green Oxidation Chemistry. Building the ligand firewalls
He is also an honorary professor at the University of Auckland in New was not easy. It required devel-
Zealand. Walter is a science journalist and author of Space Age and I’m oping a painstaking four-step
Working on That (with William Shatner). He teaches science writing at design process in which we first
Carnegie Mellon and is a vice president of communications at the imagined and then synthesized
University of Pittsburgh Medical Center. ligand constructions that we
A MOLECULAR CLEANING MACHINE
Chemists designed TAMLs to emulate the natural enzymes that catalyze reactions involving hydrogen peroxide.
TAMLs, though, are hundreds of times smaller than enzymes, so they are easier and cheaper to manufacture.
At the center of each TAML is TAML
an iron atom bonded to four KEY
nitrogen atoms; at the edge Water
ligand Iron
are carbon rings linked to form
a big outer ring called a Nitrogen
macrocycle. This linking
system acts as a firewall, Oxygen
enabling the molecule to Carbon
endure the violent reactions it Chlorine
triggers. In its solid state the
Hydrogen
TAML also has one water
molecule (H2O) attached to
the iron atom. (The
attached groups are
called ligands.)
Macrocycle
a Water
b Peroxide
c
ligand ligand
+ + Another
Hydrogen + +
expelled water
peroxide Expelled water +
molecule
+
molecule
Water
ligand
When a TAML dissolves in water, another molecule of H2O con- then discards both its hydrogen atoms and one oxygen atom in
nects to the catalyst (a). If hydrogen peroxide (H2O2) is also in the form of a water molecule, leaving one oxygen atom attached
the solution, it can replace one of the water ligands, which are to the iron (c). The oxygen pulls electrons farther away from the
loosely attached and easily expelled (b). The peroxide ligand iron atom, turning the TAML into a reactive intermediate.
Pentachlorophenol Carbon
dioxide
MELISSA THOMAS; SOURCE: Institute for Green Oxidation Chemistry

Chloride
ions
When in solution with molecules of pentachlorophenol—a toxic chemical

used in wood treatment—TAMLs and hydrogen peroxide break down the pol- Oxalic acid
lutant to nontoxic compounds and ions. The strong positive charge of the iron
atom in the reactive intermediate enables the molecule to destroy pollutants,
although scientists have not yet determined the details of the process.
CHEMISTRY GOES GREEN
The invention of TAML catalysts is just one of the many achievements of green chemistry, which strives to develop
products and processes that reduce or eliminate the use and generation of hazardous substances. Some other
accomplishments are listed below.
PROJECT PARTICIPANTS STATUS

Using plant sugars to create Patrick Gruber, Randy L. Howard, NatureWorks has built a
polylactic acids (PLAs), a family Jeffrey J. Kolstad, Chris M. factory in Nebraska to
of biodegradable polymers that Ryan and Richard C. Bopp, manufacture PLA pellets,
could replace many traditional NatureWorks LLC which are used to make
petroleum-derived plastics (a subsidiary of Cargill) water bottles, packaging
materials and other
products
Discovering synthesis reactions Chao-Jun Li, McGill University Pharmaceutical and commodity chemical companies
that allow manufacturers to are investigating the process
substitute water for many common
organic solvents, some of which
can cause cancer
Developing metathesis chemistry, Robert H. Grubbs, California Widely applied in the

a method of organic synthesis that Institute of Technology; Richard R. chemical, biotechnology
can produce drugs, plastics and Schrock, Massachusetts Institute and food industries,
other chemicals more efficiently of Technology; Yves Chauvin, this research was awarded
and with less waste French Petroleum Institute the 2005 Nobel Prize
in Chemistry
Replacing toxic petroleum-based Martyn Poliakoff, Michael George Thomas Swan & Co., a British manufacturer of
solvents with supercritical carbon and Steve Howdle, University of specialty chemicals, has built a plant that uses
dioxide, a high-temperature, Nottingham, England supercritical fluids
high-pressure fluid that has the
SOURCE: TERRENCE J. COLLINS Institute for Green Oxidation Chemistry AND PAUL ANASTAS Green Chemistry Institute
properties of both a liquid and a gas
Inventing a new method for produc- James Spavins, Geraldine Taber, The process has reduced pollution, energy and water
ing sertraline, the key ingredient in Juan Colberg and David Pfisterer, use while improving worker safety and product yield
the antidepressant Zoloft Pfizer
hoped would keep the firewall in Then we started the whole design the TAML catalyst and hydrogen
place. Second, we subjected the cycle again. peroxide, the solution quickly
catalyst to oxidative stress until After 15 years, we finally creat- turned colorless. We now knew
the firewall disintegrated. Third, ed our first working TAML. We that our firewalls were finally hold-
NATUREWORKS LLC (bottles); AP PHOTO (Nobel medal)
we looked for the precise loca- knew we had succeeded one morning up long enough to allow the
tion where the breakdown ing when Colin Horwitz, a research TAMLs to do their job. The mole-
began. (We found that ligand professor at our institute, showed cules were acting like enzymes, and
degradations always start at the off the results of a bleaching experi- yet they were much, much smaller:
most vulnerable site.) And in the ment that featured our most the molecular weight of a TAML is
final step, once we had pinpoint- advanced design at the time. We about 500 daltons (a dalton is
ed the weakest link, we replaced looked at the results, and there it equal to one twelfth the mass of
it with groups of atoms we was: every time Horwitz squirted carbon 12, the most abundant iso-
believed would hold up longer. dark dye into a solution containing tope of carbon), whereas the
weight of horseradish peroxidase, detectable contamination behind. mined how the RI breaks the
a relatively small enzyme, is about We now have more than 90 inter- chemical bonds of its targets, but
40,000 daltons. The diminutive national patents on TAML acti- current investigations may soon
TAML activators are easier and vators, with more in the pipeline, reveal the answer. We do know,
cheaper to make, and much more and we also have several com- however, that we can adjust the
versatile in their reactivity, than mercial licenses. strength of the TAMLs by
their natural counterparts. Interestingly, we still do not changing the atoms at the head
Since then, we have evolved know all the details of how the and tail of the molecule; putting
more than 20 different TAML acti- TAMLs work, but recent studies highly electronegative elements
vators by reapplying the same have provided deep insights into at those locations draws even
four-step design process that the key reactions. In their solid more negative charge away from
enabled us to create the first state, Fe-TAMLs generally have the iron and makes the RI more
working model. Each TAML has one water molecule attached as a aggressive.
its own reaction rate and lifetime, ligand to the iron atom, oriented
allowing us to tailor the catalysts perpendicularly from the four
to match the tasks we want them nitrogen ligands; when put in Industrial Strength
to perform. Most of the catalysts solution, another water molecule BUILDING TAMLS in the laborato-
incorporate elements such as car- connects to the opposite side of ry is one thing; scaling them up
bon, hydrogen, oxygen, nitrogen the iron atom. These water lig- for commercial use is another. So
and iron, all chosen for their low ands are very loosely attached— far the lab tests and field trials
toxicity. We call some of the mol- if hydrogen peroxide is also in have been promising. Tests fund-
ecules “hunter TAMLs” because the solution, a molecule of it easily ed by the National Science
they are designed to seek out and replaces one of the water mole- Foundation, for example, demon-
lock onto specific pollutants or cules. The peroxide ligand swiftly strated that Fe-TAMLs plus per-
pathogens, in much the same way reconstitutes itself, expelling both oxides could clean up the conta-
that a magnetized mine seeks out its hydrogen atoms and one oxy- mination from a bioterror attack.
the metal hull of a ship. Other gen atom (which escape as H2O, a We found that when we com-
TAMLs act as blowtorches that water molecule) and leaving one bined one TAML with tertiary
aggressively burn most of the oxygen atom attached to the butyl hydroperoxide—a varia-
oxidizable chemicals with which iron at the center of the Fe- tion of hydrogen peroxide that
they come into contact. Still oth- TAML, which is now called the replaces one of the hydrogen
ers are less aggressive and more reactive intermediate (RI). atoms with a carbon atom and
selective, so that they will, for Oxygen is much more elec- three methyl (CH3) groups—the
example, attack only certain tronegative than iron, which resulting solution could deacti-
parts of molecules or attack only means that its nucleus pulls most vate 99.99999 percent of the
the more easily oxidized mole- of the electrons in the complex spores of Bacillus atrophaeus, a
cules in a group. We expect to bond toward itself and away bacterial species very similar to
adapt TAMLs to advance green from the iron nucleus. This effect anthrax, in 15 minutes. In
chemistry for decades to come. increases the positive charge of another important potential
Although more toxicity testing the iron at the center of the application, we hope to use Fe-
must be done, the results so far TAML, making the RI reactive TAMLs and hydrogen peroxide
indicate that TAMLs break enough to extract electrons from to someday create an inexpen-
down pollutants to their non- oxidizable molecules in the solu- sive disinfectant to tackle the
toxic constituents, leaving no tion. We have not yet deter- infectious waterborne microbes
Little Green Molecules 23
that account for so much death pulp mills in the U.S. and one indrugs and agricultural chemicals
and disease worldwide. New Zealand. In New Zealand to pass intact into drinking water.
In three field trials, we we combined Fe-TAMLs and Despite the success of these
explored how well TAMLs can peroxide with 50,000 liters of trials, we have not resolved all
alleviate the pollution created effluent water. In the U.S. we the questions about TAML acti-
when paper is manufactured. directly injected Fe-TAMLs into vators. More testing on indus-
Every year the paper and wood a pulp-treatment tower or an exittrial scales remains to be
pulp industry produces more pipe over the course of several done, and it is important to
than 100 million metric tons of days to bleach the wastewater. ensure that TAMLs do not cre-
bleached pulp, which is turned Overall, the Fe-TAMLs reduced ate some form of pollution we
into white paper. Besides gener- have not yet observed. Too
the staining of the water by up to
ating dioxins, chlorophenols and 78 percent and eliminated 29 per-often chemical technologies
other hazardous organochlo- cent of the organochlorines. have seemed completely benign
rines, many pulp mills dis- The development of other when first commercialized, and
charge a coffee-colored effluent TAML applications also looks the devastating negative conse-
that stains streams and rivers exciting. Eric Geiger of Urethanequences did not become clear
and blocks light from penetrat- Soy Systems, a company based in until decades later. We want to
ing the water. The reduction of Volga, S.D., has found that Fe- do everything in our power to
light interferes with photosyn- TAMLs do an excellent job pro- avoid such surprises with
thesis, which in turn affects cessing soybean oil into useful TAMLs.
organisms that depend on polymers that display physical Cost is also an issue. Although
plants for food. The sources of TAMLs promise to be competitive
properties equal to, if not better
the staining are large colored in most applications, large corpo-
than, those of current polyurethane
fragments of lignin, the poly- products. TAMLs may even find rations are deeply invested in
the chemical
processes they
Building TAMLs in the laboratory is one thing currently use.
Shifting to new
scaling them up for commercial use is another. s y s t e m s a n d
techniques, even
if they work,
mer that binds the cellulose their way into washing machines: usually requires significant
fibers in wood. Bleaching with in another series of tests, we investments. One great advan-
chlorine dioxide removes the found that a tiny quantity of cat- tage of TAML technology,
lignin from the cellulose; the alyst in certain household laun- though, is that it does not
smaller lignin fragments are dry products eliminated the need require major retooling. What
digested by bacteria and other to separate white and colored is more, TAMLs may ultimate-
organisms in treatment pools, clothing. TAMLs can prevent ly save companies money by
but the larger pieces are too big staining by attacking dyes after offering a cost-effective way to
to be eaten, so they end up in they detach from one fabric but meet increasingly stringent
rivers and lakes. before they attach to another. We environmental laws in the
We have tested the effec- are also working on a new family U.S., Europe and elsewhere.
tiveness of Fe-TAMLs at decol- of TAMLs that can break the very The advances of green chem-
orizing these fragments at two stable molecular bonds that allow istry to date represent only a few
interim steps on the road to deal- cost can be catastrophic. New forethought. Perhaps now we
ing with the many environmen- green chemical techniques offer can take some creative steps to
tal challenges of the 21st centu- an alternative. The Industrial reverse that trend and help make
ry. The deeper question is, Are Revolution has unfolded, for the a world, and a future, that we can
we going to practice acute care most part, without design or live with.
or preventive medicine? Right
now most chemists are still
trained to create elegantly struc- MORE TO EXPLORE
tured compounds that solve the Toward Sustainable Chemistry. Terrence J. Collins in Science, Vol. 291, No. 5501,
specific problem for which they pages 48–49; January 5, 2001.
have been engineered, without Rapid Total Destruction of Chlorophenols by Activated Hydrogen Peroxide. Sayam
regard to their broader impact. Sen Gupta, Matthew Stadler, Christopher A. Noser, Anindya Ghosh, Bradley Steinhoff,
Dieter Lenoir, Colin P. Horwitz, Karl-Werner Schramm and Terrence J. Collins in
We are in effect performing
Science, Vol. 296, pages 326–328; April 12, 2002.
global-scale experiments on our More information can be found online at www.cmu.edu/greenchemistry and
ecosystems and ourselves, and www.chemistry.org/portal/a/c/s/1/acsdisplay.html?DOC=greenchemistryinstitute\
when these experiments fail the index.html
PART I
ATMOSPHERIC
CHEMISTRY AND
AIR POLLUTION
Contents of Part I
Chapter 1 Stratospheric Chemistry: The Ozone Layer
Chapter 2 The Ozone Holes
Chapter 3 The Chemistry of Ground-Level Air Pollution
Chapter 4 The Environmental and Health Consequences
of Polluted Air—Outdoors and Indoors
Chapter 5 The Detailed Chemistry of the Atmosphere
Environmental Instrumental Analysis I

 Instrumental Determination of NOX via Chemiluminescence
C H A P T E R
1
STRATOSPHERIC CHEMISTRY:
The Ozone Layer
In this chapter, the following introductory chemistry
topics are used:
 Moles; concentration units including mole fraction
 Ideal gas law; partial pressures
 Thermochemistry: H, Hf; Hess’ law
 Kinetics: rate laws; reaction mechanisms, activation
energy, catalysis
Introduction
The ozone layer is a region of the
atmosphere that is called “Earth’s nat-
ural sunscreen” because it filters out
harmful ultraviolet (UV) rays from
sunlight before they can reach the sur-
face of our planet and cause damage to
humans and other life forms. Any sub-
stantial reduction in the amount of
this ozone would threaten life as we
know it. Consequently, the appear-
ance in the mid-1980s of a large “hole”
in the ozone layer over Antarctica rep-
resented a major environmental crisis.
Although steps have been taken to
prevent its expansion, the hole will A young girl applies sunscreen to protect her skin against UV rays from
continue to appear each spring over the Sun. [Source: Lowell George/CORBIS.]
the South Pole; indeed, one of the
largest, deepest holes in history occurred in 2006. Thus it is important that
we understand the natural chemistry of the ozone layer, the subject of this
chapter. The specific processes at work in the ozone hole and the history of
27
28 Chapter 1 Stratospheric Chemistry: The Ozone Layer
the evolution of the hole are elaborated upon in Chapter 2. We begin by con-
sidering how the concentrations of atmospheric gases are reported and the
region of the atmosphere where the ozone is concentrated.
Regions of the Atmosphere

The main components (ignoring the normally ever-present but variable
water vapor) of an unpolluted version of the Earth’s atmosphere are diatomic
nitrogen, N2 (about 78% of the molecules); diatomic oxygen, O2 (about
21%); argon, Ar (about 1%); and carbon dioxide, CO2 (presently about
0.04%). (The names of chemicals important to a chapter are printed in bold,
along with their formulas, when they are introduced. The names of chemicals
less important in the present context are printed in italics.) This mixture of
chemicals seems unreactive in the lower atmosphere, even at temperatures
or sunlight intensities well beyond those naturally encountered at the Earth’s
surface.
The lack of noticeable reactivity in the atmosphere is deceptive. In fact,
many environmentally important chemical processes occur in air, whether
clean or polluted. In the next two chapters, these reactions will be explored
in detail when we discuss reactions that occur in the troposphere, the region
of the atmosphere that extends from ground level to about 15 kilometers alti-
tude and contains 85% of the atmosphere’s mass. In this chapter we will con-
sider processes in the stratosphere, the portion of the atmosphere from
approximately 15 to 50 kilometers (i.e., 9–30 miles) altitude that lies just
above the troposphere. The chemical reactions to be considered are vitally
important to the continuing health of the ozone layer, which is found in the
bottom half of the stratosphere. The ozone concentrations and the average
temperatures at altitudes up to 50 kilometers in the Earth’s atmosphere are
shown in Figure 1-1.
The stratosphere is defined as the region that lies between the altitudes
where the temperature trends display reversals: The bottom of the strato-
sphere occurs where the temperature first stops decreasing with height and
begins to increase, and the top of the stratosphere is the altitude where the
temperature stops increasing with height and begins to decrease. The exact
altitude at which the troposphere ends and the stratosphere begins varies
with season and with latitude.
Environmental Concentration Units for Atmospheric Gases

Two types of concentration scales are commonly used for gases present in air.
For absolute concentrations, the most common scale is the number of
molecules per cubic centimeter of air. The variation in the concentration of
ozone on the molecules per cubic centimeter scale with altitude is illustrated
in Figure 1-1a. Absolute concentrations are also sometimes expressed in
Introduction 29
(a) (b)
60
50
Altitude (km)
40 Stratosphere
Ozone layer
30
20
FIGURE 1-1 Variation

10
Troposphere with altitude of (a) ozone
concentration (for mid-
0 latitude regions) and
1 2 3 4 5 –75 –50 –25 0 25
(b) air temperature for
Ozone concentration in units of 1012 molecules/cm3 Temperature (°C) various regions of the
lower atmosphere.
terms of the partial pressure of the gas, which is stated in units of atmo-
spheres or kilopascals or bars. According to the ideal gas law (PV nRT),
partial pressure is directly proportional to the molar concentration n/V, and
hence to the molecular concentration per unit volume, when different gases
or components of a mixture are compared at the same Kelvin temperature T.
Relative concentrations are usually based on the chemists’ familiar mole
fraction scale (called mixing ratios by physicists), which is also the molecule
fraction scale. Because the concentrations for many constituents are so small,
atmospheric and environmental scientists often re-express the mole or mole-
cule fraction as a parts per _______ value. Thus a concentration of 100 mole-
cules of a gas such as carbon dioxide dispersed in one million (106) molecules
of air would be expressed as 100 parts per million, i.e., 100 ppm, rather than
as a molecule or mole fraction of 0.0001. Similarly, ppb and ppt stand for parts
per billion (one in 109) and parts per trillion (one in 1012).
It is important to emphasize that for gases, these relative concentration
units express the number of molecules of a pollutant (i.e., the “solute” in
chemists’ language) that are present in one million or billion or trillion mole-
cules of air. Since, according to the ideal gas law, the volume of a gas is pro-
portional to the number of molecules it contains, the “parts per” scales also
represent the volume a pollutant gas would occupy, compared to that of the
stated volume of air, if the pollutant were to be isolated and compressed until
its pressure equaled that of the air. In order to emphasize that the concentra-
tion scale is based upon molecules or volumes rather than upon mass, a v (for
volume) is sometimes shown as part of the unit, e.g., 100 ppmv or 100 ppmv.
The Physics and Chemistry of the Ozone Layer

To understand the importance of atmospheric ozone, we must consider the
various types of light energy that emanate from the Sun and consider how
UV light in particular is selectively filtered from sunlight by gases in the air.
This leads us to consider the effects on human health of UV light, and quan-
titatively how energy from light can break apart molecules. With that back-
ground, we can then investigate the natural processes by which ozone is
formed and destroyed in air.
Absorption of Light by Molecules

The chemistry of ozone depletion, and of many other processes in the strato-
sphere, is driven by energy associated with light from the Sun. For this reason,
we begin by investigating the relationship between light absorption by mole-
cules and the resulting activation, or energizing, of the molecules that enable
them to react chemically.
An object that we perceive as black in color absorbs light at all wave-
lengths of the visible spectrum, which runs from about 400 nm (violet
light) to about 750 nm (red light); note that one nanometer (nm) equals
109 meter. Substances differ enormously in their propensity to absorb light
of a given wavelength because of differences in the energy levels of their
electrons. Diatomic molecular oxygen, O2, does not absorb visible light
very readily, but it does absorb some types of ultraviolet (UV) light, which
is that having wavelengths between about 50 and 400 nm. The most envi-
ronmentally relevant portion of the electromagnetic spectrum is illustrated
in Figure 1-2. Notice that the UV region begins at the violet edge of the
visible region, hence the name ultraviolet. The division of the UV region
into components will be discussed later in this chapter. At the other end of
the spectrum, beyond the red portion of the visible region, lies infrared
light, which will become important to us when we discuss the greenhouse
effect in Chapter 6.
An absorption spectrum such as that illustrated in Figure 1-3 is a
graphical representation that shows the relative fraction of light that is
absorbed by a given type of molecule as a function of wavelength. Here, the
efficient light-absorbing behavior of O2 molecules for the UV region
between 70 and 250 nm is shown; some minuscule amount of absorption
continues beyond 250 nm, but in an ever-decreasing fashion (not shown).
Notice that the fraction of light absorbed by O2 (given on a logarithmic
scale in Figure 1-3) varies quite dramatically with wavelength. This sort of
selective absorption behavior is observed for all atoms and molecules,
although the specific regions of strong absorption and of zero absorption
vary widely, depending upon the structure of the species and the energy
levels of their electrons.
FIGURE 1-2 The
electromagnetic spectrum.
The ranges of greatest
environmental interest in
this book are shown.
10 –17
Relative extent of absorption
10 –19
10 –21
10 –23
FIGURE 1-3 Absorption

spectrum of O2. [Source:
10 –25 T. E. Graedel and P. J. Crutzen,
50 100 150 200 250 Atmospheric Change: An Earth
Wavelength (nm) System Perspective (New York:
W. H. Freeman, 1993).]
31
Filtering of Sunlight’s UV Component by

Atmospheric O2 and O3
As a result of these absorption characteristics, the O2 gas that lies above the
stratosphere filters from sunlight most of the UV light from 120 to 220 nm;
the remainder of the light in this range is filtered by the O2 in the strato-
sphere. Ultraviolet light that has wavelengths shorter than 120 nm is filtered
in and above the stratosphere by O2 and other constituents of air such
as N2. Thus no UV light having wavelengths
shorter than 220 nm reaches the Earth’s sur-
face. This screening protects our skin and
(a)
eyes, and in fact protects all biological life,
1.0
from extensive damage by this part of the
0.8
Sun’s output.
Diatomic oxygen also filters some, but
Extent of absorption
0.6 not all, of sunlight’s UV in the 220–240-nm

range. Instead, ultraviolet light in the whole
0.4 220–320-nm range is filtered from sunlight
mainly by ozone molecules, O3, that are
0.2 spread through the middle and lower strato-
sphere. The absorption spectrum of ozone in
200 210 220 230 240 250 260 270 280 290 300 this wavelength region is shown in Figure 1-4.
Wavelength (nm) Since its molecular constitution, and thus its
set of energy levels, is different from that of
(b)
diatomic oxygen, its light absorption charac-
teristics also are quite different.
Ozone, aided to some extent by O2 at the
shorter wavelengths, filters out all of the Sun’s
Extent of absorption
ultraviolet light in the 220–290-nm range,

which overlaps the 200–280-nm region known
as UV-C (see Figure 1-2). However, ozone
can absorb only a fraction of the Sun’s UV
light in the 290–320-nm range, since, as you
can infer from Figure 1-4b, its inherent ability
to absorb light of such wavelengths is quite
0
295 300 305 310 315 320 325 limited. The remaining amount of the sun-
Wavelength (nm) light of such wavelengths, 10–30% depending
upon latitude, penetrates the atmosphere to
the Earth’s surface. Thus ozone is not com-
FIGURE 1-4 Absorption spectrum of O3: (a) from 200 to 300 nm pletely effective in shielding us from light in
and (b) from 295 to 325 nm. Note that different scales are used for the UV-B region, defined as that which lies
the extent of absorption in the two cases. [Sources: (a) Redrawn from
M. J. McEwan and L. F. Phillips, Chemistry of the Atmosphere (London:
from 280 to 320 nm (although different
Edward Arnold, 1975). (b) Redrawn from J. B. Kerr and C. T. McElroy, authors vary slightly on the limits for this
Science 262: 1032–1034. Copyright 1993 by the AAAS.] parameter). Since the absorption by ozone
falls off in an almost exponential manner with

1016
wavelength in this region (see Figure 1-4b),
the fraction of solar UV-B that reaches the
troposphere increases with increasing wave-
length. At top of
Because neither ozone nor any other atmosphere
constituent of the clean atmosphere absorbs
significantly in the UV-A range, i.e., 320–
400 nm, most of this, the least biologically 1015
Relative light intensity

harmful type of ultraviolet light, does pene-
trate to reach the Earth’s surface. (Nitrogen
dioxide gas does absorb UV-A light but is
present in such small concentration in clean
air that its net absorption of sunlight is quite
small.)
The net effect of diatomic oxygen and 1014
ozone in screening the troposphere from the
At
UV component of sunlight is illustrated in surface
Figure 1-5. The curve at the left corresponds
to the intensity of light received outside the
Earth’s atmosphere, whereas the curve at the
right corresponds to the light that is transmit-
ted to the troposphere (and thus to the 1013
surface). The vertical separation at each 200 300 400 500
Wavelength (nm)
wavelength between the curves corresponds C B A
to the amount of sunlight that is absorbed in
UV light Visible light
the stratosphere and outer regions of the
atmosphere.
FIGURE 1-5 The intensity
of sunlight in the UV and in
part of the visible regions
Biological Consequences of Ozone Depletion measured outside the
A reduction in stratospheric ozone concentration allows more UV-B light to atmosphere and in the
penetrate to the Earth’s surface. A 1% decrease in overhead ozone is pre- troposphere. [Source: W. L.
Chameides and D. D. Davis,
dicted to result in a 2% increase in UV-B intensity at ground level. This Chemical and Engineering
increase in UV-B is the principal environmental concern about ozone deple- News (4 October 1982): 38–52.
tion, since it leads to detrimental consequences to many life forms, including Copyright 1982 by the American
humans. Exposure to UV-B causes human skin to sunburn and suntan; over- Chemical Society. Reprinted
exposure can lead to skin cancer, the most prevalent form of cancer. Increas- with permission.]
ing amounts of UV-B may also adversely affect the human immune system
and the growth of some plants and animals.
Most biological effects of sunlight arise because UV-B can be absorbed by
DNA molecules, which then may undergo damaging reactions. By comparing
the variation in wavelength of UV-B light of differing intensity arriving at
the Earth’s surface with the absorption characteristics

1.0 1012
Relative biological sensitivity per photon
of DNA as shown in Figure 1-6, it can be concluded
Light intensity (photons/mm2 s per nm)

Sunlight that the major detrimental effects of sunlight absorp-
1011
tion will occur at about 300 nm. Indeed, in light-
10 –2 10 10 skinned people, the skin shows maximum UV
absorption from sunlight at about 300 nm.
109 Most skin cancers in humans are due to overexpo-
sure to UV-B in sunlight, so any decrease in ozone is
10–4 108 expected eventually to yield an increase in the inci-
DNA dence of this disease. Fortunately, the great majority of
107 skin cancer cases are not the often-fatal (25% mortal-
ity rate) malignant melanoma, but rather one of the
10–6 106 slowly spreading types that can be treated and that
280 320 360
Wavelength (nm)
collectively affect about one in four Americans at some
point in their lives. The plot in Figure 1-7, which is
based on health data from seven countries at different
FIGURE 1-6 The absorption spectrum for DNA and latitudes that therefore receive different amounts of
the intensity of sunlight at ground level versus wave- ground-level UV, shows that the rise in the incidence
length. The degree of absorption of light energy by DNA of nonmelanoma skin cancer with exposure to UV is
reflects its biological sensitivity to a given wavelength.
[Source: Adapted from R. B. Setlow, Proceedings of the
exponential; the reason is that the logarithm of the
National Academy of Science USA 71 (1974): 3363–3366.] incidence is linearly related to the UV intensity. For
example, the skin cancer rate in Europe is only about
half that in the United States.
The incidence of the malignant melanoma form of skin cancer, which
affects about 1 in 100 Americans, is thought to be related to short periods of
very high UV exposure, particularly early in life. Especially susceptible are
fair-skinned, fair-haired, freckled people who burn easily and who have moles
with irregular shapes or colors. The incidence of malignant melanoma is also
related to latitude. White males living in sunny climates such as Florida or
Texas are twice as likely to die from this disease as those in the more northerly
states, although part of this greater incidence is probably due to different pat-
terns of personal behavior, such as choice of clothing, as well as to increased
UV-B content in the sunlight. Curiously, indoor workers—who have inter-
mittent exposure to the Sun—are more susceptible than are tanned, outdoor
workers! The lag period between first exposure and melanoma is 15–25 years.
If malignant melanoma is not treated early, it can spread via the bloodstream
to body organs such as the brain and the liver.
The phrase full spectrum is sometimes used to denote sunscreens that
block UV-A as well as UV-B light. The use of sunscreens that block UV-B,
but not UV-A, may actually lead to an increase in melanoma skin cancer,
since sunscreen usage allows people to expose their skin to sunlight for pro-
longed periods without burning. The substances used in sunscreen lotions
(e.g., particles of inorganic compounds such as zinc oxide or titanium oxide)
either reflect or scatter sunlight or absorb its UV component

2.6
(e.g., water-insoluble organic compounds such as octinoxate—
octyl methoxycinnamate—for UV-B absorption and oxyben-
zone for UV-A) before it can reach and be absorbed by the 2.2
Log incidence
skin. Sunscreens were one of the first consumer products to
use nanoparticles, i.e., tiny particles only a few dozen or a few 1.8
hundred nanometers (109 m) in size. Since such particles are
so tiny and do not absorb or reflect visible light, the sun-
screens appear transparent. 1.4
Potential sunscreen compounds are eliminated if they
undergo an irreversible chemical reaction when they absorb
sunlight, because this would quickly reduce the effectiveness 100 200 300 400
of the application and because the reaction products could Intensity of annual ultraviolet
radiation (W s/cm2)
be toxic to the skin. Also, the commonly used sunscreen
component PABA (p-aminobenzoic acid) is no longer gener-
ally used because of evidence that it can itself cause cancer. FIGURE 1-7 Incidence
The SPF (Sun Protection Factor) of a sunscreen measures the multiply- (logarithmic scale) for
ing factor by which a person can stay exposed to the Sun without burning. nonmelanoma skin
cancer per 100,000 males
Thus an SPF of 15 means that he or she can stay in the Sun fifteen times versus annual UV light
longer than without the sunscreen. To receive that protection, however, the intensity, using data from
sunscreen must be reapplied at least every few hours. various countries. [Source:
Because of the long time lag (30–40 years) between exposure to UV and Redrawn from D. Gordon and
the subsequent manifestation of nonmalignant skin cancers, it is unlikely H. Silverstone, in R. Andrade
et al., Cancer of the Skin
that effects from ozone depletion are observable as yet. The rise in skin can- (Philadelphia: W. B. Saunders,
cer that has occurred in many areas of the world—and that is still occurring, 1976), pp. 405–434.]
especially among young adults—is probably due instead to greater amounts
of time spent by people outdoors in the Sun over the past few decades.
For example, the incidence of skin cancer among residents of Queensland,
Australia, most of whom are light-skinned, rose to about 75% of the popula-
tion as lifestyle changes increased their exposure to sunlight years before
ozone depletion began. As a consequence of its experience with skin cancer,
Australia has led the world in public health awareness of the need for protec-
tion from ultraviolet exposure.
In addition to skin cancer, UV exposure has been linked to several other
human conditions. The front of the eye is the one part of the human anatomy
where ultraviolet light can penetrate the human body. However, the cornea
and lens filter out about 99% of UV from light before it reaches the retina.
Over time, the UV-B absorbed by the cornea and lens produces highly reac-
tive molecules called free radicals that attack the structural molecules and
can produce cataracts. Indeed, there is some evidence that increased UV-B
levels give rise to an increased incidence of eye cataracts, particularly among
the nonelderly (see Figure 1-8). UV exposure has also been linked to an
increase in the rate of macular degeneration, the gradual death of cells in the
FIGURE 1-8 (a) A normal

human eye and (b) a human
eye with cataract. [Sources:
(a) Martin Dohrn/Photo
Researchers; (b) Sue Ford/Photo
Researchers.] (a) (b)
central part of the retina. Increased UV-B exposure also leads to a suppression
of the human immune system, probably with a resulting increase in the inci-
dence of infectious diseases, although this has not yet been extensively
researched.
However, sunlight does have some positive effects on human health.
Vitamin D, which is synthesized from precursor chemicals by the absorption of
UV by the skin, is an anticancer agent. Recent research has established that
sunlight during the winter is too weak a source of vitamin D synthesis for
people living in mid- to high latitudes and that supplementary sources of the
vitamin may be advisable. Insufficient vitamin D can reduce the rate of bone
regeneration—since the vitamin is required for calcium utilization by the
body—and thereby lead to increased fragility among middle-aged and elderly
adults. Some controversial research indicates that moderate exposure to the
Sun can reduce the incidence of multiple sclerosis and several types of cancer.
Humans are not the only organisms affected by ultraviolet light. It is
speculated that increases in UV-B exposure can interfere with the efficiency
of photosynthesis, and plants may respond by producing less leaf, seed, and
fruit. All organisms that live in the first five meters or so below the surface in
bodies of clear water would also experience increased UV-B exposure arising
from ozone depletion and may be at risk. It is feared that production of the
microscopic plants called phytoplankton near the surface of seawater may be
at significant risk from increased UV-B; this would affect the marine food
chain for which phytoplankton forms the base. Experiments indicate that
there is a complex interrelationship between plant production and UV-B
intensity, since the latter also affects the survival of insects that feed off
the plants.
Variation in Light’s Energy with Wavelength

As Albert Einstein realized, light can not only be considered a wave phenom-
enon but also to have particle-like properties in that it is absorbed (or emit-
ted) by matter only in finite packets, now called photons. The quantity of
energy, E, associated with each photon is related to the frequency, ␯, and the
wavelength, ␭, of the light by the formulas
E h␯ or E hc ␭ since ␭␯ c
Here h is Planck’s constant (6.626218 1034 J s) and c is the speed of light

(2.997925 108 m s1). From the equation, it follows that the shorter the
wavelength of the light, the greater the energy it transfers to matter when absorbed.
Ultraviolet light is high in energy content, visible light is of intermediate
energy, and infrared light is low in energy. Furthermore, UV-C is higher in
energy than UV-B, which in turn is more energetic than is UV-A.
For convenience, the product hc in the equation above can be evaluated
on a molar basis to yield a simple formula relating the energy absorbed by
1 mole of matter when each molecule in it absorbs one photon of a particular
wavelength of light. If the wavelength is expressed in nanometers, the value
of hc is 119,627 kJ mol1 nm, so the equation becomes
E 119,627/␭
where E is in kJ mol1 if ␭ is in nm.

The photon energies for light in the UV and visible regions are of the
same order of magnitude as the enthalpy (heat) changes, H°, of chemical
reactions, including those in which atoms dissociate from molecules. For
example, it is known that the dissociation of molecular oxygen into its
monatomic form requires an enthalpy change of 498.4 kJ mol1:
O2 9: 2 O H° 498.4 kJ mol1
In general, we can calculate enthalpy changes for any reaction by recalling

from introductory chemistry that for any reaction, H° equals the sum
of the enthalpies of formation, Hf°, of the products minus those of the
reactants:
H° 兺Hf° (products) 兺Hf° (reactants)
In the case of the reaction above,
H° 2 Hf° (O, g) Hf° (O2, g)
From data tables, we find that Hf° (O, g) 249.2 kJ/mol, and we know
that Hf° (O2, g) 0 since O2 gas is the stablest form of the element. By
substitution,
H° 2 249.2 0 498.4

To a good approximation, for a dissociation reaction, H° is equal to the

energy required to drive the reaction. Since all the energy has to be supplied
by one photon per molecule (see below), the corresponding wavelength for
the light is
␭ 119,627 kJ mol1 nm/498.4 kJ mol1 240 nm
Thus any O2 molecule that absorbs a photon from light of wavelength 240 nm
or shorter has sufficient excess energy to dissociate.
O2 UV photon (␭ 240 nm) 9: 2 O
If energy in the form of light initiates a reaction, it is called a photochem-

ical reaction. The oxygen molecule in the above reaction is variously said to
be photochemically dissociated or photochemically decomposed or to have under-
gone photolysis.
Atoms and molecules that absorb light (in the ultraviolet or visible
region) immediately undergo a change in the organization of their electrons.
They are said to exist temporarily in an electronically excited state; to
denote this, their formulas are followed by a superscript asterisk (*). How-
ever, atoms and molecules generally do not remain in the excited state, and
therefore do not retain the excess energy provided by the photon, for very
long. Within a tiny fraction of a second, they must either use the energy to
react photochemically or return to their ground state—the lowest energy
(most stable) arrangement of the electrons. They quickly return to the
ground state either by emitting a photon themselves or by converting the
excess energy into heat that becomes shared among several neighboring free
atoms or molecules as a result of collisions (i.e., molecules must “use it or
lose it”).
reaction
M photon M* M photon
M heat
Consequently, molecules normally cannot accumulate energy from sev-

eral photons until they receive sufficient energy to react; all the excess energy
required to drive a reaction usually must come from a single photon. There-
fore, light of 240 nm or less in wavelength can result in the dissociation of O2
molecules, but light of longer wavelength does not contain enough energy to
promote the reaction at all, even though certain wavelengths of such light
can be absorbed by the molecule (see Figure 1-3). In the case of an O2 mole-
cule, the energy from a photon of wavelength greater than 240 nm can, if
absorbed temporarily, raise the molecules to an excited state, but the energy
is rapidly converted to an increase in the energy of its own motion and that
of the molecules that surround it.
O2 photon (␭ 240 nm) 9: O2* 9: O2 heat

O2 photon (␭ 240 nm) 9: O2* 9: 2 O or O2 heat
P R O B L E M 1-1
What is the energy, in kilojoules per mole, associated with photons having
the following wavelengths? What is the significance of each of these wave-
lengths? [Hint: See Figure 1-2.]
(a) 280 nm (b) 400 nm (c) 750 nm (d) 4000 nm
P R O B L E M 1-2
The H° for the decomposition of ozone into O2 and atomic oxygen is
105 kJ mol1:
O3 9: O2 O
What is the longest wavelength of light that could dissociate ozone in this
manner? By reference to Figure 1-2, decide the region of sunlight (UV, visi-
ble, or infrared) in which this wavelength falls.
P R O B L E M 1-3
Using the enthalpy of formation information given below, calculate the max-
imum wavelength that can dissociate NO2 to NO and atomic oxygen. Recal-
culate the wavelength if the reaction is to result in the complete dissociation
into free atoms (i.e., N 2 O). Is light of these wavelengths available in
sunlight?
Hf° values (kJ mol1): NO2: 33.2; NO: 90.2; N: 472.7; O: 249.2
Of course, in order that a sufficiently energetic photon supply the energy

to drive a reaction, it must be absorbed by the molecule. As you can infer
from the examples of the absorption spectra of O2 and O3 (Figures 1-3 and
1-4), there are many wavelength regions in which molecules simply do not
absorb significant amounts of light. Thus, for example, because ozone mole-
cules do not absorb visible light near 400 nm, shining light of this wavelength
on them does not cause them to decompose, even though 400-nm photons
carry sufficient energy to dissociate them to atomic and molecular oxygen
(see Problem 1-2). Furthermore, as discussed above, the fact that molecules of
a substance absorb photons of a certain wavelength and such photons are suf-
ficiently energetic to drive a reaction does not mean that the reaction neces-
sarily will occur; the photon energy can be diverted by a molecule into other
processes undergone by the excited state. Thus the availability of light with
sufficient photon energy is a necessary, but not a sufficient, condition for reac-
tion to occur with any given molecule.
Creation of Ozone in the Stratosphere

In this section, the formation of ozone in the stratosphere and its destruction
by noncatalytic processes are analyzed. As we shall see, the formation reac-
tion generates sufficient heat to determine the temperature in this region of
the atmosphere. Above the stratosphere, the air is very thin and the concen-
tration of molecules is so low that most oxygen exists in atomic form, having
been dissociated from O2 molecules by UV-C photons from sunlight. The
eventual collision of oxygen atoms with each other leads to the re-formation
of O2 molecules, which subsequently dissociate photochemically again when
more sunlight is absorbed.
In the stratosphere itself, the intensity of the UV-C light is much lower
because much of it is filtered by the diatomic oxygen that lies above. In addi-
tion, since the air is denser than it is higher up, the molecular oxygen concen-
tration is much higher in the stratosphere. For this combination of reasons,
most stratospheric oxygen exists as O2 rather than as atomic oxygen. Because
the concentration of O2 molecules is relatively large and the concentration of
atomic oxygen is so small, the most likely fate of the stratospheric oxygen
atoms that are created by the photochemical decomposition of O2 is not their
mutual collision to re-form O2 molecules. Rather, they are more likely at such
altitudes to collide and react with undissociated, intact diatomic oxygen mol-
ecules, an event that results in the production of ozone:
O O2 9: O3 heat
Indeed, this reaction is the source of all the ozone in the stratosphere. During
daylight hours, ozone is constantly being formed by this process, the rate of
which depends upon the amount of UV light and consequently the concen-
tration of oxygen atoms and molecules at a given altitude.
At the bottom of the stratosphere, the abundance of O2 is much greater
than that at the top because air density increases progressively as one
approaches the surface. However, relatively little of the oxygen at this level is
dissociated and thus little ozone is formed because almost all the high-energy
UV has been filtered from sunlight before it descends to this altitude. For this
reason, the ozone layer does not extend much below the stratosphere. Indeed,
the ozone present in the lower stratosphere is largely formed at higher altitudes
and over equatorial regions and is transported there. In contrast, at the top of
the stratosphere, the UV-C intensity is greater, but the air is thin and therefore
relatively little ozone is produced since the oxygen atoms collide and react
with each other rather than with the small number of intact O2 molecules.
Consequently, the production of ozone reaches a maximum where the prod-
uct of UV-C intensity and O2 concentration is maximum. The maximum
density of ozone occurs lower—at about 25 km over tropical areas, 21 km
over mid-latitudes, and 18 km over subarctic regions—since much of it trans-
ported downward after its production. Collectively, most of the ozone is
located in the region between 15 and 35 km, i.e., the lower and middle strat-
osphere, known informally as the ozone layer (see Figure 1-1a).
A third molecule, which we will designate as M, such as N2 or H2O or
even another O2 molecule, is required to carry away the heat energy gener-
ated in the collision between atomic oxygen and O2 that produces ozone.
Thus the reaction above is written more realistically as
O O2 M 9: O3 M heat
The release of heat by this reaction results in the temperature of the strato-
sphere as a whole being higher than the air that lies below or above it, as indi-
cated in Figure 1-1b .
Notice from Figure 1-1b that within the stratosphere, the air at a given
altitude is cooler than that which lies above it. The general name for this
phenomenon is a temperature inversion. Because cool air is denser than hot
air (ideal gas law), it does not rise spontaneously, due to the force of gravity;
consequently, vertical mixing of air in the stratosphere is a very slow process
compared to mixing in the troposphere. The air in this region therefore is
stratified—hence the name stratosphere.
In contrast to the stratosphere, there is extensive vertical mixing of air
within the troposphere. The Sun heats the ground, and hence the air in con-
tact with it, much more than it does the air a few kilometers higher. It is for
this reason that the air temperature falls with increasing altitude in the tro-
posphere; the rate of decline of temperature with height is called the lapse
rate. The less dense, hotter air rises from the surface and gives rise to exten-
sive vertical exchange of air within the troposphere.
P R O B L E M 1-4
Given that the total concentration of molecules in air decreases with increas-
ing altitude, would you expect the relative concentration of ozone, on the ppb
scale, to peak at a higher or a lower altitude or the same altitude compared to
the peak for the absolute concentration of the gas?
Destruction of Stratospheric Ozone

The results for Problem 1-2 show that photons of light in the visible range
and even in portions of the infrared range of sunlight possess sufficient energy
to split an oxygen atom from a molecule of O3. However, such photons are
not efficiently absorbed by ozone molecules; consequently, their dissociation
by such light is not important, except in the lower stratosphere where little
UV penetrates. As we have seen previously, ozone does efficiently absorb UV
light with wavelengths shorter than 320 nm, and the excited state thereby
produced does undergo a dissociation reaction. Thus absorption of a UV-C or
UV-B photon by an ozone molecule in the stratosphere results in the decom-
position of that molecule. This photochemical reaction accounts for much of
the ozone destruction in the middle and upper stratosphere:
O3 UV photon (␭ 320 nm) 9: O2* O*
The oxygen atoms produced in the reaction of ozone with UV light have an
electron configuration that differs from the configuration that has the lowest
energy, and they therefore exist in an electronically excited state; the oxygen
molecules also are produced in an excited state.
P R O B L E M 1-5
By reference to the information in Problem 1-2, calculate the longest wave-
length of light that decomposes ozone to O* and O2*, given the following
thermochemical data:
O 9: O* H° 190 kJ mol1
O2 9: O2* H° 95 kJ mol1
[Hints: Express the overall reaction of O3 decomposition as a sum of simpler reac-
tions for which H° values are available, and combine their H° values according
to Hess’ law, which states that H° for an overall reaction is the sum of the H°
values for the simpler reactions that are added together.]
Most oxygen atoms produced in the stratosphere by photochemical

decomposition of ozone or of O2 subsequently react with intact O2 molecules
to re-form ozone. However, some of the oxygen atoms react instead with
intact ozone molecules and in the process destroy them, since they are con-
verted to O2:
O3 O 9: 2 O2
In effect, the unbonded oxygen atom extracts one oxygen atom from the
ozone molecule. This reaction is inherently inefficient since, although it is an
exothermic reaction, its activation energy is 17 kJ mol1, a sizable one for
atmospheric reactions to overcome. Consequen- O

tly, few collisions between O3 and O occur with
sufficient energy to result in reaction. UV-C O2
O2 O O3
To summarize the processes, ozone in the
stratosphere is constantly being formed, decom-
posed, and re-formed during daylight hours by a
UV-B
series of reactions that proceed simultaneously,
though at very different rates depending upon FIGURE 1-9 The
altitude. Ozone is produced in the stratosphere because there is adequate Chapman mechanism.
UV-C from sunlight to dissociate some O2 molecules and thereby produce
oxygen atoms, most of which collide with other O2 molecules and form
ozone. The ozone gas filters UV-B and UV-C from sunlight but is destroyed
temporarily by this process or by reaction with oxygen atoms. The average
lifetime of an ozone molecule at an altitude of 30 kilometers is about half an
hour; in the lower stratosphere, it lasts for months.
Ozone is not formed below the stratosphere due to a lack of the UV-C
required to produce the O atoms necessary to form O3, because this type of
sunlight has been absorbed by O2 and O3 in the stratosphere. Above the
stratosphere, oxygen atoms predominate and usually collide with other
O atoms to eventually re-form O2 molecules.
The ozone production and destruction processes discussed above consti-
tute the so-called Chapman mechanism (or cycle), shown in Figure 1-9.
Recall that the series of simple reaction steps that document how an overall
chemical process, such as ozone production and destruction, occurs at the
molecular level is called a reaction mechanism.
Even in the ozone-layer portion of the stratosphere, O3 is not the gas of
greatest abundance or even the dominant oxygen-containing species; its rel-
ative concentration never exceeds 10 ppm. Thus the term ozone layer is some-
thing of a misnomer. Nevertheless, this tiny concentration of ozone is
sufficient to filter all the remaining UV-C and much of the UV-B from sun-
light before it reaches the lower atmosphere. Perhaps the alternative name
ozone screen is more appropriate than ozone layer.
As in the case of stratospheric ozone, it is not uncommon to find that the
concentration of a substance, natural or synthetic, in some compartment of
the environment or in an organism does not change much with time. This
does not necessarily mean that there are no inputs or outputs of the sub-
stance. More often, the concentration does not vary much with time because
the input rate and the rate at which the substance decays or is eliminated
from some compartment in the environment have become equal: we say that
the substance has achieved a steady state. Equilibrium is a special case of the
steady state; it arises when the decay process is the exact opposite of the
input. Box 1-1 explores the mathematical implications of the steady state in
common situations involving reactive substances.
BOX 1-1 The Steady-State Analysis of Atmospheric Reactions
The Steady-State Approximation The net rate of change of O atom concen-

If we know the nature of the creation and tration with time equals the rate of its forma-
destruction reaction steps for a reactive sub- tion minus the rate of its destruction:
stance, we can often algebraically derive a use- rate of change of [O] 2 ki[O2] – 2 kii[O]2[M]
ful equation for its steady-state concentration.
When atomic oxygen is at a steady state, this
As a simple example, consider the forma-
net rate must be zero, and thus the right-hand
tion and destruction of oxygen atoms above
side of the equation above must also be zero.
the stratosphere. As mentioned previously,
As a consequence, it follows that
the atoms are formed by the photochemical
dissociation of molecules of diatomic oxygen: kii[O]2[M] ki[O2]
O2 9: 2 O (i) By rearrangement of this equation, we obtain
a relationship between the steady-state con-
The atoms re-form diatomic oxygen when two centrations of O and of O2:
of them collide simultaneously with a third
molecule, M, which can carry away most of [O]ss2兾[O2]ss ki兾(kii[M])
the energy released by the newly formed O2 We see now why the ratio of oxygen atoms to
molecule: diatomic molecules increases as we go higher
O O M 9: O2 M (ii) and higher above the stratosphere: it is because
the air pressure drops, and therefore so does [M],
Recall from introductory chemistry that so the O2 re-formation rate decreases.
the rates of the individual steps in reaction
mechanisms can be calculated from the con- Steady-State Analysis of the
centrations of the reactants and from the rate Chapman Mechanism
constant, k, for the step. Thus the rate of reac- After this introduction, we now are ready to
tion (i) equals ki[O2]. The rate constant ki here apply the steady-state analysis to the Chapman
incorporates the intensity of the light imping- mechanism. The four reactions of concern are
ing upon the molecular oxygen. Since two shown again below. Notice that the recombi-
O atoms are formed for each O2 molecule that nation of O atoms, i.e., reaction (ii) above, is
dissociates, not included because its rate in the mid- and
rate of formation of O atoms 2 ki[O2] low stratosphere is not competitive with other
reactions, since the oxygen atom concentra-
The rate of destruction of oxygen atoms by tion is small there.
reaction (ii) is
O2 9: 2 O (1)
rate of destruction of O atoms 2 kii[O]2[M]
O O2 M 9: O3 M (2)
where we square the oxygen atom concentra-
tion because two of them are involved as reac- O3 9: O2 O (3)
tants in the step. O3 O 9: 2 O2 (4)
Noting that O is produced or consumed in all It is known from experiment that rate2 (and
four reactions, we obtain four terms in its over- rate3) is much larger than rate1, so the latter
all rate expression and assume it is in a steady can be neglected here, giving simply
state:
rate3 rate2
rate of change of [O] 2 rate1 rate2
rate3 rate4 Using the expressions for these two reaction
rates in terms of the concentrations of their
0 (A) reactants,
Other useful information about concen- k3[O3] k2[O][O2][M]
trations can be obtained by considering the
steady-state expression for the ozone concen- Rearranging this equation, we can solve for
tration: the ratio of ozone to atomic oxygen:
rate of change of [O3] rate2 rate3 [O3]兾[O] k2[O2][M]兾k3 (D)
rate4
Equations (C) and (D) give us two equa-
0 (B) tions in the two unknowns, [O] and [O3]. Mul-
If we add together the expressions for the rates tiplying their left sides together and equating
of change in [O] and in [O3], i.e., equations the result to the product of their right sides
(A) and (B) above, we find that the rates for eliminates [O] and leaves us with an equation
reactions 2 and 3 cancel, and we obtain for the ozone concentration:
2 rate1 2 rate4 0 [O3]2 [O2]2 [M] k1k2兾k3k4

Using the expressions for these two rates in or, taking the square root of both sides, we
terms of reactant concentrations, we find obtain an expression for the steady-state con-
centration of ozone in terms of the diatomic
2 k1[O2] – 2 k4[O3][O] 0 oxygen concentration:
or [O3]ss兾[O2]ss [M]0.5 (k1k2兾k3k4)0.5 (E)
[O3][O] k1[O2]兾k4 (C) Thus the steady-state ratio of ozone to
Another useful expression can be obtained diatomic oxygen depends on the square root of
by subtracting equation (B) from (A). We the air density through [M]. The ratio is also
obtain proportional to the square root of the product
of the rate constants for the reactions, 1 and 2,
2 rate1 2 rate2 2 rate3 0 in which atomic oxygen and then ozone are
which by rearrangement and cancellation produced, and inversely proportional to the
becomes square root of the product of the ozone destruc-
tion reaction rate constants. Substitution of
rate3 rate2 rate1 (continued on p. 46)
BOX 1-1 The Steady-State Analysis of Atmospheric Reactions (continued)
numerical values for the rate constants k and Substitution of equation (E) into (C)
for [M] into equation (E) predicts the correct allows us to deduce an expression for the steady-
order of magnitude for the ozone/diatomic state concentration of free oxygen atoms:
oxygen ratio, i.e., about 104 in the mid-
stratosphere. Ozone is never the main oxygen- [O]ss (k1k3兾k2k4)0.5兾[M]0.5
containing species in the atmosphere, not even
in “the ozone layer.” Thus the concentration of atomic oxygen is
Equation (E) predicts that the concentra- predicted to increase with altitude as [M]
tion of ozone relative to that of diatomic oxy- declines—as in our previous analysis for the
gen should fall slowly as we climb in the upper atmosphere—and as k1 and k3 increase,
atmosphere, given that it is proportional to since UV light intensity increases with
the square root of the air density, through the increasing altitude. Indeed, atomic oxygen
[M] dependence. This occurs because the for- dominates over ozone at high altitudes,
mation reaction of ozone, through step 2, will whereas below about 50 km, ozone is always
slow down as [M] declines. This decline with dominant.
increasing altitude is observed in the upper The production of ozone through reaction
stratosphere and above. Below about 35 km, (2) is critically dependent upon the supply of
however, the more important change in the free oxygen atoms in reaction (1). The rate of
terms of equation (E) involves k1; conse- oxygen atom production, in turn, is highly
quently, the [O3]兾[O2] ratio is not simply pro- dependent upon the intensity of UV-C sun-
portional to [M]0.5. light. As we have noted, this intensity falls
The rate constant k1 incorporates the sharply as we descend through the strato-
intensity of sunlight capable of dissociating sphere. The UV-C light intensity also depends
diatomic oxygen into its atoms. Since the UV-C strongly upon latitude, being strongest over
sunlight required (␭ 242 nm) is successively the Equator and declining continuously
filtered by absorption as the light beam toward the poles. Thus ozone production is
descends toward the Earth’s surface, the value greatest over the Equator.
of k1 declines especially rapidly in the low The qualitative behavior of the predicted
stratosphere and below. Thus the concentra- variation of ozone concentration with altitude
tion of ozone predicted by applying the steady- predicted by equation (E) is correct, but the
state analysis to the Chapman mechanism predicted amounts of ozone exceed the
successfully predicts that the ozone concentra- observed—by about a factor of 2 near the peak
tion will peak in the stratosphere. However, as concentration. Scientists eventually found
discussed above, the actual peak of ozone that they had underestimated the rate of the
concentration (⬃25 km, above the Equator) ozone destruction reaction (4) by about a fac-
occurs rather lower in the stratosphere than tor of 4, since there are catalysts in the strato-
the altitude of maximum production (⬃40 km) sphere that greatly speed up the overall
because horizontal air movement transports reaction. These reactions are discussed in the
ozone downward. next section.
PROBLEM 1 PROBLEM 2
Consider the following 3-step mechanism for Perform a steady-state analysis for d[Cl]兾dt
the production and destruction of excited oxy- and for d[ClO]/dt in the following mechanism:
gen atoms, O*, in the atmosphere:
Cl2 9: 2 Cl (1)
light
*
O2 9: O O Cl O3 9: ClO O2 (2)
*
O M 9: O M 2 ClO 9: 2 Cl O2 (3)
*
O H2O 9: 2 OH ClO NO2 9: ClONO2 (4)
Develop an expression for the steady-state Obtain expressions for the steady-state con-
concentration of O* in terms of the concen- centrations of Cl and ClO and hence for the
trations of the other chemicals involved. rate of destruction of ozone.
Catalytic Processes of Ozone Destruction

In the early 1960s it was realized that there are mechanisms for ozone destruc-
tion in the stratosphere in addition to the processes described in the Chapman
mechanism. These additional processes all involve catalysts present in air.
In the material that follows, we investigate two general reaction mechanisms
by which stratospheric ozone is catalytically destroyed, paying particular atten-
tion to the role of chlorine and bromine.
There exist a number of atomic and molecular species, designated in gen-
eral as X, that react efficiently with ozone by abstracting (removing) an oxygen
atom from it:
X O3 9: XO O2
In those regions of the stratosphere where the atomic oxygen concentration
is appreciable, the XO molecules react subsequently with oxygen atoms to
produce O2 and to re-form X:
XO O 9: X O2
The overall reaction corresponding to this reaction mechanism is obtained
by algebraically summing the successive steps that occur in air over and over
again an equal number of times. In the case of the additional steps of the
mechanism, the reactants in the two steps are added together and become the
reactants of the overall reaction, and similarly for the products:
X O3 XO O 9: XO O2 X O2
Molecules that are common to both sides of the reaction equation, in this
case X and XO, are then canceled, and common terms collected, yielding the
balanced overall reaction:
O3 O 9: 2 O2 overall reaction
Thus the species X are catalysts for ozone destruction in the stratosphere
since they speed up a reaction (here, between O3 and O), but they are even-
tually re-formed intact and are able to begin the cycle again—with, in this
case, the destruction of further ozone molecules.
O3 X O XO O2
O2
As previously discussed (Chapman cycle), the above overall reaction can

occur as a simple collision between an ozone molecule and an oxygen atom
even in the absence of a catalyst, but almost all such direct collisions are inef-
fective in producing a reaction. The X catalysts greatly increase the efficiency
of this reaction, i.e., they effectively increase the value of its rate constant
and thereby decrease the steady-state concentration of ozone. All the envi-
ronmental concerns about ozone depletion arise from the fact that we are
inadvertently increasing the stratospheric concentrations of several X cata-
lysts by the release at ground levels of certain gases, especially those contain-
ing chlorine and bromine. Such an increase in the catalyst concentration
leads to a reduction in the concentration of ozone in the stratosphere by the
mechanism shown above and by one discussed later.
Most ozone destruction by the catalytic mechanism (i.e., the combina-
tion of sequential steps) described above, hereafter designated Mechanism I,
occurs in the middle and upper stratosphere, where the ozone concentration
is low to start with. Chemically, all the catalysts X are free radicals, which are
atoms or molecules containing an odd number of electrons. As a consequence
of the odd number, one electron is not paired with one of opposite spin char-
acter (as occurs for all the electrons in almost all stable molecules). Free rad-
icals are usually very reactive, since there is a driving force for their unpaired
electron to pair with one of the opposite spin, even if it is located in a differ-
ent molecule. The determination of the appropriate bonding structure for
simple free radicals is described in Chapter 5.
An analysis of which free-radical reactions are and are not feasible in air
is given in Box 1-2.
BOX 1-2 The Rates of Free-Radical Reactions
he rate of a given chemical reaction is exothermic radical reaction with a small

T affected by a number of parameters, most
notably the magnitude of the activation energy
energy barrier is
required before the reaction can occur. Thus Cl O3 9: ClO O2

reactions with appreciable activation energies The activation energy here is only 2 kJ/mol.
are inherently very slow processes and can Reactions involving the combining of two
often be ignored compared to alternative, faster free radicals generally are exothermic, since
processes for the chemicals involved. In gas- a new bond is formed, so they too proceed
phase reactions involving simple free radicals quickly with little activation energy, provided
as reactants, the activation energy exceeds that that the radical concentrations are high
imposed by their endothermicity by only a enough that the reactants do in fact collide
small amount. Thus we can assume, con- with each other at a fast rate.
versely, that all exothermic free-radical reac- In contrast, endothermic reactions in the
tions will have only a small activation energy atmosphere will be much slower since the acti-
(Figure 1a). Therefore, exothermic free-radical vation barrier must of necessity be much larger
reactions usually are fast (providing, of course, (see Figure 1b). At atmospheric temperatures,
the reactants exist in reasonable concentra- few if any collisions between the molecules
tions in the atmosphere). An example of an would have energy sufficient to overcome this
(continued on p. 50)
(a) (b)
Ea
ΔH > 0
Ea
Potential energy
ΔH < 0
FIGURE 1 Potential
energy profiles for
typical atmospheric
free-radical reactions,
Reactants Products Reactants Products
showing (a) exothermic
Extent of reaction and (b) endothermic
patterns.
BOX 1-2 The Rates of Free-Radical Reactions (continued)
large barrier and allow reaction to occur. An water of a hydrogen atom by ground-state
example is the endothermic reaction: atomic oxygen, given that the reaction is
OH HF 9: H2O F endothermic by about 69 kJ/mol. On the
same diagram, show the energy profile for the
Its activation energy must be at least equal to reaction of O* with H2O to give the same
its H° 69 kJ/mol, and consequently the products, given that O* lies above ground-
reaction would be so very slow at stratospheric state atomic oxygen (O) by 190 kJ/mol. From
temperatures that we can ignore it completely. these curves, predict why abstraction by O*
occurs quickly but that by O is extremely slow
PROBLEM 1
in the atmosphere.
Draw an energy profile diagram, i.e., one sim-
ilar to Figure 1b, for the abstraction from
Catalytic Destruction of Ozone by Nitric Oxide

The catalytic destruction of ozone occurs even in a “clean” atmosphere (one
unpolluted by artificial contaminants) since small amounts of the X catalysts
have always been present in the stratosphere. One important “natural” ver-
sion of X—i.e., one of the species responsible for catalytic ozone destruction
in a nonpolluted stratosphere—is the free-radical molecule nitric oxide, NO.
It is produced when molecules of nitrous oxide, N2O, rise from the tropo-
sphere to the stratosphere, where they may eventually collide with an excited
oxygen atom produced by photochemical decomposition of ozone. Most of
these collisions will yield N2 O2 as products, but a few of them result in the
production of nitric oxide:
N2O O* 9: 2 NO
We can ignore the possibility that NO produced in the troposphere will

migrate to the stratosphere; as explained in Chapter 3, the gas is efficiently
oxidized to nitric acid, which is then readily washed out of the tropospheric
air, before this process can occur.
The NO molecules that are the products of the above reaction catalyti-
cally destroy ozone by extracting an oxygen atom from ozone and forming
nitrogen dioxide, NO2; i.e., they act as X in Mechanism I:
NO O3 9: NO2 O2
NO2 O 9: NO O2
overall O3 O 9: 2 O2
P R O B L E M 1-6
Not all XO molecules such as NO2 survive long enough to react with oxygen
atoms; some are photochemically decomposed to X and atomic oxygen,
which then reacts with O2 to re-form ozone. Write out the three steps
(including one for ozone destruction) for this process and add them together
to deduce the net reaction. Does this sequence destroy ozone overall, or is it
a null cycle, which is defined as one that involves a sequence of steps with no
chemical change overall?
Another important X catalyst in the stratosphere is the hydroxyl free

radical, OH. It originates from the reaction of excited oxygen atoms O* with
water or methane, CH4, molecules:
O* CH4 9: OH CH3
The methane originates with emissions from the Earth’s surface, a small frac-
tion of which survive sufficiently long to migrate up to the stratosphere.
P R O B L E M 1-7
Write out the two-step mechanism by which the hydroxyl free radical cat-
alytically destroys ozone by Mechanism I. By adding the steps together,
deduce the overall reaction.
P R O B L E M 1-8
By analogy with its reaction with methane, write a balanced equation for the
reaction by which O* produces OH from water vapor.
Catalytic Destruction of Ozone Without Atomic Oxygen:

Mechanism II
A factor that minimizes the catalyzed gas-phase destruction of ozone by Mech-
anism I is the requirement for atomic oxygen to complete the cycle by reacting
with XO in order to permit the regeneration of the X catalyst in a usable form.
XO O 9: X O2
As discussed above, the concentration of oxygen atoms is very low in the
lower stratosphere (15–25 km altitude), so the gas-phase destruction of ozone
by reactions that require atomic oxygen is sluggish there.
There is another general catalytic sequence, henceforth designated
Mechanism II, that depletes ozone in the lower stratosphere, particularly
when the concentrations of the catalysts X are relatively high. First, two
ozone molecules are destroyed by the same catalysts discussed previously and
by the same initial reaction:
X O3 9: XO O2
X
O3 9: X
O O2
We have used X
to symbolize the catalyst in the second equation to indicate
that it need not be chemically identical to the X in the first equation. Either X
or X
must be a chlorine atom.
In the steps that follow the first, the two molecules XO and X
O that have
added an oxygen atom react with each other. As a consequence, the catalysts
X and X
are ultimately regenerated, usually after the combined but unstable
molecule XOOX
has formed and been decomposed by either heat or light:
XO X
O 9: [XOOX
] 9: X X
O2
(By convention in chemistry, a species shown in square brackets is one with a

transient existence.) When we sum these steps, the overall reaction is seen to be
2 O3 9: 3 O2
We shall see several examples of catalytic Mechanism II in operation in the

ozone holes (Chapter 2) and in the mid-latitude lower stratosphere. Indeed,
most ozone loss in the lower stratosphere occurs according to this net reaction.
Mechanisms I and II are summarized in Figure 1-10.
Finally, we note that while the rate of production of ozone from oxygen
depends only upon the concentrations of O2 and O3 and of UV light at a
given altitude, what determines the rate of ozone destruction is somewhat
more complex. The rate of ozone decomposition by UV-B or by catalysts
depends upon ozone’s concentration multiplied by either the sunlight inten-
sity or the catalyst concentration, respectively. In general, the concentration
of ozone will rise until the net rate of destruction just meets the rate of pro-
duction, and then it will remain constant at this steady-state level as long as
the intensity of sunlight remains the same. If, however, the rate of destruction
is temporarily increased by the introduction of additional molecules of a
Mechanism II
Mechanism I
X O3 : XO O2
X O3 : XO O2 X
O3 : X
O O2
FIGURE 1-10 Summary of XO O : X O2 XO X
O : : X X
O2
catalytic ozone destruction
by Mechanisms I and II. O3 O : 2 O2 overall 2 O3 : 3 O2 overall
catalyst, the steady-state concentration of ozone must then decrease to a new,

lower value at which the rates of formation and destruction are again equal.
However, it should be clear from the discussion above that due to its constant
re-formation reactions, atmospheric ozone cannot be permanently and
totally destroyed, no matter how great the level of catalyst. It should also be
realized that any decrease in the concentration of ozone at higher altitudes
allows more UV penetration to lower altitudes, which produces more ozone
there; thus there is some “self-healing” of total ozone loss.
Atomic Chlorine and Bromine as X Catalysts

The decomposition of synthetic chlorine-containing gases in the strato-
sphere over the last few decades has generated a substantial amount of atomic
chlorine, Cl, in this region. As the stratospheric chlorine concentration
increases, so does the potential for ozone destruction, since the free radical Cl
is an efficient X catalyst.
However, synthetic gases are not the only suppliers of chlorine to the
ozone layer. There always has been some chlorine in the stratosphere as a
result of the slow upward migration of the methyl chloride gas, CH3Cl (also
called chloromethane), produced at the Earth’s surface—mainly in the oceans
as a result of the interaction of chloride ion with decaying vegetation.
Recently another large source of methyl chloride, from tropical plants, has
been discovered; this may be the missing source of the compound for which
scientists have been searching.
Only a portion of the methyl chloride molecules are destroyed in the tro-
posphere. When intact molecules of it reach the stratosphere, they are pho-
tochemically decomposed by UV-C or attacked by OH radicals. In either
case, atomic chlorine, Cl, is eventually produced:
UV-C
CH3Cl 9: Cl CH3
or
OH CH3Cl 9: Cl other products
Chlorine atoms are efficient X catalysts for ozone destruction by Mechanism I:

Cl O3 9: ClO O2
ClO O 9: Cl O2
overall O3 O 9: 2 O2
Each chlorine atom can catalytically destroy many tens of thousands
of ozone molecules in this manner. At any given time, however, the great
majority of stratospheric chlorine normally exists not as Cl nor as the free

radical chlorine monoxide, ClO, but in a form that is not a free radical and
that is inactive as a catalyst for ozone destruction. The two main catalytically
inactive (or reservoir) molecules containing chlorine in the stratosphere are
hydrogen chloride gas, HCl, and chlorine nitrate gas, ClONO2.
The chlorine nitrate is formed by the combination of chlorine monoxide
and nitrogen dioxide; after a few days or hours, a given ClONO2 molecule is
photochemically decomposed back to its components, and thus the catalyti-
cally active ClO is re-formed.
ClO NO2 Δ ClONO2

sunlight
However, under normal circumstances, more chlorine exists at steady state as

ClONO2 than as ClO. (Processes similar to the reaction above occur for
several other constituents of the stratosphere; as we shall see at the end of
Chapter 5, the reactions are easily systematized, thereby greatly reducing the
number of processes that have to be learned.)
The other catalytically inactive form of chlorine, HCl, is formed when
atomic chlorine abstracts a hydrogen atom from a molecule of stratospheric
methane:
Cl CH4 9: HCl CH3
This reaction is slightly endothermic, so its activation energy is nonzero, and
it therefore proceeds at a slow but significant rate (see Box 1-2). The methyl
free radical, CH3, does not operate like the X catalysts since it combines with
an oxygen molecule and is degraded eventually to carbon dioxide by reac-
tions discussed in Chapter 5. Eventually, each HCl molecule is reconverted
to the active form, i.e., chlorine atoms, by reaction with the hydroxyl
radical:
OH HCl 9: H2O Cl
Again, usually much more chlorine exists as HCl rather than as atomic chlo-
rine at any given time under normal steady-state conditions.
O
Cl O3 ClO O2
CH4 OH NO2 light
HCl ClONO2
When the first predictions concerning stratospheric ozone depletion

were made in the 1970s, it was not realized that about 99% of stratospheric
chlorine usually is tied up in the inactive forms. When the existence of inac-
tive chlorine was discovered in the early 1980s, the predicted amounts of
stratospheric ozone loss in the future were lowered appreciably. As we shall
see, however, there are conditions under which inactive chlorine can become
temporarily activated and can massively destroy ozone, a discovery that was
not made until the late 1980s.
Although there has always been some chlorine in the stratosphere due
to the natural release of CH3Cl from the surface, in recent decades it has
been completely overshadowed by much larger amounts of chlorine pro-
duced from synthetic chlorine-containing gaseous compounds that are
released into air during their production or use. Most of these substances are
chlorofluorocarbons (CFCs); their nature, usage, and replacements will be dis-
cussed in Chapter 2.
As with methyl chloride, large quantities of methyl bromide, CH3Br, are
also produced naturally and some of it eventually reaches the stratosphere,
where it is decomposed photochemically to yield atomic bromine. Like chlo-
rine, bromine atoms can catalytically destroy ozone by Mechanism I:
Br O3 9: BrO O2
BrO O 9: Br O2
In contrast to chlorine, almost all the bromine in the stratosphere remains

in the active free-radical forms Br and BrO, since the inactive forms, hydro-
gen bromide, HBr, and bromine nitrate, BrONO2, are efficiently decomposed
photochemically by sunlight. In addition, the formation of HBr from attack of
atomic bromine on methane is a slower reaction than is the analogous process
involving atomic chlorine because it is much more endothermic and therefore
has a higher activation energy:
Br CH4 9: HBr CH3
A lower percentage of stratospheric bromine exists in inactive form than does

chlorine because of the slower speed of this reaction and because of the effi-
ciency of the photochemical decomposition reactions. For that reason,
stratospheric bromine is more efficient at destroying ozone than is chlorine
(by a factor of 40 to 50), but there is much less of it in the stratosphere, so
overall it is less important.
When molecules such as HCl and HBr eventually diffuse from the strato-
sphere back into the upper troposphere, they dissolve in water droplets and are
subsequently carried to lower altitudes and then transported to the ground by
rain. Thus, although the lifetime of chlorine and bromine in the stratosphere
is long, it is not infinite and the catalysts are eventually removed. However,
the average chlorine atom destroys about 10,000 molecules of ozone before it
is removed!
Review Questions
The questions below, and the comparable ones in 8. Write the equation for the chemical reaction
succeeding chapters, are designed to test your knowl- by which ozone is formed in the stratosphere. What
edge mainly of some of the factual material presented are the sources for the different forms of oxygen
in the chapter. used here as reactants?
The problems within the chapter, and the more
9. Write the two reactions that, in addition to the
elaborate ones given below as Additional Problems,
catalyzed reactions, contribute most significantly to
are designed to test your problem-solving abilities.
ozone destruction in the stratosphere.
1. Which three gases constitute most of Earth’s 10. What is meant by the phrase excited state as
atmosphere? applied to an atom or molecule? Symbolically, how
is an excited state signified?
2. What range of altitudes constitutes the tropo-
sphere? The stratosphere? 11. Explain why the phrase ozone layer is a
misnomer.
3. What is the wavelength range for visible light?
Does ultraviolet light have shorter or longer wave- 12. Define the term free radical, and give two
lengths than visible light? examples relevant to stratospheric chemistry.
4. Which atmospheric gas is primarily responsible 13. What are the two steps, and the overall reac-
for filtering sunlight in the 120–220-nm region? tion, by which a species X, such as ClO, catalyti-
Which, if any, gas absorbs most of the Sun’s rays in cally destroys ozone in the middle and upper
the 220–320-nm region? Which absorbs primarily stratosphere via Mechanism I?
in the 320–400-nm region?
14. What is meant by the term steady state as applied
5. What is the name given to the finite packets of to the concentration of ozone in the stratosphere?
light absorbed by matter?
15. Explain why, atom for atom, stratospheric
6. What are the equations relating photon energy bromine destroys more ozone than does chlorine.
E to light’s frequency ␯ and wavelength ␭?
16. Explain why ozone destruction via the reaction
7. What is meant by the expression photochemically of O3 with atomic oxygen does not occur to a sig-
dissociated as applied to stratospheric O2? nificant extent in the lower stratosphere.
Additional Problems
1. A possible additional mechanism that could fate of the two oxygen atoms, and what would be
exist for the creation of ozone in the high strato- the overall reaction once this fate is included?
sphere begins with the creation of (vibrationally)
2. In the nonpolluted atmosphere, an important
excited O2 and ground-state atomic oxygen from
mechanism for ozone destruction in the lower
the absorption by ozone of photons with wave-
stratosphere is:
lengths less than 243 nm. The O2* reacts with a
ground-state O2 molecule to produce ozone and
another atom of oxygen. What is the net reaction OH O3 9: HOO O2
from these two steps? What do you predict is the HOO O3 9: OH 2 O2
Does this pair of steps correspond to Mechanism I? supersonic transport airplanes fly if they emit sub-
If not, what is the overall reaction? stantial amounts of nitrogen oxides in their
exhaust?
3. A proposed mechanism for ozone destruction in
the late spring over northern latitudes in the lower 7. At an altitude of about 35 kilometers, the aver-
stratosphere begins with the photochemical age concentrations of O* and of CH4 are approxi-
decomposition of ClONO2 to Cl and NO3, fol- mately 100 and 1 1011 molecules cm3,
lowed by photochemical decomposition of the respectively; the rate constant k for the reaction
latter to NO and O2. Deduce a catalytic ozone between them is approximately 3 1010 cm3
destruction cycle, requiring no atomic oxygen, that molecules1 s1. Calculate the rate of destruction
incorporates these reactions. What is the overall of methane in molecules per second per cubic cen-
reaction? timeter and in grams per year per cubic centimeter
under these conditions. [Hint: Recall that the rate
4. Deduce possible reaction step(s), none of which
law for a simple process is its rate constant k times
involve photolysis, for Mechanism II that follow(s)
the product of the concentrations of its reactant
the X O3 9: XO O2 step, such that the
concentrations.]
sum of all the mechanism’s steps does not destroy
or create any ozone. 8. The rate constants for the reactions of atomic
chlorine and of hydroxyl radical with ozone are
5. As will be discussed in Chapter 2, atomic chlo-
given by 3 1011 e250/T and 2 1012 e940/T,
rine is produced under ozone-hole conditions by the
where T is the Kelvin temperature. Calculate the
dissociation of diatomic chlorine, Cl2. Given that
ratio of the rates of ozone destruction by these
diatomic chlorine gas is the stablest form of the
catalysts at 20 km, given that at this altitude the
element and that the Hf° value for atomic chlo-
average concentration of OH is about 100 times
rine is 121.7 kJ mol1, calculate the maximum
that of Cl and that the temperature is about
wavelength of light that can dissociate diatomic
50°C. Calculate the rate constant for ozone
chlorine into the monatomic form. Does such a
destruction by chlorine under conditions in the
wavelength correspond to light in the visible or
Antarctic ozone hole, when the temperature is
the UV-A or the UV-B region?
about 80°C and the concentration of atomic
6. Under conditions of low oxygen atom concen- chlorine increases by a factor of 100 to about
tration, the radical HOO can react reversibly with 4 105 molecules per cubic centimeter and that
NO2 to produce a molecule of HOONO2: of O3 is 2 1012 molecules/cm3.
HOO NO2 9: HOONO2 9. The Arrhenius equation (see your introductory
chemistry textbook) relates reaction rates to tem-
(a) Deduce why the addition of nitrogen oxides to perature via the activation energy. Calculate the
the lower stratosphere could lead to an increase in ratio of the rates at 30°C (a typical stratospheric
the steady-state ozone concentration as a conse- temperature) for two reactions having the same
quence of this reaction. Arrhenius A factor and initial concentrations, one
(b) Deduce how the addition of nitrogen oxides to of which is endothermic and has an activation
the middle and upper stratosphere could decrease energy of 30 kJ mol1 and the other which is
the ozone concentration there as a consequence of exothermic with an activation energy of 3 kJ mol1.
other reactions. In energy units, R 8.3 J K1 mol1.
(c) Given the information stated in parts (a) and
(b), in what regions of the stratosphere should
Further Readings
1. S. A. Montzka et al., “Present and future trends 4. (a) S. Madronich and F. R. de Gruijl, “Skin
in the atmospheric burden of ozone-depleting cancer and UV radiation,” Nature 366 (1993): 23.
halogens,” Nature 398 (1999): 690–693. (b) J.-S. Taylor, “DNA, sunlight, and skin cancer,”
Journal of Chemical Education 67 (1990): 835–841.
2. R. McKenzie, B. Connor, and G. Bodeker,
“Increased summertime UV Radiation in New 5. C. Biever, “Bring me sunshine,” New Scientist
Zealand in Response to Ozone Loss,” Science 285 (9 August 2003): 30–33.
(1999): 1709–1711.
3. T. K. Tromp et al., “Potential Environmental
Impact of a Hydrogen Economy on the Strato-
sphere,” Science 300 (2003): 1740.
Log on to www.whfreeman.com/envchem4/ and click on Chapter 1.
C H A P T E R
2
THE OZONE HOLES
topics are used:
 Kinetics: Mechanisms; catalysis; reaction order
Background from Chapter 1 used in this chapter:

 Photochemical decomposition
 Mechanism II
 Free radicals
Introduction
In Chapter 1, the gas-phase chemistry of the unpolluted stratosphere was
explored. Since the late 1970s, however, the normal functioning of the
stratosphere’s ozone screen—and the protection it provides us—has been
periodically upset by anthropogenic chlorine-containing chemicals in the
atmosphere. Most famously, these substances now cause an ozone hole to
open each spring season above the South Pole. Ozone levels in the strato-
sphere over the North Pole as well, and to some extent even that over our
heads, have also been depleted. In this chapter, the extent of these strato-
spheric ozone losses are documented, and the special chemical processes that
produce such destruction are described. We also document how knowledge of
this chemistry led to action by humankind to prevent even more drastic loss
of ozone, which should eventually heal the stratosphere.
We begin by describing how the amount of overhead ozone is reported
and the history of how the ozone hole over the Antarctic was first discovered.
Dobson Units for Overhead Ozone

Ozone, O3, is a gas that is present in small concentrations throughout the
atmosphere. The total amount of atmospheric ozone that lies over a given
point on Earth is measured in terms of Dobson units (DU). One Dobson unit
is equivalent to a 0.01-mm (0.001-cm) thickness of pure ozone at the density
59
60 Chapter 2 The Ozone Holes
it would possess if it were brought to ground-level (1 atm) pressure and

0°C temperature.
On average, this total overhead ozone at temperate latitudes amounts to
about 350 DU; thus if all the ozone were to be brought down to ground level,
the layer of pure ozone would be only 3.5 mm thick. Because of stratospheric
winds, ozone is transported from tropical regions, where most of it is pro-
duced, toward polar regions. Thus, ironically, the closer to the Equator you
live, the smaller the total amount of ozone that protects you from ultraviolet
light. Ozone concentrations in the tropics usually average 250 DU, whereas
those in subpolar regions average 450 DU, except, of course, when holes
appear in the ozone layer over such areas. There is natural seasonal variation
of ozone concentration, with the highest levels in the early spring and the
lowest in the fall.
The Annual Ozone Hole Above Antarctica

The Antarctic ozone hole was discovered by Dr. Joe C. Farman and his col-
leagues in the British Antarctic Survey. They had been recording ozone levels
over this region since 1957. Their data indicated that the total amounts of
ozone each October had been gradually falling each year, especially during the
mid-September to mid-October period, with precipitous declines beginning in
the late 1970s. This is illustrated in Figure 2-1b, where the average minimum
daily amount of overhead ozone is plotted against the year. The period from
September to November corresponds to the spring season at the South Pole
and follows a period of very cold 24-hour nights common to polar winters. By
the mid-1980s, the springtime loss in ozone at some altitudes over Antarctica
was complete, resulting in a loss of more than 50% of the total overhead
amount. It is therefore appropriate to speak of a “hole” in the ozone layer that
now appears each spring over the Antarctic and lasts for several months. The
average geographic area covered by the ozone hole has increased substantially
since it began (see Figure 2-1a) and now is comparable in size to that of the
North American continent.
The seasonal evolution and decline of the Antarctic ozone hole in a
recent year (2006) is illustrated in Figure 2-2. For reasons that will be
explained later in the chapter, substantial ozone depletion does not start to
occur until late August (Figures 2-2a, b) and begins to decline in November,
as the stratospheric temperature rises (Figure 2-2c).
Initially it was not clear whether the hole was due to a natural phenom-
enon involving meteorological forces or to a chemical mechanism involving
air pollutants. In the latter case, the suspect chemical was chlorine, produced
mainly from gases that were released into the air in large quantities as a con-
sequence of their use, for example, in air conditioners. Scientists had pre-
dicted that the chlorine would destroy ozone, but only to a small extent and
only after several decades had elapsed. The discovery of the Antarctic ozone
Introduction 61
(a)
30
1998: 26 2006: 26
25
Area (millions of km2)
20
15
10
0
1980 1990 2000
(b)
250
1979: 225
200
Amount (Dobson units)
150 2006: 100

1998: 96
100
50
0
1980 1990 2000
FIGURE 2-1 Historical evaluation of the Antarctic ozone hole. (a) Area covered by the hole
(average for September 7 to October13), and (b) minimum overhead ozone (average for Sep-
tember 21 to October 16). Extreme ozone depletion occurred in 1998 and 2006, as indicated.
No data were acquired during the 1995 season. [Source: NASA, at http://ozonewatch.gsfc.nasa.gov/]
hole came as a complete surprise to everyone. Subsequent research, however,

confirmed that the hole indeed does occur as a result of chlorine pollution.
The complicated chemical processes that cause ozone depletion are now
understood and are discussed in this chapter. Based upon this knowledge, we
can predict that the hole will continue to reappear each spring until about
the middle of this century and that a corresponding hole may appear above
the Arctic region.
(a)
Ozone-hole area (millions of km2)

Sep. 24: 29
Jul. 1: 0 Dec. 31: 0
(b)
Minimum ozone (Dobson units)
Jul. 1: 233
Dec. 31: 224
Oct. 8: 85
(c)
Minimum stratospheric temperature (K)
Dec. 31: 217

FIGURE 2-2 Evolution of
the 2006 Antarctic ozone
hole. (a) Area covered by
the hole in millions of
square kilometers; Jul. 1: 184
(b) minimum daily amount
of overhead ozone in Aug. 7: 179
Dobson units; and
(c) minimum daily
temperature in the lower
stratosphere in degrees
Kelvin. [Source: NASA, at http: Jul. Aug. Sep. Oct. Nov. Dec.
ozonewatch.gsfc.nasa.gov/]
4
(a) 1996–2005
2
Trend (DU/yr)
–2 FIGURE 2-3 Changes in

average overhead ozone
at different latitudes.
(b) 1979–1995
(a) Increases 1996–2005;
–4 (b) decreases 1979–1995.
–60 –30 Equator 30 60
[Source: E. C. Weatherland and
Latitude (degrees) S. B. Anderson, Nature 441
(2006): 39.]
As a consequence of these discoveries, governments worldwide moved

quickly to legislate a phase-out in production of the responsible chemicals. Thus
the situation was not made much worse by the development of even more
severe ozone depletion over populated areas, with the corresponding threat to
the health of humans and other organisms that this increase would bring.
Ozone Depletion in Temperate Areas

Ozone was being depleted not just in the air above Antarctica but to some
extent worldwide. The average overhead ozone loss at mid-latitudes amounted
to about 3% in the 1980s. As indicated by the lengths of the vertical black bars
in Figure 2-3b, the losses during the 1980s and early 1990s were greater the
higher the latitude in both the Northern and Southern Hemispheres. How-
ever, this trend in ozone loss was reversed in the period from 1996 to 2005, the
gains in the Northern Hemisphere in this period approximately canceling the
earlier losses (Figure 2-3a). Although some of the recovery could be due to
controls on emissions, much of it probably occurred because of natural trends
in that period toward higher ozone levels due to the solar cycle and a lack of
volcanic activity as well as to relatively warm Arctic winters.
The Ozone Hole and Other Sites

of Ozone Depletion
As discussed previously, scientists discovered in 1985 that stratospheric ozone
over Antarctica is reduced by about 50% for several months each year, due
mainly to the action of chlorine. An episode of this sort, during which there is
said to be a hole in the ozone layer, occurs from September to early November,
corresponding to spring at the South Pole. The hole has been appearing
since about 1979, as was shown in Figure 2-1, which illustrates the variation
in the minimum September–October ozone concentrations above the
Antarctic as a function of year. Extensive research in the late 1980s led to an
understanding of the chemistry of this phenomenon. In this section, we dis-
cuss the peculiar process by which chlorine in the stratosphere becomes
activated to destroy ozone and look at the detailed mechanism by which
destruction occurs. We then consider the various measures of ozone-hole size,
which allow us to investigate whether the hole above the Antarctic has been
declining over time, whether a hole exists above the North Pole, and the
effects of the holes on the amount of UV light to which we are exposed at
ground level.
The Activation of Catalytically Inactive Chlorine

The ozone hole occurs as a result of special polar winter weather conditions in
the lower stratosphere, where ozone concentrations usually are highest, that
temporarily convert all the chlorine that is stored in the catalytically inactive
forms HCl and ClONO2 into the active forms Cl and ClO, all of which were
discussed in Chapter 1. Consequently, the high concentration of active chlo-
rine causes a large, though temporary, annual depletion of ozone.
The conversion of inactive to active chlorine occurs at the surface of par-
ticles formed by a solution of water, sulfuric acid (H2SO4), and nitric acid
(HNO3), the latter formed by combination of hydroxyl radical (OH) with
nitrogen dioxide (NO2) gas. The same conversion reactions could potentially
occur in the gas phase but are so slow there as to be of negligible importance;
they become rapid only when they occur on the surfaces of cold particles.
In most parts of the world, even in winter, the stratosphere is cloudless.
Condensation of water vapor into liquid droplets or solid crystals that would
constitute clouds doesn’t normally occur in the stratosphere since the con-
centration of water in that region is exceedingly small, although there are
always small liquid droplets consisting largely of sulfuric acid present, as well
as some solid sulfate particles. However, the temperature in the lower strato-
sphere drops so low (80°C) over the South Pole in the sunless winter
months that condensation does occur. The usual stratospheric warming
mechanism—the release of heat by the O2 O reaction—is absent because
of the lack of production of atomic oxygen from O2 and O3 when there is
total darkness. In turn, because the polar stratosphere becomes so cold during
the total darkness at mid-winter, the air pressure drops since it is proportional
to the Kelvin temperature, according to the ideal gas law, PV nRT. This
pressure phenomenon, in combination with the Earth’s rotation, produces
a vortex, a whirling mass of air in which wind speeds can exceed 300 km
(180 miles) per hour. Since matter cannot penetrate the vortex, the air inside
it is isolated and remains very cold for many months. At the South Pole, the
vortex is sustained well into the springtime (October). (The vortex around
the North Pole usually breaks down in February or early March, before much
sunlight has returned to the area, but recently there have been exceptions to
this generalization, as discussed later.)
The particles produced by condensation of the gases within the vortex
form polar stratospheric clouds, or PSCs. As the temperature drops, the first
crystals to form are small ones containing water and sulfuric and nitric acids.
When the air temperature drops a few degrees more, below –80°C, a larger
type of crystal—consisting mainly of frozen water ice and perhaps also nitric
acid—also forms.
Chemical reactions that lead ultimately to ozone destruction occur in a
thin aqueous layer present at the surface of the PSC ice crystals. Upon con-
tact, gaseous chorine nitrate, ClONO2, reacts at the surface with water mol-
ecules to produce hypochlorous acid, HOCl:
ClONO2(g) H2O(aq) 9: HOCl(aq) HNO3(aq)
Also in the aqueous layer, gaseous hydrogen chloride, HCl, dissolves and
forms ions:
aqueous
layer
HCl(g) 9: H(aq) Cl(aq)
Reaction of the two forms of dissolved chlorine pro-

duces molecular chlorine, Cl2, which escapes to the Cl Cl
surrounding air:
;9
99
Cl(aq) HOCl(aq) 9: Cl2(g) OH(aq) ClONO2 light
9
9 ;9 Cl2
This process is illustrated schematically in Figure 2-4. 9
9
;
99
Overall, when the steps are added together, the
HCl
process corresponds to the net reaction
HCl
HCl(g) ClONO2(g) 9: Cl2(g) HNO3(aq) HCl
Crystal
;9 Aqueous
since the ions H and OH re-form water. Similar HCl
layer
reactions probably also occur on the surface of solid
particles. HCl
HCl
During the dark winter months, molecular chlo-
rine accumulates within the vortex in the lower
stratosphere and eventually becomes the predomi- FIGURE 2-4 A scheme illustrating the production of
nant chlorine-containing gas. Once a little sunlight molecular chlorine from inactive forms of chlorine in the
reappears in the very early Antarctic spring, or the winter and spring in the stratosphere in polar regions.
air mass moves to the edge of the vortex where there is some sunlight, the
chlorine molecules are decomposed by the light into atomic chlorine:
Cl2 sunlight 9: 2 Cl
Similarly, any gaseous HOCl molecules released from the surface of the crys-
tals undergo photochemical decomposition to produce hydroxyl radicals and
atomic chlorine:
HOCl sunlight 9: OH Cl
Massive catalytic destruction of ozone by atomic chlorine then ensues.

Since stratospheric temperatures above the Antarctic remain below
–80°C even in the early spring (Figure 2-2c), the crystals persist for months.
Any of the Cl that is converted back to HCl by the reaction with methane
is subsequently reconverted to Cl2 on the crystals and then back to Cl by
sunlight. Inactivation of chlorine monoxide, ClO, by conversion to
ClONO2 does not occur, since all the NO2 necessary for this reaction is tem-
porarily bound as nitric acid in the crystals. The larger crystals move down-
ward under the influence of gravity into the upper troposphere, thereby
removing NO2 from the lower stratosphere over the South Pole and further
preventing the deactivation of chlorine. This denitrification of the lower
stratosphere extends the life of the Antarctic ozone hole and increases the
ozone depletion.
Only when the PSCs and the vortex have vanished does chlorine return
predominantly to the inactive forms. The liberation of HNO3 from the
remaining crystals into the gas phase results in its conversion to NO2 by the
action of sunlight:
HNO3 UV 9: NO2 OH
More importantly, air containing normal amounts of NO2 mixes with polar
air once the vortex breaks down in late spring. The nitrogen dioxide quickly
combines with chlorine monoxide to form the catalytically inactive chlorine
nitrate. Consequently, the catalytic destruction cycles largely cease operation
and the ozone concentration builds back up toward its normal level a few
weeks after the PSCs have disappeared and the vortex has ceased, as illustrated
in Figure 2-2. Thus the ozone hole closes for another year, though the ozone
levels nowadays never quite return to their natural levels, even in the fall.
However, before the ozone levels build back up in the spring, some of the
ozone-poor air mass can move away from the Antarctic and mix with sur-
rounding air, temporarily lowering the stratospheric ozone concentrations in
adjoining geographic regions, such as Australia, New Zealand, and the south-
ern portions of South America.
Reactions That Create the Ozone Hole

In the lower stratosphere—the region where the PSCs form and chlorine is
activated—the concentration of free oxygen atoms is small; few atoms are
produced there on account of the scarcity of the UV-C light that is required
to dissociate O2. Furthermore, any atomic oxygen produced in this way
immediately collides with the abundant O2 molecules to form ozone, O3.
Thus, ozone destruction mechanisms based upon the O3 O 9: 2 O2 reac-
tion, even when catalyzed, are not important here.
Rather, most of the ozone destruction in the ozone hole occurs via the
process called Mechanism II in Chapter 1, with both X and X
being atomic
chlorine and with the overall reaction being 2 O3 9: 3 O2. Thus the sequence
starts with the reaction of chlorine with ozone:
Step 1: Cl O3 9: ClO O2
In Figure 2-5 the experimental ClO and O3 concentrations are plotted as a
function of latitude for part of the Southern Hemisphere during the spring of
1987. As anticipated, the two species display opposing trends, i.e., they anti-
correlate very closely. At sufficient distances away from the South Pole
(which is at 90°S), the concentration of ozone is relatively high and that of
ClO is low, since chlorine is mainly tied up in inactive forms. However, as
one travels closer to the pole and enters the vortex region, the concentration
of ClO suddenly becomes high and simultaneously that of O3 falls off sharply
(Figure 2-5): Most of the chlorine has been activated and most of the ozone
has consequently been destroyed. The latitude at which the concentrations
both change sharply marks the beginning of the ozone hole, which continues
through to the region above the South Pole. The anticorrelation of ozone
and ClO concentrations shown in Figure 2-5 was considered by researchers to
2.5
ClO
1.0 O3
Chlorine monoxide (ppb)
2.0
Ozone (ppm)
1.5 FIGURE 2-5 Stratospheric

0.5 ozone and chlorine
monoxide concentrations
1.0 versus latitude near the
O3
South Pole on September 16,
ClO 1987. [Source: Reprinted with
0.5
permission from P. S. Zurer,
0
Chemical and Engineering News
63°S 72°S
(30 May 1988): 16. Copyright
Latitude, approximate 1988 by the American Chemical
Society.]
be the “smoking gun,” proving that anthropogenic chlorine compounds such

as CFCs emitted into the atmosphere were indeed the cause of ozone-hole
formation.
In the next reaction in the sequence, two ClO free radicals, produced in
two separate step 1 events, combine temporarily to form a nonradical dimer,
dichloroperoxide, ClOOCl (or Cl2O2):
Step 2a: 2 ClO 9: Cl9O9O9Cl
The rate of this reaction becomes important to ozone loss under these condi-
tions because the chlorine monoxide concentration rises steeply due to the
activation of the chlorine. Once the intensity of sunlight has risen to an
appreciable amount in the Antarctic spring, the dichloroperoxide molecule
ClOOCl absorbs UV light and splits off one chlorine atom. The resulting
ClOO free radical is unstable, so it subsequently decomposes (in about a day),
releasing the other chlorine atom:
Step 2b: ClOOCl UV light 9: ClOO Cl

Step 2c: ClOO 9: O2 Cl
Adding steps 2a, 2b, and 2c, we see that the net result is the conversion of
two ClO molecules to atomic chlorine via the intermediacy of the dimer
ClOOCl, which corresponds to the second stage of Mechanism II:
light
2 ClO 9: [ClOOCl] 9: 2 Cl O2
By these processes ClO returns to the ozone-destroying form of chlorine,

Cl. If we add the above reaction to two times step 1 (the factor of 2 being
required to produce the two intermediate ClO species needed in reaction
2a so that none remains in the overall equation), we obtain the overall
reaction
2 O3 9: 3 O2
Thus a complete catalytic ozone destruction cycle exists in the lower
stratosphere under these special weather conditions, i.e., when a vortex is
present. The cycle also requires very cold temperatures, since under warmer
conditions ClOOCl is unstable and reverts back to two ClO molecules before
it can undergo photolysis, thereby short-circuiting any ozone destruction.
Before appreciable sunlight becomes available in the early spring, most of the
chlorine exists as ClO and Cl2O2 since step 2b requires fairly intense light
levels; such an atmosphere is said to be primed for ozone destruction.
About three-quarters of the ozone destruction in the Antarctic ozone
hole occurs by the mechanism set forth above, in which chlorine is the only
catalyst. This ozone destruction cycle contributes greatly to the creation of

the ozone hole. Each chlorine destroys about 50 ozone molecules per day dur-
ing the spring. The slow step in the mechanism is step 2a, which is the com-
bination of 2 ClO molecules. Since the rate law for step 2a is second order
in ClO concentration (i.e., its rate is proportional to the square of the ClO
concentration), it proceeds at a substantial rate, and the destruction of
ozone is significant, only when the ClO concentration is high. The abrupt
appearance of the ozone hole is consistent with the quadratic rather than
linear dependence of ozone destruction upon chlorine concentration by the
Cl2O2 mechanism. Let us hope that there are not many more environmental
problems whose effects will display such nonlinear behavior and similarly
surprise us!
P R O B L E M 2-1
A minor route for ozone destruction in the ozone hole involves Mechanism II
with bromine as X
and chlorine as X (or vice versa). The ClO and BrO free-
radical molecules produced in these processes then collide with each other
and rearrange their atoms to eventually yield O2 and atomic chlorine and
bromine. Write out the mechanism for this process, and add up the steps to
determine the overall reaction.
P R O B L E M 2-2
Suppose that the concentration of chlorine continues to rise in the strato-
sphere but that the relative increase in bromine does not rise proportion-
ately. Will the dominant mechanism involving dichloroperoxide or the
“chlorine plus bromine” mechanism of Problem 2-1 become relatively more
important or less important as the destroyer of ozone in the Antarctic
spring?
P R O B L E M 2-3
Why is the mechanism involving dichloroperoxide of negligible importance
in the destruction of ozone, compared to the mechanism that proceeds by
ClO O, in the upper levels of the stratosphere?
In the lower stratosphere above Antarctica, an ozone destruction rate of

about 2% per day occurs each September due to the combined effects of the
various catalytic reaction sequences. As a result, by early October almost all
the ozone is wiped out between altitudes of 15 and 20 km, just the region in
which its concentration normally is highest over the South Pole. This result
is illustrated in Figure 2-6, which shows

30
the measured ozone partial pressure as a
function of altitude over the Antarctic in
25
mid-spring in the years preceding the
ozone-hole formation (black curve) and in
Altitude (kilometers)
20 2001 (green curve). Notice that the deple-

tion from 13 to 19 km was more complete
15 in 2001 than on average in the preceding
years (dashed curve).
10 In summary, the special vortex weather
conditions in the lower stratosphere above
5 the Antarctic in winter cause denitrifica-
tion and lead to the conversion of inactive
0 chlorine into Cl2 and HOCl. These two
0 5 10 15 compounds produce atomic chlorine when
Ozone abundance (mPa) sunlight appears. The chlorine atoms effi-
ciently destroy ozone via Mechanism II.
FIGURE 2-6 The typical vertical distribution of ozone over Antarc-
Once the vortex disappears in the late
tica in mid-spring (October) in 1962–1971 (black curve, before the spring, the ice particles on which the acti-
ozone hole started), in the 1991–2001 period (dashed curve), and in vation of chlorine compounds occurs disap-
2001 (green curve). Ozone partial pressure is in millipascals. [Source: pear, the chlorine returns to inactive forms,
WMO/UNEP Scientific Assessment of Ozone Depletion 2006, Figure Q11-3.] and the hole heals.
The Size of the Antarctic Ozone Hole

Because (as explained later) the stratospheric concentration of chlorine
continued to increase until the end of the twentieth century, the extent of
Antarctic ozone depletion increased from the early 1980s at least until the
late 1990s. There are several relevant measures of the extent of ozone
depletion.
• One measure is the surface area covered by low overhead ozone; Figure 2-1a
shows the area within the 220-DU contour line for the mid-September to
mid-October period as a function of year. This area grew rapidly and approx-
imately linearly during the 1980s; the size of the hole in maximum depletion
years (1998, 2006) is somewhat larger than in the 1980s, though smaller
holes have appeared in some recent years.
• Similarly, the sharp decrease in the minimum amount of overhead ozone
in the spring that occurred from 1978 to the late 1980s has been replaced by
a slower decline, which now may have largely ceased (see Figure 2-1b).
• The average length of time during which ozone depletion occurs has also
increased in recent years. Some reduction in ozone levels is now usually seen
both in mid-winter (at least in the outer portions of the continent where
Ozone destruction step

O3 Cl !: O2 ClO
Atomic chlorine reconstitution

Mid-stratosphere Ozone hole/low stratosphere
ClO O !: Cl O2 2 ClO !: ClOOCl
ClOOCl UV !: ClOO Cl
ClOO !: Cl O2
Inactivation of chlorine
Cl CH4 !: HCl CH3
ClO NO2 !: ClONO2
Activation of chlorine on particle surfaces

H2O
HCl(g) !: H(aq) Cl(aq)
H2O(aq) ClONO2(g) !: HOCl(aq) HNO3(aq)
FIGURE 2-7 A summary
Cl(aq) HOCl(aq) !: Cl2(g) OH(aq) of the main ozone
destruction reaction cycles
Cl2(g) sunlight !: 2 Cl(g)
operating in the Antarctic
H(aq) OH(aq) !: H2O(aq) ozone hole.
there is some sunshine at that time) and in the summer as well as the spring,
and, indeed, there is now some persistence of the depletion from one year to
the next.
• The vertical region over which almost total ozone depletion occurs,
12–22 km, has not increased since the mid-1990s.
A review of the possible signs of recovery of the ozone layer published in
2006 pointed out that natural variations, such as the solar cycle and polar
temperatures, could mask any trends in stratospheric ozone-hole recovery of
the magnitude expected to date and indeed for the next few decades.
The various reactions that lead to catalytic ozone destruction by atomic
chlorine by various mechanisms are summarized in Figure 2-7.
Stratospheric Ozone Destruction over the Arctic Region

Given the similarity in climate, it may seem surprising that an ozone hole
above the Arctic did not start to form at the same time as one occurred in the
Antarctic. Episodes of partial springtime ozone depletion over the Arctic
region have occurred several times since the mid-1990s. The phenomenon is
less severe than in Antarctica because the stratospheric temperature over the
Arctic does not fall as low for as long and air circulation to surrounding areas
is not as limited. The flow of tropospheric air over mid-latitude mountain
ranges (Himalayas, Rockies) in the Northern Hemisphere creates waves of
air that can mix with polar air, warming the Arctic stratosphere. Because
the air is generally not as cold, polar stratospheric clouds form less frequently
over the Arctic than over the Antarctic and do not last as long. In the past,
only small crystals were formed; these are not large enough to fall out of the
stratosphere and thereby denitrify it. However, during the extended polar
night, the chlorine nitrate and hydrogen chloride do react on the surface of
the small particles to produce molecular chlorine, which then dissociates to
atomic chlorine and by reaction with an ozone molecule becomes chlorine
monoxide, as illustrated in Figure 2-8. Notice that, although HCl is con-
verted completely in the PSCs, the ClONO2, which is present in excess, is
not completely eliminated in the stratosphere above the North Pole. Once
the PSCs disappear as air temperatures rise, chlorine nitrate initially domi-
nates since it forms rapidly from ClO and nitrogen dioxide. The reaction of
atomic chlorine with methane is a slower process, and consequently the HCl
concentration is slower to rise.
Polar night Sunlight

Cl2 2 Cl ClO
Recovery
HNO3 NO X
ClO + NO2 ClONO2
NO + ClO Cl + NO2
3 CH4 + Cl HCl + CH3
PSC
chemistry
ClO + 2 Cl2O2
Concentration (ppb)
ClONO2 ClONO2
1 HCl
HCl
FIGURE 2-8 The
ClO
evolution of stratospheric
chlorine chemistry with
time above the Arctic in 0
winter and spring. [Source: Time
O3 loss
Redrawn from C. R. Webster
et al., Science 261 (1993): 1130.]
Before the mid-1990s, the vortex containing the cold air mass above the
Arctic broke up by late winter; therefore NO2-containing air mixed with vor-
tex air before much sunlight returned to the polar region in the spring. Since
the stratospheric air temperature usually rose above –80°C by early March,
the nitric acid in the particles was converted back to gaseous nitrogen diox-
ide before the intense spring sunlight could drive the Cl2O2 mechanism. Due
to increases in NO2 from both these sources, the activated chlorine was
mostly transformed back to ClONO2 before it could destroy much ozone
(Figure 2-8). Thus the total extent of ozone destruction over the Arctic area
was much less than that over the Antarctic in the past.
Unfortunately, there have been ominous signs in recent decades that
springtime conditions above the Arctic have been changing for the worse,
with the result that ozone depletion there accelerated in the lower strato-
sphere in some years. The Arctic vortex in the winter and spring of
1995–1996 was exceptionally cold and persistent, resulting in significant
chlorine-catalyzed losses of ozone as late as mid-April. Large, nitric acid–
containing particles were formed, and persisted long enough to fall out of
the stratosphere, thereby denitrifying certain regions. In addition, the
often-irregular shape of the Arctic vortex means that there are frequent
occasions when an “arm” of it passes over a sunlit area in late winter (before
the bulk of the vortex is illuminated); temporary ozone depletion occurs
within such arms. For example, a portion of the vortex passed across Great
Britain during March 1996, producing record lows of 195 DU in northern
Scotland.
However, the extent of winter–spring ozone loss over Arctic regions has
been very inconsistent, with almost no depletion in some recent winters but
significant depletion in others, as indicated in Figure 2-9. The amount of
ozone loss correlated linearly with the area associated with polar stratospheric
clouds (Figure 2-9). Both the maximum extent of ozone depletion and the
maximum vortex area appear to be increasing with time, although these
extremes are achieved only every few years when the vortex of cold air
above the Arctic remains stable into the late winter and early spring. The
greatest ozone depletion over the Arctic observed so far, about 135 DU,
occurred in the very cold winter of 2004–2005; that for 2005–2006 was con-
siderably less since the temperatures were not as cold.
For reasons that will be explained in Chapter 6, both the depletion
of ozone and the increase in carbon dioxide levels cool the stratosphere,
which will lead to even more depletion if cooling occurs in the springtime
and thereby extends the period in which PSCs remain. Some scientists
predict that recovery from ozone depletion will be slower in the Arctic than
in the Antarctic because of the cooling effects of CO2 and O3. Scientists
do not yet know whether or not the abrupt cooling in the winter of
2004–2005 that produced record ozone depletion was due largely to the
effects of increased CO2.
140
120 ’05
’96
100
Loss of ozone (DU)

’95 ’00
80
’93
FIGURE 2-9 Loss of
60 ’03
overhead ozone over the ’94
Artic versus the size of the ’97
polar stratospheric cloud in 40
recent years. [Source: Redrawn
from M. Rex et al., “Arctic 20
Winter 2005: Implications for
’98
’99
Stratospheric Ozone Loss and 0
Climate Change,” Geophysical 0 10 20 30 40 50
Research Letters 31 (2006): Area of polar stratospheric cloud (millions of km2)
L04116.]
Because the magnitude of ozone depletion above the Arctic in some

recent winters was about the same as that observed over the South Pole in
the early 1980s, some atmospheric scientists have stated that an Arctic ozone
hole now forms in some years. Since depletion of overhead ozone is never
100% complete, the definition of what conditions constitute a hole is some-
what arbitrary.
The chemistry underlying mid-latitude losses in stratospheric ozone is
discussed in Box 2-1. A systematic view of the various atmospheric chemical
reactions discussed in this chapter is given in Chapter 5, after the correspon-
ding reactions in the troposphere have been discussed.
Increases in UV at Ground Level

Experimentally, the amount of UV-B from sunlight (see Chapter 1) reaching
ground level increases by a factor of 3 to 6 in the Antarctic during the early
part of the spring because of the appearance of the ozone hole. Biologically,
the most dangerous UV doses under hole conditions occur in the late spring
(November and December), when the Sun is higher in the sky than in ear-
lier months and low overhead ozone values still prevail. Abnormally high
UV levels have also been detected in southern Argentina when ozone-
depleted stratospheric air from the Antarctic traveled over the area.
Increases in ground-level UV-B intensity have also been measured in
the spring months in mid-latitude regions in North America, Europe, and
BOX 2-1 The Chemistry Behind Mid-Latitude Decreases

in Stratospheric Ozone
s noted earlier, there was a worldwide and measurable ozone depletion was noted for
A decrease of several percent in the steady-
state ozone concentration in the stratosphere
several years after the eruption of El Chichon
in Mexico in 1982. There were dips signifi-
over nonpolar areas during the 1980s and an cantly below the trend for the ozone levels—
additional short-term major decrease from 1992 both of these periods temporarily increased
to 1994. The extent of depletion closely mir- the concentration of sulfuric acid droplets in
rored the total ozone concentration for any the lower stratosphere.
given month; the greatest depletion occurred in The other relevant reaction that takes
the March–April period and the least in the place on the surface of the sulfuric acid droplets
early fall. results in some denitrification of stratospheric
Scientists have had a harder time track- air. In the gas-phase steps of the sequence,
ing down the source of the mid-latitude ozone ozone itself converts some nitrogen dioxide,
depletion than that over polar regions. As in NO2, to nitrogen trioxide, NO3, which then
Antarctica, almost all the ozone loss in non- combines with other NO2 molecules to form
polar regions occurs in the lower stratosphere. dinitrogen pentoxide, N2O5:
Some scientists have speculated that reac-
tions leading to ozone destruction could occur NO2 O3 9: NO3 O2
not only on ice crystals but also on the sur- NO2 NO3 9: N2O5
faces of other particles present in the lower
stratosphere. They suggested that the reac- These gas-phase processes normally are
tions could occur on cold liquid droplets con- reversible and do not remove much NO2 from
sisting mainly of sulfuric acid that occur the air, but in the presence of high levels of
naturally in the lower stratosphere at all lati- liquid droplets, a conversion of N2O5 to nitric
tudes. The liquid droplets would have to be acid occurs instead:
cold enough for them to take up significant
amounts of gaseous HCl, or no net reaction H2SO4
droplets
would take place. There always exists a small N2O5 H2O(droplets) 9: 2 HNO3
background amount of the acid, due to the oxi-
dation of the naturally occurring gas carbonyl By this mechanism, much of the NO2 that
sulfide, COS, some of which survives long normally would be available to tie up chlorine
enough to reach the stratosphere. However, monoxide as the nitrate ClONO2 becomes
the dominant though erratic source of the unavailable for this purpose; hence a greater
H2SO4 at these altitudes is direct injection proportion of the chlorine atoms occur in the
into the stratosphere of sulfur dioxide gas emit- catalytically active form and destroy ozone. It
ted from volcanoes, followed by its oxidation should be realized, however, that even in the
to the acid. Indeed, the steep decline in ozone absence of particles, some NO2 is converted to
in 1992–1993 followed the June 1991 massive nitric acid as a result of its reaction with the
eruption of Mt. Pinatubo in the Phillipines, hydroxyl radical. This nitric acid eventually
BOX 2-1 The Chemistry Behind Mid-Latitude Decreases

in Stratospheric Ozone (continued)
undergoes photochemical decomposition in PROBLEM 1

daylight hours to reverse this reaction and to
produce species that are catalytically active in Deduce the overall reaction equation for the
ozone destruction. reaction sequence shown at left.
In the mid-latitude lower stratosphere, This mechanism explains why, in the cur-
the most important catalytic ozone destruc- rent high-chlorine lower stratosphere, large
tion reactions involving halogens employ volcanic eruptions can deplete mid-latitude
Mechanism II, with X being atomic chlorine stratospheric ozone for a few years, but it does
or bromine and X
being the hydroxyl not account for the overall trend of decreasing
radical: ozone in the 1980s. Some of the decrease is
probably due to the mechanism operating on
the background concentration of sulfuric acid
Cl O3 9: ClO O2
particles in the lower stratosphere; its magni-
tude would have increased continuously in
OH O3 9: HOO O2 this time period since the chlorine levels were
continuously increasing. Chlorine and bromine
ClO HOO 9: HOCl O2 increases combined resulted in about a 4%
decline in mid-latitude ozone levels in the
sunlight 1979–1995 period. However, much of the
HOCl 9: OH Cl gradual decline over mid-latitudes is believed
to be due to other factors, such as springtime
and similarly for the case where bromine dilution of ozone-depleted polar air and its
replaces chlorine. The reaction sequence transport out of the polar regions, changes in
involving collision of ClO with BrO discussed the solar cycle, and both natural and anthro-
for the Antarctic ozone hole is also operative pogenic changes in the pattern of atmospheric
here. transport and temperatures.
New Zealand. Calculations indicate that the extent of UV increases since

the 1980s over mid- and high-latitude regions amounts to 6–14%. The most
definitive experimental evidence comes from New Zealand, where long-
term summertime increases in UV-B, but as expected not in UV-A,
amounted to 12% by 1998–1999. The situation over mid-latitudes is compli-
cated by the facts that some UV-B is absorbed by the ground-level ozone
produced by pollution reactions (as explained in Chapter 3), thereby mask-
ing any changes in UV-B due to small amounts of stratospheric ozone deple-
tion, and that records of UV received at the Earth’s surface were started only
in the 1990s.
The Chemicals That Cause Ozone Destruction

The increase in levels of stratospheric chlorine and bromine that occurred in
the last half of the twentieth century was due primarily to the release into the
atmosphere of organic compounds containing chlorine and bromine that are
anthropogenic, that is to say, they are man-made. These anthropogenic con-
tributions to stratospheric halogen levels completely overshadowed the natu-
ral input. In this section, we investigate
• why the levels of chlorine and bromine increased due to the release into
the air of compounds having certain characteristics,
• how international agreements were put in place to control such substances,
• the strategy underlying the formulations of compounds to replace the orig-
inal halogen compounds, and the practical difficulties and controversy about
phasing out methyl bromide, and
• how two practical replacements developed by green chemistry for the
now-banned chemicals can be employed.
The chlorine- and bromine-containing compounds that give rise to

increased levels of the halogens in the stratosphere are those that do not have
a sink—i.e., a natural removal process such as dissolution in rain or oxidation
by atmospheric gases—in the troposphere. After a few years of traveling in the
troposphere, they begin to diffuse into the stratosphere, where eventually they
undergo photochemical decomposition by UV-C from sunlight and thereupon
release their halogen atoms.
The variation in the total concentration of stratospheric chlorine and
bromine atoms, expressed as the equivalent of chlorine in terms of ozone
destruction power, measured over the course of the last quarter-century and
projected to the middle of the twenty-first century, is illustrated by the top-
most curve in Figure 2-10. The peak chlorine-equivalent concentration of
about 3.8 ppb that occurred in the late 1990s was almost four times as great
as the “natural” level due to methyl chloride and methyl bromide releases
from the sea. The Antarctic ozone hole appeared first when the chlorine
concentration reached about 2 ppb (dotted horizontal line).
CFC Decomposition Increases Stratospheric Chlorine

As is clear from inspection of Figure 2-10, the recent increase in stratospheric
chlorine is due primarily to the use and release of chlorofluorocarbons—
compounds containing only chlorine, fluorine, and carbon, which are
commonly called CFCs. In the 1980s, about 1 million tonnes (i.e., metric
tons, 1000 kg each) of CFCs were released annually to the atmosphere.
These compounds are nontoxic, nonflammable, nonreactive, and have useful
4
Total Methyl bromide
Equivalent chlorine concentration (ppb)

chlorine Halons
HCFCs
3
Methyl chloroform
2
FIGURE 2-10 Actual and Chlorine level at
Carbon CFCs which Antarctic
projected concentration of
tetrachloride ozone hole appeared
stratospheric chlorine ver-
sus time, showing the con- 1
tributions of various gases.
“Natural” methyl bromide
Note that ozone-depleting “Natural” methyl chloride
effects of bromine atoms in
halons and methyl bromide 0
1979 ’84 ’89 ’94 ’99 2004 ’09 ’14 ’19 ’24 ’29 ’34 ’39 ’44 ’49 ’54
have been converted to
their chlorine equivalents. Year
[Source: DuPont.]
condensation properties (making them suitable for use as coolants, for exam-
ple); because of these favorable characteristics, they found a multitude of
uses. Large volumes of several CFCs were manufactured commercially and
employed worldwide throughout the mid-to-late 1900s. Most of the amounts
produced eventually leaked from the devices in which they were originally
placed and entered the atmosphere as gases.
CFCs have no tropospheric sink, so all their molecules eventually rise to
the stratosphere. In contrast to intuitive expectation, this vertical transport
in the atmosphere is not affected by the fact that the mass of such molecules
is greater than the average molecular mass of nitrogen and oxygen in air,
because the differential force of gravity is much less than that due to the con-
stant collisions of other molecules, which randomize the directions of even
heavy molecules.
The CFC molecules eventually migrate to the middle and upper parts of
the stratosphere where there is sufficient unfiltered UV-C from sunlight to
photochemically decompose them, thereby releasing chlorine atoms. CFCs
do not absorb sunlight with wavelengths greater than 290 nm, and they
generally require light of 220 nm or less for photolysis. The CFCs must rise
to the mid-stratosphere before decomposing, since UV-C does not pene-
trate to lower altitudes. Because vertical motion in the stratosphere is slow,
their atmospheric lifetimes are long. It is because of their long stratospheric
lifetimes that the chlorine concentration in Figure 2-10 falls so slowly
with time.
P R O B L E M 2-4
Reactions of the type
OH CF2Cl2 9: HOF CFCl2
are conceivable tropospheric sinks for CFCs. Can you deduce why they don’t
occur, given that C9F bonds are much stronger than O9F bonds?
Other Chlorine-Containing, Ozone-Depleting Substances

Another widely used carbon–chlorine compound that lacks a tropospheric
sink—although some of it ends up dissolving in ocean waters—is carbon
tetrachloride, CCl4, which also is photochemically decomposed in the strato-
sphere. Like CFCs, then, it is classified as an ozone-depleting substance
(ODS). Commercially, carbon tetrachloride was used as a solvent and was an
intermediate in the manufacture of several CFCs, during the production of
which some was lost to the atmosphere. Its use as a dry-cleaning solvent was
discontinued in most developed countries some decades ago, but until recently
it has continued to be used in many other countries. Because of its relatively
long atmospheric lifetime (26 years), it will continue to make a significant con-
tribution to stratospheric chlorine for several more decades (Figure 2-10).
Methyl chloroform, CH39CCl3, or 1,1,1-trichloroethane, was produced
in large quantities and used in metal cleaning in such a way that much of it
was released into the atmosphere. Although about half of it is removed from
the troposphere by reaction with the hydroxyl radical, the remainder survives
long enough to migrate to the stratosphere. Because its average lifetime is
only five years and its production has been largely phased out, its concentra-
tion in the atmosphere has declined rapidly since the 1990s. According to
Figure 2-10, the contribution of methyl chloroform to stratospheric chlorine
was substantial in the 1990s but by 2010 will become negligible.
Green Chemistry: The Replacement of CFC and

Hydrocarbon Blowing Agents with Carbon Dioxide
in Producing Foam Polystyrene
Polystyrene is a common polymer that is used to make many everyday items.
This polymer varies in appearance from a rigid solid plastic to foam poly-
styrene. Rigid plastic polystyrene is used in disposable silverware; audiocas-
sette, CD, and DVD cases; and appliance casings. Foam polystyrene is utilized
as insulation in coolers and houses, foam cups, meat and poultry trays, egg
cartons; in some countries it is still used in fast-food containers. Globally,
about 10 million tonnes of polystyrene are produced on an annual basis, with
approximately half used to produce the foam form.
In order to produce foam polystyrene, the melted polymer is combined

with a gas under pressure. This mixture is then extruded into an environment
of lower pressure where the gas expands, leaving a foam which is about 95%
gas and 5% polymer.
In the past, CFCs were employed as blowing agents for rigid plastic
foams, and foam polystyrene is no exception. When these foams are crushed
or they degrade, the CFCs are released into the atmosphere where they can
migrate to the stratosphere and act to destroy ozone. Low-molecular-weight
hydrocarbons, such as pentane, have also been used as blowing agents;
although these compounds do not deplete the ozone layer, they do contribute
to ground-level smog when they are emitted into the atmosphere, as we will
see in Chapter 3. Low-molecular-weight hydrocarbons are also very flammable
and reduce worker safety.
The search for a replacement for CFC and hydrocarbon blowing agents
led the Dow Chemical Company of Midland, Michigan, to develop a process
employing 100% carbon dioxide as a blowing agent for polystyrene foam
sheets. For this discovery, Dow was the recipient of a Presidential Green
Chemistry Challenge Award in 1996. Carbon dioxide, CO2, is not flammable
nor does it deplete the ozone layer. Nonetheless, we will see in Chapter 6 that
it is a greenhouse gas and thus contributes to the environmental problem of
global warming, so one might wonder whether we are trading one environ-
mental problem for another. However, waste carbon dioxide from other
processes (natural gas production and the preparation of ammonia) that
would otherwise be emitted into the atmosphere can be captured and used as
a blowing agent. In addition, we will see in Chapter 6 that CFCs not only
dramatically affect the ozone layer but also are greenhouse gases significantly
more potent than carbon dioxide.
Dow Chemical found an added advantage with the polystyrene foam
sheets made with carbon dioxide in that they remained flexible for a much
longer period of time than those made with CFCs. This results in less break-
age during use and a longer shelf life. In addition, foam sheets made with
CFCs had to be degassed of the CFCs prior to recycling them, while carbon
dioxide rapidly escapes from the polystyrene, leaving a sheet composed of
95% air and 5% polystyrene within a few days.
CFC Replacements
Compounds such as CFCs and CCl4 have no tropospheric sinks because they
do not undergo any of the normal removal processes: They are not soluble in
water and thus are not rained out from air; they are not attacked by the
hydroxyl radical or any other atmospheric gases and so do not decompose; and
they are not photochemically decomposed by either visible or UV-A light.
The compounds being implemented as the direct replacements for CFCs
all contain hydrogen atoms bonded to carbon. Consequently, a majority
(though not necessarily 100%) of the molecules will be removed from the
troposphere by a sequence of reactions which begins with hydrogen abstrac-

tion by OH:
|
OH H9C9 9: H2O C-centered free radical 9:
| CO2 and other products eventually
Reactions of this type are discussed in more detail in Chapters 3 and 5.
Because methyl chloride, methyl bromide, and methyl chloroform each con-
tain hydrogen atoms, a fraction of such molecules are removed in the tropo-
sphere before they have a chance to rise to the stratosphere.
The temporary replacements for CFCs employed in the 1990s and the
early years of the twenty-first century contain hydrogen, chlorine, fluorine,
and carbon; they are called HCFCs, hydrochlorofluorocarbons. One impor-
tant example is CHF2Cl, the gas called HCFC-22 (or just CFC-22). It is
employed in modern domestic air conditioners and in some refrigerators and
freezers, and it has found some use in blowing foams such as those used in food
containers. Since it contains a hydrogen atom and thus is mainly removed
from air before it can rise to the stratosphere, its long-term ozone-reducing
potential is small—only 5% of that of the CFC that it replaced. This advan-
tage is offset, however, by the fact that HCFC-22 decomposes to release chlo-
rine more quickly than does the CFC, so its short-term potential for ozone
destruction is greater than that implied by this percentage. But because most
HCFC-22 is destroyed within a few decades after its release, it is responsible
for almost no long-term ozone destruction. However, most concerns about
stratospheric ozone destruction are centered on the next few decades, before
substantial reduction of stratospheric chlorine occurs from the phase-out of
CFCs. Notice the contributions of HCFCs to the curve in Figure 2-10. They
should be significant only until about 2030.
Reliance exclusively on HCFCs as CFC replacements would have even-
tually led to a renewed buildup of stratospheric chlorine, because the volume
of HCFC consumption would presumably rise with increasing world population
and affluence. Products that are entirely free of chlorine, and that therefore
pose no hazard to stratospheric ozone, will be the ultimate replacements for
CFCs and HCFCs.
Hydrofluorocarbons, HFCs, substances that contain hydrogen, fluorine,
and carbon, are the main long-term replacements for CFCs and HCFCs. The
compound CH2F9CF3, called HFC-134a, has an atmospheric lifetime of
several decades before finally succumbing to OH attack. HFC-134a is now
used as the working fluid in new refrigerators and air conditioners for the
North American market, including those in automobiles. All HFCs eventu-
ally react to form hydrogen fluoride, HF. Unfortunately, one atmospheric
degradation pathway for HFC-134a, and for several HCFCs as well, produces
trifluoroacetic acid, TFA (CF39COOH), as an intermediate, which is then
removed from the air by rainfall. Some scientists worry that TFA represents
an environmental hazard to wetlands since it will accumulate in aquatic
plants and could inhibit their growth. However, some of the TFA in the envi-
ronment arises from the degradation under heating of polymers such as
Teflon, not from CFC replacements. Polyfluorocarboxylic acids, of which the
acid form of TFA is an example, have been used in certain commercial prod-
ucts but are now being phased out, as discussed in Chapter 12.
Another environmental concern with HFCs involves their accumula-
tion in air after their inadvertent release during use. While present in the tro-
posphere, before they are destroyed, HFCs contribute to global warming by
enhancing the greenhouse effect, a topic discussed in detail in Chapter 6.
Outside North America, industry usually uses cyclopentane or isobutane,
rather than an HFC, as a refrigerant. Such hydrocarbons have a much shorter
lifetime in air than HFCs. Some environmentalists hope that developing
countries will follow the hydrocarbon rather than the HFC route when they
start to manufacture goods requiring coolants. Fully fluorinated compounds
are unsuitable replacements for CFCs because they have no tropospheric or
stratospheric sinks, and if released into the air, they would contribute to
global warming for very long periods of time.
Halons
Halon chemicals are bromine-containing, hydrogen-free substances such as
CF3Br and CF2BrCl. Because they have no tropospheric sinks, they eventu-
ally rise to the stratosphere. There they are photochemically decomposed,
with the release of atomic bromine (and chlorine, if present), which, as we
have already discussed, is an efficient X catalyst for ozone destruction. Thus
halons also are ozone-depleting substances. Bromine from halons will con-
tinue to account for a significant fraction of the ozone-destroying potential of
stratospheric halogen catalysts for decades to come (Figure 2-10).
Halons are used in fire extinguishers. They operate to quell fires by releas-
ing atomic bromine, which combines with the free radicals in the combustion
to form inert products and less reactive free radicals. The halons release their
bromine atoms even at moderately high temperatures, since their C9Br bonds
are relatively weak. Since they are nontoxic and leave no residues upon evapo-
ration, halons are very useful for fighting fires, particularly in inhabited,
enclosed spaces, such as military aircraft, and those housing electronic equip-
ment, such as computer centers. The substitution of other chemicals for halons
in the testing of the extinguishers drastically reduces halon emissions to the
atmosphere, since only a minority of the releases are from the fighting of actual
fires. Fine sprays of water can be substituted for halons in fighting many fires.
Fluorine atoms are liberated in the stratosphere as a result of the decom-
position of halons, as well as CFCs, HCFCs, and HFCs. In principle, the flu-
orine atoms could catalytically destroy ozone (see Problem 2-6). However,
the reaction of atomic fluorine with methane and other hydrogen-containing
molecules in the stratosphere is rapid and produces HF, a very stable molecule.
Because the H9F bond is much stronger than the O9H bond, the reactiva-
tion of fluorine by the attack of the hydroxyl radical on hydrogen fluoride
molecules is very endothermic. Consequently, its activation energy is high
and the reaction is extremely slow at atmospheric temperatures (see Box 1-2).
Thus fluorine is quickly and permanently deactivated before it can destroy
any significant amount of ozone.
P R O B L E M 2-5
The free radical CF3O is produced during the decomposition of HCF-134a.
Show the sequence of reactions by which it could destroy ozone acting as an
X catalyst in a manner reminiscent of OH. (Note that it is too short-lived to
actually destroy much ozone.)
P R O B L E M 2-6
(a) Write the set of reactions by which atomic fluorine could operate as an X
catalyst by Mechanisms I and II in the destruction of ozone. (b) An alterna-
tive to the second step of Mechanism I in the case of X F is the reaction
between FO and ozone to give atomic fluorine and two molecules of oxygen.
Write out this mechanism, and deduce its overall reaction.
International Agreements That Restrict ODSs

In contrast to almost all other environmental problems, such as global warm-
ing (Chapter 7), international agreement on remedies to stratospheric ozone
depletion was obtained and successfully implemented in a fairly short period
of time. The use of CFCs in most aerosol products was banned in the late
1970s in North America and some Scandinavian countries. This decision was
made on the basis of predictions, made by Sherwood Rowland and Mario
Molina, chemists at the University of California, Irvine, concerning the
effect of chlorine on the thickness of the ozone layer. There was no experi-
mental indication of any depletion at the time of their prediction. Rowland
and Molina, together with the German chemist Paul Crutzen, were jointly
awarded the Nobel Prize in Chemistry in 1995 to honor their work in
researching the science underlying ozone depletion.
The growing awareness of the seriousness of chlorine buildup in the
atmosphere led to international agreements to phase out CFC production in
the world. The breakthrough came at a conference in Montreal, Canada,
in 1987 that gave rise to the Montreal Protocol; this agreement has been
strengthened at several follow-up conferences. As a result of this interna-
tional agreement, all ozone-depleting chemicals are now destined for phase-
out in all nations. All legal CFC production in developed countries ended in
1995. Developing countries have been allowed until 2010 to reach the same
goal. Figure 2-11 shows how the tropospheric concentrations of the two most
600
500 CFC-12
Concentration (ppt)
400
300
CFC-11
200
FIGURE 2-11 Tropo-

spheric concentrations of 100
CFC-11 and CFC-12.
1978 1982 1986 1990 1994 1998 2002 2006
[Source: NOAA, at Year
www.esrl.noaa.gov/gmd/aggi/]
widely used CFCs have changed in recent decades. The level of CFC-11
(CFCl3), the average atmospheric lifetime of which is about 50 years, peaked
about 1994, seven years after its production and emission started a precipitous
decline, and has dropped slowly since then; the level of CFC-12 (CF2Cl2),
which has a lifetime of more than 100 years, did not peak until about 2002.
The production of carbon tetrachloride and methyl chloroform has been
phased out. Developed countries have agreed to end production of HCFCs by
2030, and developing countries by 2040, with no increases allowed after 2015.
Halon production was halted in developed countries in 1994 by the
terms of the Montreal Protocol. However, use of existing stocks continues, as
do releases from fire-fighting equipment. In addition, in the 1990s, China and
Korea—which, as developing countries, have until 2010 to terminate pro-
duction—increased their production of these chemicals. For these reasons,
the atmospheric concentration of this chemical continued to rise.
The other bromine-containing ODS is the pesticide gas methyl bromide,
CH3Br. Scientifically we do not yet have a good handle on atmospheric
methyl bromide. In particular:
• Significant new sources of natural emission of the gas to the atmosphere
continue to be discovered. Consequently, even the approximate ratio of syn-
thetic to natural emissions is uncertain, as is the lifetime of about one year.
• The tropospheric concentration of the gas has changed much more since
1999 than had been anticipated by production levels and controls. Its con-
centration is still declining, though now at a slower rate.
Methyl bromide was added to the Montreal Protocol during the 1992
revision of the international treaty. It was agreed that developed countries
would phase out methyl bromide production and importation completely in
2005. Its consumption in all developing countries combined, which amounted
to less than half the U.S. usage, was to have been frozen at 1995–1998 levels
in 2002, was to have been reduced by 20% in 2005, and is to be completely
eliminated by 2015. However, its phase-out has been strongly resisted by some
U.S. farmers, and planned reductions have been deferred. The pros and cons
of implementing the Montreal Protocol controls on this controversial chemi-
cal are discussed in the online Case Study Strawberry Fields—The Banning of
Methyl Bromide on the website associated with this chapter.
As a direct result of the implementation of the gradual phase-out of
ozone-depleting substances, the tropospheric concentration of chlorine peaked
in 1993–1994, and had declined by about 5% by 2000. Much of the initial drop
was due to the phase-out of methyl chloroform, which has a short atmo-
spheric lifetime. The concentrations of CFCs are slow to drop because they
were used in many applications such as foams and cooling devices that only
slowly emit them to the atmosphere. The stratospheric chlorine-equivalent
level was predicted to have peaked, at less than 4 ppb, at the turn of the cen-
tury, with a gradual decline predicted thereafter (see Figure 2-10). Observa-
tions in 2000 indicated that the actual chlorine content in the stratosphere
had peaked, but the bromine abundance was still increasing. The slowness in
the decline of the stratospheric chlorine level is due to
• the long time it takes molecules to rise to the middle or upper strato-
sphere and to then absorb a photon and dissociate to atomic chlorine,
• the slowness of the removal of chlorine and bromine from the strato-
sphere, and
• the continued input of some chlorine and bromine into the atmosphere.
Because ozone is formed (and destroyed) in rapid natural processes, its
level responds very quickly to a change in stratospheric chlorine concentra-
tion. Thus the Antarctic ozone hole probably will not continue to appear after
the middle of the twenty-first century, that is, once the chlorine-equivalent
concentration is reduced back to the 2-ppb level it had in the years before the
hole began to form (Figure 2-10). Without the Montreal Protocol agreements,
catastrophic increases in chlorine, to many times the present level, would
have occurred, particularly since CFC usage and atmospheric release in
developing countries would have increased dramatically. A further doubling
of stratospheric chlorine levels would probably have led to the formation of a
substantial ozone hole each spring over the Arctic region. And with significant
ozone depletion over temperate areas would have come a catastrophic
increase in skin cancers.
P R O B L E M 2-7
Given that their C9H bonds are not quite as strong as those in CH4, can you
rationalize why ethane, C2H6, or propane, C3H8, is a better choice than
methane to inactivate atomic chlorine in the stratosphere?
P R O B L E M 2-8
No controls on the release of CH3Cl, CH2Cl2, or CHCl3 have been proposed.
What does that imply about their atmospheric lifetimes, compared to those
for CFCs, CCl4, and methyl chloroform?
Green Chemistry: Harpin Technology—Eliciting

Nature’s Own Defenses Against Diseases
Earlier in the chapter, we learned that methyl bromide is used as a pesticide
(more specifically, as a soil fumigant), some of which finds its way into the
stratosphere, where it becomes involved in the destruction of the ozone layer.
An interesting development, which offers an alternative to methyl bromide,
is known as harpin technology. This technology was developed by EDEN
Bioscience Corporation in Bothell, Washington, for which it was awarded a
Presidential Green Chemistry Challenge Award in 2001.
Harpin is a naturally occurring bacterial protein that was isolated from
the bacteria Erwinia amylovora at Cornell University. When applied to the
stems and leaves of plants, harpin elicits the plant’s natural defense mecha-
nisms to diseases caused by bacteria, viruses, nematodes, and fungi. Hypersen-
sitive response (HR), which is induced by harpin, is an initial defense by
plants to invading pathogens that results in cell death at the point of infec-
tion. The dead cells surrounding the infection act as a physical barrier to the
spread of the pathogen. In addition, the dead cells may release compounds
that are lethal to the pathogen.
Pests often build up immunity to pesticides. However, since harpin does
not directly affect the pest, it is unlikely that immunity will occur with it.
In addition to using traditional pesticides to control infestations in plants,
more recently a second approach to this problem has been to develop
genetically altered plants. The DNA in such plants has been altered to pro-
vide the plant with a means to ward off various pests. Although this
approach is often quite successful, it is not without its critics, especially in
Europe, where genetically altered plants face serious restrictions. In con-
trast, harpin has no effect on the plant’s DNA: It simply activates defenses
that are innate to the plant.
Traditional pesticides are generally made by chemists employing lengthy
chemical syntheses, which invariably create large quantities of waste, which is
often toxic. In addition, the compounds (chemical feedstocks) from which the
pesticides are produced are derived from petroleum. Approximately 2.7% of
all petroleum is used to produce chemical feedstocks, and thus the production
of these compounds is in part responsible for the depletion of this nonrenew-
able resource. In contrast, harpin is made from a genetically altered benign
laboratory strain of the Escherichia coli bacteria through a fermentation
process. After the fermentation is complete, the bacteria are destroyed and the
harpin protein is extracted. Most of the wastes are biodegradable. Thus the
production of harpin produces only nontoxic biodegradable wastes and does
not require petroleum.
Harpin has very low toxicity. In addition, it is applied at 0.002–0.06 kg/
acre, which represents an approximately 70% reduction in quantity when
compared to conventional pesticides. Harpin is rapidly decomposed by UV
light and microorganisms, which is in part responsible for its lack of contam-
ination and buildup in soil, water, and organisms as well as the fact that it
leaves no residue in foods.
An added benefit of harpin is that it also acts as a plant growth stimulant.
Harpin is thought to aid in photosynthesis and nutrient uptake, resulting in
increased biomass, early flowering, and enhanced fruit yields. Harpin is sold
as a 3% solution in a product called Messenger.
Review Questions
1. What is a Dobson unit? How is it used in relation 6. What are two effects on human health that sci-
to atmospheric ozone levels? entists believe will result from ozone depletion?
2. If the overhead ozone concentration at a point 7. Define what is meant by a tropospheric sink.
above the Earth’s surface is 250 DU, what is the
8. Explain what HCFCs are, and state what sort of
equivalent thickness in millimeters of pure ozone at
reaction provides a tropospheric sink for them. Is
1.0 atm pressure?
their destruction in the troposphere 100% com-
3. Describe the process by which chlorine plete? Why are HCFCs not considered to be suit-
becomes activated in the Antarctic ozone-hole able long-term replacements for CFCs?
phenomenon.
9. What types of chemicals are proposed as long-
4. What are the steps in Mechanism II by which term replacements for CFCs?
atomic chlorine destroys ozone in the spring over
10. Chemically, what are halons? What was their
Antarctica?
main use?
5. Explain why full-scale ozone holes have not yet
11. What gases are being phased out according to
been observed over the Arctic.
the Montreal Protocol agreements?
Green Chemistry Questions

See the discussion of focus areas and the principles (a) Into which of the three focus areas for these
of green chemistry in the Introduction before awards does this award best fit?
attempting these questions. (b) List two of the twelve principles of green chem-
1. The development of carbon dioxide as a blowing istry that are addressed by the green chemistry of
agent for foam polystyrene won a Presidential the carbon dioxide process.
Green Chemistry Challenge Award.
2. What environmental advantages does the use (b) List four of the twelve principles of green
of carbon dioxide as a blowing agent have over the chemistry that are addressed by the green chemistry
use of CFCs and hydrocarbons? in the use of harpin.
3. Does the carbon dioxide that is used as a blow- 5. Why is there little concern that pests will
ing agent contribute to global warming? develop immunity to harpin?
4. The development of harpin won a Presidential 6. Why is harpin not expected to accumulate in
Green Chemistry Challenge Award. the environment?
(a) Into which of the three focus areas for these
awards does this award best fit?
Additional Problems
1. (a) Some authors use milliatmosphere centime- 4. Using the information in Additional Problem 2,
ter (matm cm) rather than the equivalent Dobson show that 134 is the appropriate code number for
unit for the amount of overhead ozone; 1 matm cm CH2FCF3. Why is an a or b designation also
1 DU. Prove that the number of moles of over- required to uniquely characterize this compound?
head ozone over a unit area on the Earth’s surface
5. The chlorine dimer mechanism is not impli-
is proportional to the height of the layer, as speci-
cated in significant ozone destruction in the lower
fied in the definition of Dobson unit, and that
stratosphere at mid-latitudes even when the parti-
1 DU is equal to 1 matm cm.
cle concentration is enhanced by volcanoes.
(b) Calculate the total mass of ozone that is present Deduce two reasons why this mechanism is not
in the atmosphere if the average overhead amount important under these conditions.
is 350 Dobson units, and given that the radius of
6. As discussed in the text, the seriousness of the
the Earth is about 5000 km. [Hints: The volume of
Antarctic ozone hole in any given year can be
a sphere, which you can approximate the Earth to be,
analyzed in terms of (a) the minimum ozone
is 4␲r3/3. You may assume that ozone behaves as an
concentration reached, (b) the average October
ideal gas.]
(or mid-September to mid-October) ozone con-
2. The chemical formula for any CFC, HCFC, centration, (c) the geographic area that the hole
or HFC can be obtained by adding 90 to its code covers, or (d) the number of days or weeks that
number. The three numerals in the result represent very low ozone values are recorded. By consulting
the number of C, H, and F atoms, respectively. The several of the websites listed for this chapter at
number of Cl atoms can then be determined using www.whfreeman.com/envchem/, construct
the condition that the number of H, F, and Cl up-to-date graphs of the variation in each of these
atoms must add up to 2n 2, where n is the num- parameters. Is the annual hole showing signs yet
ber of C atoms. From the information, deduce the of reduction in seriousness according to any of
formulas for compounds with the following codes: these parameters?
(a) 12 (b) 113 (c) 123 (d) 124 7. If bromine, rather than chlorine, had been used
to make CFC-like compounds, would stratospheric
3. Using the information discussed in Additional ozone depletion have been worse or not as severe
Problem 2, deduce the code numbers for each of over mid-latitude regions? [Hint: Recall that more
the following compounds: bromine normally exists in catalytically active form than
does chlorine.]
(a) CH3CCl3 (b) CCl4 (c) CH3CFCl2
8. When Mechanism II for ozone destruction oper- that equal numbers of moles of each were released
ates with X Cl and X
Br, the radicals ClO and into the air at ground level, rank these four com-
BrO react together to reform atomic chlorine and pounds in terms of their potential to catalytically
bromine (see Problem 2-1). A fraction of the latter destroy ozone in the stratosphere. Explain your
process proceeds by the intermediate formation of ranking.
BrCl, which undergoes photolysis in daylight. At
10. What would be the advantages of using
night, however, all the bromine eventually ends up
hydrocarbons rather than CFCs or HCFCs as
as BrCl, which does not decompose and restart the
aerosol propellant to replace CFCs? What is their
mechanism until dawn. Deduce why all the bromine
major disadvantage? What type of agent should be
exists as BrCl at night, even though only a fraction
added to aerosol cans containing hydrocarbon
of the ClO with BrO collisions yields this product.
propellants to overcome this disadvantage and
9. Consider the following set of compounds: make them safer?
CFCl3, CHFCl2, CF3Cl, and CHF3. Assuming
Further Readings
1. M. J. Molina and F. S. Rowland, “Stratospheric Layer,” Nature 441 (2006): 39–45. (b) S. Solomon,
Sink for Chlorofluoromethanes: Chlorine Atom- “The Hole Truth,” Nature 427 (2004): 289–291.
Catalyzed Destruction of Ozone,” Nature 249
4. (a) A. E. Waibel et al., “Arctic Ozone Loss Due
(1974): 810–812. [The original article concerning
to Denitrification,” Science 283 (1999): 2064–2068.
CFC destruction of ozone.]
(b) G. Walker, “The Hole Story,” New Scientist (25
2. S. Solomon, “Stratospheric Ozone Depletion: March 2000): 24–28.
A Review of Concepts and History,” Journal of
5. M. Rex et al., “Arctic Winter 2005: Implica-
Geophysics 37 (1999): 275–316.
tions for Stratospheric Ozone Loss and Climate
3. (a) E. C. Weatherhead and S. B. Andersen, Change,” Geophysical Research Letters 31 (2006):
“The Search for Signs of Recovery of the Ozone L04116.
Log on to www.whfreeman.com/envchem4/ and click on Chapter 2. Several
of them show trends and up-to-date satellite data (often as color contour
diagrams, some with animation) concerning stratospheric ozone depletion in
polar regions.
C H A P T E R
3
THE CHEMISTRY
OF GROUND-LEVEL
AIR POLLUTION
In this chapter, the following introductory chemistry this most excellent canopy,
topics are used: the air,
look you, this excellent
 Ideal gas law o’erhanging
 Equilibrium concept, including redox reactions and their firmament, this magestic roof
fretted
balancing
with golden fire, why, it
 Acid–base theory, including pH and weak acid appears
calculations no other thing to me than a
foul
Background from Chapter 1 used in this chapter: and pestilent congregation of
vapours
 Excited states
William Shakespeare, Hamlet, Act II,
 Photon energies Scene 2
 Gas-phase catalysis
 Sink concept
Introduction
One of the most important features of the Earth’s atmosphere is that it is an
oxidizing environment, a phenomenon due to the large concentration of
diatomic oxygen, O2, that it contains. Almost all the gases that are released
into the air, whether “natural” substances or “pollutants,” are eventually
completely oxidized in the atmosphere and the end-products subsequently
deposited on the Earth’s surface. The oxidation reactions are vital to the
cleansing of the air. The best-known example of air pollution is the smog
that occurs in many cities throughout the world. The reactants that produce
the most common type of smog are mainly emissions from cars and electric
power plants, although in rural areas some of the ingredients are supplied by
emissions from forests. The operation of motor vehicles produces more air
91
92 Chapter 3 The Chemistry of Ground-Level Air Pollution
pollution than does any other single human activity. Ironically, diatomic
oxygen is also involved in the generation of smog.
In this chapter, the chemistry underlying the pollution of tropospheric air
is examined. As background, we begin the chapter by discussing the concentra-
tion units by which gases in the lower atmosphere are reported as well as the
constitution and chemical reactivity of clean air. The effects of polluted air
upon the environment and upon human health are discussed in Chapter 4.
Concentration Units for Atmospheric Pollutants

There is no consensus regarding the appropriate units by which to express
concentrations of substances in air. In Chapter 1, ratios involving numbers of
molecules—the “parts per” system—were emphasized as a measure. Other
measures are often also encountered and will be used in this chapter:
Molecules of a gas per cubic centimeter of air, molecules/cm3
Micrograms of a substance per cubic meter of air, ␮g/m3
Moles of a gas per liter of air, moles/L
Given the lack of a consensus on a single appropriate scale, it is impor-
tant to be able to convert gas concentrations from one set of units to another.
This form of manipulation is discussed in Box 3-1. Note as well that gas par-
tial pressures stated in atmospheres are synonymous with concentrations on
the “parts per” scales, so, for example, a partial pressure of 0.002 atm in air is
equivalent to 2000 ppm, since 2000 106 0.002.
The Chemical Fate of Trace Gases in Clean Air

In addition to the well-known stable constituents of the atmosphere (N2, O2,
Ar, CO2, H2O), the troposphere contains a number of gases that are present
in only trace concentrations, since they have efficient sinks and thus do not
accumulate.
From biological and volcanic sources, the atmosphere regularly receives
inputs of the partially oxidized gases carbon monoxide, CO, and sulfur dioxide,
SO2, and of several gases that are simple compounds of hydrogen, some of
whose atoms are in a highly reduced form (e.g., H2S, NH3); the most impor-
tant of these “natural” substances are listed in Table 3-1 on page 95.
Although most of these natural gases are gradually oxidized in air, none
of them react directly with diatomic oxygen molecules. Rather, their reac-
tions begin when they are attacked by the hydroxyl free radical, OH, even
though the concentration of this species in air is exceedingly small, a few
million molecules per cubic centimeter on average (see Problem 3-1). In
clean tropospheric air, as in the stratosphere, the hydroxyl radical is pro-
duced when a small fraction of the excited oxygen atoms resulting from the
photochemical decomposition of trace amounts of atmospheric ozone, O3,
Introduction 93
BOX 3-1 The Interconversion of Gas Concentrations
he number of moles of a substance is pro- Now PV nRT, so

T portional to the number of the molecules
of it (Avogadro’s number, 6.02 1023, is the
V nRT兾P
proportionality constant), and the partial pres- 1.66 1018 mol
sure of a gas is proportional to the number of
0.082 L atm/mol K
moles of it. Thus, a concentration, for exam-
ple, of 2 ppm for any pollutant gas present in 298 K/1 atm
air means
4.06 1017 L
2 molecules of the pollutant in 1 million mol-
Since 1 L 1000 cm3, then V 4.06
ecules of air
1014 cm3. Since 2 molecules of pollutant
2 moles of the pollutant in 1 million moles occupy 4.06 1014 cm3, it follows that the
of air concentration in the new units is 2.0 molecules/
2 106 atm partial pressure of pollutants per 4.06 1014 cm3, or 4.9 1013 molecules/ cm3.
1 atm total air pressure In general, the most straightforward
strategy to use to change the value of a concen-
2 L of pollutant in 1 million liters of air (when tration a/b from one scale to its value p/q on
the partial pressures and temperatures of pollu- another is to independently convert the units
tant and air have been adjusted to be equal) of the numerator a to the units of the numera-
Let us convert a concentration of 2 ppm tor p (both of which involve only the pollu-
to its value in molecules (of pollutant) per tant) and then convert the denominator b to
cubic centimeter (cm3) of air for conditions of its new value q (both of which involve the
1 atm total air pressure and 25°C. Since the total air sample).
value of the numerator, 2 molecules, in the To convert a value in molecules/cm3 or
new concentration scale is the same as in ppm to mol/L, we must change the molecules
the original, all we need to do is establish the of pollutant to the number of moles of pollu-
volume, in cubic centimeters, that 1 million tant; for a pollutant concentration, again of
molecules of air occupy. This volume is easy to 2 ppm, we can write
evaluate using the ideal gas law (PV nRT ), moles of pollutant
since we know that
(2 molecules 1 mol)/
P 1.0 atm
T 25 273 298 K (6.02 1023 molecules)
n (106 molecules)/ 3.3 1024 mol

(6.02 1023 molecules/mol) Thus the molarity is (3.3 1024 mol)/
1.66 1018 mol (4.06 1017 L), or 8.2 108 M.
An alternative way to approach these con-
and the gas constant R 0.082 L atm/mol K. versions is to use the definition that 2 ppm
BOX 3-1 The Interconversion of Gas Concentrations (continued)
means 2 L of pollutant per 1 million liters of air Now 40.7 mol 6.02 1023 molecules/mol
and to find the number of moles and molecules 2.45 1025 molecules, or 2.45 1016 billion
of pollutant contained in a volume of 2 L at the molecules of air.
stated pressure and temperature. Thus the SO2 concentration is
A unit often used to express concentra-
tions in polluted air is micrograms per cubic
3.01 * 1018 molecules of SO2
meter, i.e., ␮g/m3. If the pollutant is a pure sub-
stance, we can interconvert such values into 2.45 * 1016 billion molecules of air
the molarity and the “parts per” scales, pro- 123 ppb
vided that the pollutant’s molar mass is known.
Consider as an example the conversion
of 320 ␮g/m3 to the ppb scale if the pollutant Note that the conversion of moles to mole-
is SO2, the total air pressure is 1.0 atm, and cules was not strictly necessary, as Avogadro’s
the temperature is 27°C. Initially the concen- number cancels from numerator and denomi-
tration is nator. As stated previously, ppb refers to the
ratio of the number of moles as well as to the
320 mg of SO2 ratio of the number of molecules.
It is vital in all interconversions to distin-
1 m3 of air guish between quantities associated with the
pollutant and those of air.
First we convert the numerator from grams of
SO2 to moles, since from there we can obtain
the number of molecules of SO2:
PROBLEM 1
1 mol SO2 Convert a concentration of 32 ppb for any
320 * 10 - 6 g SO2 *
64.1 g SO2 pollutant to its value on
6.02 * 10 molecules of SO2
23
(a) the ppm scale,
*
1 mol SO2
(b) the molecules per cm3 scale, and
= 3.01 * 1018 molecules of SO2
(c) the molarity scale.
Then, using the ideal gas law, we can change
the volume of air to moles and then molecules, Assume 25°C and a total pressure of 1.0 atm.
using 1 L 1 dm3 (0.1 m)3:
n PV兾RT 1.0 atm 1.0 m3

PROBLEM 2
1L
n 0.082 L atm Convert a concentration of 6.0 1014 mole-
(0.1 m)3 cules/cm3 to the ppm scale and to the moles per
*
mole K * 300 K liter (molarity) scale. Assume 25°C and 1.0 atm
40.7 mol total air pressure.
Introduction 95
PROBLEM 3 PROBLEM 4
Convert a concentration of 40 ppb of ozone, The average outdoor concentration of carbon
O3, into monoxide, CO, is about 1000 ␮g/m3. What is
this concentration expressed on the ppm
(a) the number of molecules per cm3, and
scale? On the molecules per cm3 scale? Assume
(b) micrograms per m3. that the outdoor temperature is 17°C and that
the total air pressure is 1.04 atm.
Assume the air mass temperature is 27°C and
its total pressure is 0.95 atm.
react with gaseous water to abstract one hydrogen atom from each H2O
molecule:
UV-B
O3 9: O2 O*
O* H2O 9: 2 OH
The average tropospheric lifetime of a given hydroxyl radical is only about
one second, since it reacts quickly with one or another of many atmospheric
gases. Because the lifetime of hydroxyl radicals is short and sunlight is
Some Important Gases Emitted into the Atmosphere

TABLE 3-1 from Natural Sources
Main Natural Atmospheric

Formula Name Source Lifetime
NH3 Ammonia Anaerobic biological decay Days

H2S Hydrogen sulfide Anaerobic biological decay Days
HCl Hydrogen chloride Anaerobic biological decay, volcanoes
SO2 Sulfur dioxide Volcanoes Days
NO Nitric oxide Lightning Days
CO Carbon monoxide Fires; CH4 oxidation Months
CH4 Methane Anaerobic biological decay Years
CH3Cl Methyl chloride Oceans Years
CH3Br Methyl bromide Oceans Years
CH3I Methyl iodide Oceans
required to form more of them, the OH concentration drops quickly at night-

fall. Recall from Problem 1 of Box 1-2 that because the corresponding reac-
tion involving unexcited atomic oxygen atoms is endothermic, its activation
energy is high and consequently it occurs far too slowly to be a significant
source of atmospheric OH. Although OH participates in many atmospheric
reactions, it has been found recently that its concentration is directly propor-
tional to the O* concentration at any given time.
P R O B L E M 3-1
In one study, the concentration of OH in air at the time was found to be
8.7 106 molecules per cubic centimeter. Calculate its molar concentration
and its concentration in parts per trillion, assuming that the total air pressure
is 1.0 atm and the temperature is 15°C.
The hydroxyl free radical is reactive toward a wide variety of other mole-
cules, including the hydrides of carbon, nitrogen, and sulfur listed in Table 3-1,
and many molecules containing multiple bonds (double or triple bonds),
including CO and SO2. Although suspected for decades of playing a pivotal
role in air chemistry, the presence of OH in the troposphere was confirmed
only recently since its concentration is so very small. The great importance of
the hydroxyl radical to tropospheric chemistry arises because it, not O2, initi-
ates the oxidation of all the gases in Table 3-1 other than HCl. Without OH
and its related reactive species HOO, most of these gases would not be effi-
ciently removed from the troposphere, nor would most pollutant gases such as
the unburned hydrocarbons emitted from vehicles. Indeed, OH has been
called the “tropospheric vacuum cleaner” or “detergent.” The reactions that
it initiates correspond to a flameless, ambient-temperature “burning” of the
reduced gases of the lower atmosphere. If these gases were to accumulate, the
atmospheric composition would be quite different, as would the forms of life
that are viable on Earth. Interestingly, hydroxyl is unreactive to molecular
oxygen—in contrast to the behavior of O2 with many other free radicals—
and to molecular nitrogen, so it survives long enough to react with so many
other species.
An example of the reactions initiated by hydroxyl radical is the net oxi-
dation of methane gas, CH4, into the completely oxidized product carbon
dioxide, CO2:
OH catalyst
CH4 2 O2 999: CO2 2 H2O
As we shall see in Chapter 5, this overall reaction occurs by a sequence of

reactions, the first of which involves the reaction of hydroxyl radical with
methane, and the next-to-last of which involves the reaction of OH with
carbon monoxide. Indeed, this pair of reactions accounts for the fate of most
hydroxyl radicals in a clean atmosphere. However, since a new hydroxyl rad-
ical is also produced eventually in the multistep reaction sequence, it is act-
ing as a catalyst. Since the OH is originally produced from O3, the case can
be made that it is really ozone that causes the oxidation of most atmospheric
gases. Diatomic molecular oxygen reacts with some of the free-radical species
produced by OH reactions, so it does appear in the overall equation as the
substance that oxidizes the reactants.
The hydrogen halides (HF, HCl, HBr) and fully oxidized gases such as car-
bon dioxide are relatively unreactive (from the oxidation–reduction point of
view) in the troposphere because no further oxidation occurs with them; they
eventually are deposited on the Earth’s surface, often as a result of dissolving
in raindrops.
Urban Ozone: The Photochemical Smog Process

The Origin and Occurrence of Smog
Many urban centers in the world undergo episodes of air pollution during
which relatively high levels of ground-level ozone—an undesirable con-
stituent of air if present in appreciable concentrations at low altitudes in the
air that we breathe—are produced as a result of the light-induced chemical
reaction of pollutants. This phenomenon is called photochemical smog and
is sometimes characterized as “an ozone layer in the wrong place,” to contrast
it with the beneficial stratospheric ozone discussed in Chapter 1. The word
smog is a combination of smoke and fog. The process of smog formation
involves hundreds of different reactions, involving dozens of chemicals,
occurring simultaneously. Indeed, urban atmospheres have been referred to as
giant chemical reactors. The most important reactions that occur in such air
masses will be discussed in detail in Chapter 5. In the material below, we
investigate the nature and origin of the pollutants—especially nitrogen
oxides—that combine to produce photochemical smog.
The chief original reactants in an episode of photochemical smog are
molecules of nitric oxide, NO, and of unburned and partially oxidized hydro-
carbons that are emitted into the air as pollutants from internal combustion
engines; nitric oxide is also released from electric power plants. The concen-
trations of these chemicals are orders of magnitude greater than are found in
clean air. Gaseous hydrocarbons and partially oxidized hydrocarbons are also
present in urban air as a result of the evaporation of solvents, liquid fuels, and
other organic compounds. Collectively, the substances, including hydrocar-
bons and their derivatives, that readily vaporize into the air are called volatile
organic compounds, or VOCs. (Formally, VOCs are defined as organic com-
pounds having boiling points that lie between 50°C and 260°C.) For exam-
ple, vapor is released into the air when a gasoline tank is filled unless the
hose’s nozzle is specially designed to mini-

100 mize this loss. Evaporated, unburned gaso-
line is also emitted from the tailpipe of a
90 vehicle before its catalytic converter has
been warmed sufficiently to operate. Two-
Percentage of the emission, by sector
80
cycle engines such as those in outboard
70
motor boats are particularly notorious for
emitting significant proportions of their
60 gasoline unburned into the air. Personal
watercraft manufactured in the 1990s,
50 before pollution controls came into effect,
emitted more smog-producing emissions in
40 a day’s operation than an automobile of
the same era driven for several years!
30 Regulations proposed recently in California
would require new lawn mowers to be out-
20 fitted with a catalytic converter, though
this issue is controversial since some mower
10
manufacturers claim that a hot converter
could pose a fire hazard to the engine.
0
Nitrogen Sulfur Volatile organic Another vital ingredient in photo-
oxides dioxide compounds chemical smog is sunshine, which increases
the concentration of free radicals that
Transportation Fuel combustion participate in the chemical processes of
smog formation. Although the reactants—
Industrial processes Other
NO and VOCs—are relatively innocuous,
the final products of the smog reaction—
FIGURE 3-1 North American emissions of primary gaseous air
ozone, nitric acid, HNO3, and partially
pollutants from various sectors. [Source: U.S. EPA 1999 National Air oxidized (and in some cases nitrated)
Quality Trends Report.] organic compounds—are much more toxic.
VOCs NO O2 sunlight 9: 9: mixture of O3, HNO3, organics
Substances such as NO, hydrocarbons, and other VOCs that are emitted
directly into air are called primary pollutants; the substances into which
they are transformed, such as O3 and HNO3, are called secondary pollutants.
A summary of the relative importance of various economic sectors in emis-
sions of the primary pollutants sulfur dioxide, nitrogen oxides, and VOCs in
the United States and Canada is given in Figure 3-1.
Other than those that absorb sunlight and subsequently decompose,
most atmospheric molecules that are transformed in air begin by reacting
with the hydroxyl free radical, OH, which consequently is the key reactive
species in the troposphere. The most reactive VOCs in urban air are
hydrocarbons that contain a carbon–carbon double bond, CRC, and alde-

hydes, since their reactions with OH—and also with sunlight in the latter
case—are very fast. Other hydrocarbons such as methane are also present
in air, but due to the higher activation energy required, their reaction with
OH is sluggish. However, their reaction can become important in late
stages of photochemical smog episodes.
Nitrogen Oxide Production During Fuel Combustion

Nitrogen oxide gases are produced by two different reactions whenever a fuel
is burned in air with a hot flame. Some nitric oxide is produced from the oxi-
dation of nitrogen atoms contained in the fuel itself; it is called fuel NO.
About 30–60% of a fuel’s nitrogen is converted to NO during combustion.
However, most fuels do not contain much nitrogen, so this process accounts
for only a small fraction of NO emissions.
Nitric oxide, produced by the oxidation at high combustion temperatures
of atmospheric nitrogen, is called thermal NO. At high flame temperatures,
some of the nitrogen and oxygen gases in the air passing through the flame
combine to form NO:
hot flame
N2 O2 99: 2 NO
The higher the flame temperature, the more NO is produced. Since this
reaction is very endothermic, its equilibrium constant is very small at normal
temperatures but increases rapidly as the temperature rises. One might expect
that the relatively high concentrations of NO that are produced under com-
bustion conditions would revert back to molecular nitrogen and oxygen as
the exhaust gases cool, since the equilibrium constant for the above reaction
is much smaller at lower temperatures. However, the activation energy for the
reverse reaction is also quite high, so the process cannot occur to an apprecia-
ble extent except at high temperatures. Thus the relatively high concentra-
tions of nitric oxide produced during combustion are maintained in the
cooled exhaust gases; equilibrium cannot be quickly re-established, and the
nitrogen is “frozen” as NO.
Because the reaction between N2 and O2 has a high activation energy, it
is negligibly slow except at very high temperatures, such as occur in the mod-
ern combustion engines of vehicles—particularly when they are traveling at
high speeds—and in power plants. Very little NO is produced by the burning
of wood and other natural materials since the flame temperatures involved in
such combustion processes are relatively low.
Two distinct mechanisms are involved in the initiation of the reaction of
molecular nitrogen and oxygen to produce thermal nitric oxide; in one it is
atomic oxygen that attacks intact N2 molecules, whereas in the other it is free
radicals, such as CH, that are derived from the decomposition of the fuel. The
initial reaction steps of the first mechanism are
O2 Δ 2 O
O N2 9: NO N
The rate of the second, slower step is proportional to [O] [N2]. However, since,
from the equilibrium in the first step, [O] is proportional to the square root
of [O2], it follows that the rate of NO formation will be proportional to
[N2] [O2]1/2.
The nitric oxide released into air is gradually oxidized to nitrogen dioxide,
NO2, over a period of minutes to hours, the rate depending upon the concen-
tration of the pollutant gases present. Collectively, NO and NO2 in air is
referred to as NOX, pronounced “nox.” The yellow-brown color in the atmos-
phere of a smog-ridden city is due in part to the nitrogen dioxide present,
since this gas absorbs visible light, especially near 400 nm (see its spectrum in
Figure 3-2), removing sunlight’s purple component while allowing most yel-
low light to be transmitted. The small levels of NOX in clean air result in part
from the operation of the above reaction in the very energetic environment
of lightning flashes and in part from the release of NOX and of ammonia,
NH3, from biological sources. Recently it has been discovered that NOX is
emitted from coniferous trees when sunlight shines on them and when the
ambient concentrations of these gases are low.
Relative absorption
FIGURE 3-2 Absorption

spectrum of NO2 in the
solar ultraviolet region.
290 300 310 320 330 340 350 360 370 380 390 400 410 420
[Source: Reprinted from A. M.
Bass et al., J. Res. U.S. Natl. Bur.
Wavelength (nm)
Stand. A80 (1976): 143.]
Ground-Level Ozone in Smog

Photochemical smog is a widespread phenomenon in the modern world. If we
are to prevent or limit its formation, we must understand the main chemical
reactions that occur in it. Although the detailed reaction mechanism in smog
is quite complicated (discussed further in Chapter 5), its most important
aspects are discussed below.
In order for a city to generate photochemical smog, several conditions
must be fulfilled. First, there must be substantial vehicular traffic to emit
sufficient NO, reactive hydrocarbons, and other VOCs into the air. Second,
there must be warmth and ample sunlight in order for the crucial reactions,
some of them photochemical, to proceed at a rapid rate. Finally, there must
be relatively little movement of the air mass so that the reactants are not
quickly diluted. For reasons of geography (e.g., the presence of mountains)
and dense population, cities such as Los Angeles, Denver, Mexico City,
Tokyo, Athens, Sao Paulo, and Rome all fit the bill splendidly and conse-
quently are subject to frequent smog episodes. Indeed, the photochemical
smog phenomenon was first observed in Los Angeles in the 1940s and has
generally been associated with that city ever since, although pollution con-
trols have partially alleviated the smog problem in recent decades.
As in the stratosphere, ground-level ozone is produced by the reaction of
oxygen atoms with diatomic oxygen. The main source of the oxygen atoms in
the troposphere, however, is the photochemical dissociation by sunlight of
nitrogen dioxide molecules:
UV-A
NO2 9: NO O
O O2 9: O3
According to the results of Problem 1-3, light having wavelength less than
394 nm is capable of producing photochemical decomposition of NO2. The
absorption spectrum of nitrogen dioxide gas in the UV-A region, shown in
Figure 3-2, indicates that the gas does indeed absorb in this region, and sun-
light having wavelengths of about 394 nm or shorter is found to efficiently
induce decomposition.
As discussed above, it is predominantly NO rather than NO2 that is
emitted from vehicles and power plants into the air. In episodes of photo-
chemical air pollution, NO is oxidized to the dioxide gradually over a period
of several hours in complex reaction sequences that involve free radicals as
catalysts (see Figure 3-3). Indeed, one can see (Figure 3-4) the concentration
of NO first rising from emissions from early-morning vehicle traffic and then
falling during the morning as it is converted to NO2 in urban atmospheres on
smog days.
The concentration of ozone does not rise significantly in a city generating
smog until late in the morning (see Figure 3-4), when the NO concentration
free radicals
O2
HNO3, organic nitrates, H2O2
O2
NO free radicals NO2 O O3
sunlight
R R R
O2, NO sunlight, NO
C"C free radicals
C"O free radicals
more free radicals
FIGURE 3-3 Summary of
photochemical smog reac- H H H
tions discussed in detail in an ethene an aldehyde
Chapter 5. derivative
has been greatly reduced. This happens because residual nitric oxide reacts
with and destroys ozone formed in the morning to re-create nitrogen dioxide
and oxygen, a reaction that also occurs in the stratosphere:
NO O3 9: NO2 O2
The sum of the last three reactions above constitutes a null cycle, whereby there
is no net buildup of ozone or oxidation of NO to NO2 by this mechanism.
In fact, the oxidation of NO to NO2 does occur rapidly, before the pollu-
tion has diffused away, partly because of weather conditions and partly
because of the high concentration of catalytic free radicals that are generated
during a smog episode. More free radicals are produced than are consumed in
0.6
Hydrocarbons
0.5 Aldehydes
Pollutant concentration (ppm)
Ozone
NO2
0.4
NO
0.3
0.2
FIGURE 3-4 Time-of-day
(diurnal) variation in the
concentration of gases dur- 0.1
ing days of marked eye irri-
tation in Los Angeles in the 0
1960s. [Source: Redrawn from 4 6 8 10 12 2 4 6
D. J. Speeding, Air Pollution a.m. noon p.m.
(Oxford: Oxford University Diurnal time scale
Press, 1974).]
smog because of the reactions of VOCs, especially those containing highly

reactive bonds such as CRC and CRO. For example, ethene and its deriv-
atives react in a complex sequence of reactions with NO, free radicals, and
atmospheric oxygen to produce nitrogen dioxide and aldehydes, the concen-
trations of which rise rapidly in the morning (see Figure 3-4). The aldehydes
absorb sunlight with ␭ 350 nm, i.e., UV-B and some UV-A light; some of
them photochemically decompose in sunlight to produce additional free rad-
icals, thereby increasing their concentration (see Figure 3-3). Once produced
in significant amounts by decomposition of nitrogen dioxide—and not
quickly destroyed since the level of NO has abated—some of the ozone also
reacts with VOCs to yield more hydroxyl radicals, further accelerating the
smog reaction process.
Although our analysis above has identified ozone as the main product of
smog, the situation is actually more complicated, as a detailed study in Chap-
ter 5 indicates. Some of the nitrogen dioxide reacts with hydroxyl radical
to generate nitric acid, HNO3, and some reacts with organic free radicals to
produce organic nitrates.
Governmental Goals for Reducing Ozone Concentrations

Many countries individually, as well as the World Health Organization
(WHO), have established goals for maximum allowable ozone concentra-
tions in air of about 100 ppb or less, averaged over a one-hour period. For
example, the standard in Canada is 82 ppb, and that of WHO is 75–100 ppb.
The United States has adopted a standard in which the ozone level over an
eight-hour period is what is regulated, rather than the one-hour average; the
average eight-hour limit was set at 80 ppb in 1997 for the United States, com-
pared to the WHO eight-hour standard of 50–60 ppb. Generally speaking,
the longer the period over which the concentration is averaged in a regula-
tion, the lower the stated limit, since it is presumed that exposure to a higher
level is acceptable only if it occurs for a short time.
The ozone level in clean air amounts to only about 30 ppb. By way of con-
trast, the levels of ozone in Los Angeles air used to reach 680 ppb, but peak
levels have now declined to 300 ppb. Many major cities in North America,
Europe, and Japan exceed ozone levels of 120 ppb typically for 5 to 10 days
each summer.
The electrical power blackout that occurred in August 2003 in eastern
North America yielded some interesting information concerning the contri-
bution of power plants to air pollution in that region. Measurements over
Pennsylvania taken 24 hours after the blackout began found that SO2 levels
were down 90%, and ozone levels down about 50%, compared to a similarly
hot, sunny day a year earlier, and that visibility increased by about 40 km
because haze from particulates had decreased by 70%.
Photochemical Smog Around the World

The air in Mexico City is so polluted by ozone, particulate matter, and other
components of smog, and by airborne fecal matter, that it is estimated to be
responsible for thousands of premature deaths annually; indeed, in the center
of the city residents can purchase pure oxygen from booths to help them
breathe more easily! In 1990, Mexico City exceeded the WHO air guidelines
on 310 days, though peak levels have steadily declined since then. In contrast
to temperate areas where photochemical smog attacks occur almost exclu-
sively in the summer—when the air is sufficiently warm to sustain the chem-
ical reactions—Mexico City suffers its worst pollution in the winter months,
when temperature inversions prevent pollutants from escaping. Some of the
smog in Mexico City originates from butenes that are a minor component of
the liquefied gas that is used for cooking and heating in homes, some of which
apparently leaks into the air.
Athens and Rome, as well as Mexico City, attempt to limit vehicular
traffic during smog episodes. One strategy used by Athens and Rome is to
allow only half the vehicles to be driven on alternate days, the allocation
being based upon the license plate numbering (odd or even numbers).
Due to long-range transport of primary and secondary pollutants in air
currents, many areas which themselves generate few emissions are subject to
regular episodes of high ground-level ozone and other smog oxidants. Indeed,
some rural areas, and even small cities, that lie in the path of such polluted air
masses experience higher levels of ozone than do nearby larger urban areas.
This occurs because in the larger cities, some of the ozone transported from
elsewhere is eliminated by reaction with nitric oxide released locally by cars
into the air, as illustrated previously in the reaction of NO with O3. Ozone
concentrations of 90 ppb are common in polluted rural areas.
When hot summertime weather conditions produce large amounts of
ozone in urban areas but do not allow much vertical mixing of air masses as
they travel to rural sites, elevated ozone levels are often observed in eastern
North America and western Europe in zones that extend for 1000 km
(600 miles) or more. Thus, ozone control is a regional rather than a local air
quality problem, in contrast to what was usually assumed in the past. Indeed,
on occasion, polluted air from North America moves across the Atlantic to
Europe, northern Africa, and the Middle East; that from Europe can move
into Asia and the Arctic; and that from Asia can reach the west coast of
North America. Some analysts believe that by 2100, even the background
level of ozone throughout the Northern Hemisphere will probably exceed
current ozone standards.
A plot of ozone concentration contours for summer afternoon smog con-
ditions in North America is shown in Figure 3-5a. At each point along any
solid line, the concentration of ozone has the same value; hence contours
connect regions having equal levels of ozone. The highest levels (100 ppb)
(a)
60
FIGURE 3-5a Ninetieth
60 60 percentile contours of
80
summer afternoon ozone
concentrations (ppb)
100 measured in surface air
over the United States.
Ninetieth percentile means
80
that concentrations are
60 higher than this 10% of the
100 time. [Adapted from A. M.
80
Fiore, D. J. Jacob, J. A. Logan,
80 and J. H. Yin, “Long-Term Trends
60 60
in Ground-Level Ozone over
the Contiguous United States,
60 1980–1995,” J. Geo-phys. Res.
103 (1998): 1471–1480.]
(b)
105
95
85 FIGURE 3-5b Maximum

surface ozone levels, in
75 ppb, for 1996–1998 in
eastern North America.
65
[Source: Environment Canada,
“Interim Plan 2001 on Particu-
late Matter and Ozone,” Gov-
ernment of Canada Publication
(Ottawa: 2001).]
occur in the Los Angeles and New York–Boston areas, but note the 80-ppb
contour over a wide area south of the Great Lakes and into the Southeast, as
well as one surrounding Houston. Ozone levels are particularly high over
Houston—reaching 250 ppb on occasion—because of emissions of highly
reactive VOCs containing CRC bonds from the region encompassing the
petrochemical industry. Indeed, as of the late 1990s, Houston had overtaken

Los Angeles for the number of days per year in which ozone standards were
exceeded.
Considerable ozone is transported from its origin in the U.S. Midwest to
surrounding states and Canadian provinces, especially around the Great
Lakes (see Figure 3-5b). An example of a rural area subject to high ozone con-
centrations is the farmland in southwest Ontario, which often receives
ozone-laden air from industrial regions in the United States that lie across
Lake Erie.
Elevated levels of ozone also affect materials: It hardens rubber, reducing
the useful lifespan of consumer products such as automobile tires, and it
bleaches color from some materials such as fabrics.
The photochemical production of ozone also occurs during dry seasons in
rural tropical areas where the burning of biomass for the clearing of forests or
brush is widespread. Although most of the carbon is transformed immediately
to CO2, some methane and other hydrocarbons are released, as is some NOX.
Ozone is produced when these hydrocarbons react with the nitrogen oxides
under the influence of sunlight.
Limiting VOC and NO Emissions to Reduce

Ground-Level Ozone
In order to improve the air quality in urban environments that are subject to
photochemical smog, the quantity of reactants, principally NOX and hydro-
carbons containing CRC bonds plus other reactive VOCs, emitted into the
air must be reduced. The control strategies in place in the United States have
resulted in some ozone level reduction over the past few decades, notwith-
standing the huge increase in total vehicle-miles driven—up to 100% more
in the last 25 years.
For economic and technical reasons, the most common control strategy
has been to reduce hydrocarbon emissions. However, except in downtown
Los Angeles, the percentage reduction in ozone and other oxidants that is
achieved usually has been much less than the percentage reduction in
hydrocarbons. This happens because usually there is initially an overabun-
dance of hydrocarbons relative to the amount of nitrogen oxides, and cut-
ting back hydrocarbon emissions simply reduces the excess without slowing
down the reactions significantly. In other words, it is usually the nitrogen
oxides, rather than reactive hydrocarbons, that determine the overall rate of
the reaction. This is especially true for rural areas that lie downwind of pol-
luted urban centers.
Due to the large number of reactions that occur in polluted air, the func-
tional dependence of smog production upon reactant concentration is com-
plicated, and the net consequence of making moderate decreases in primary
pollutants is difficult to deduce without computer simulation. Computer
0.28
Ozone =
0.24 80 ppb
160 ppb
0.20 B 240 ppb
VOC-
limited FIGURE 3-6 The rela-
NOX (ppm)
0.16 region tionship between NOX and

VOC concentrations in air
0.12 and the resulting levels of
ozone produced by their
0.08 reaction. Points A, B, and C
denote conditions discussed
C in the text. [Source: Redrawn
0.04 A NOX-limited region
from National Research
Council, Rethinking the Ozone
0 Problem in Urban and
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
Regional Air Pollution
VOC (ppm of carbon) (Washington, DC: National
Academy Press, 1991).]
modeling indicates that NOX reduction, rather than VOC reduction, would
be much more effective in reducing ozone in almost all of the eastern United
States. An example of the predictions that arise from the modeling studies
is shown in Figure 3-6. The relationships between the NOX and the VOC
concentrations that produce contours for three different values for the
concentration of ozone are shown. Point A represents a typical set of condi-
tions in which the ozone production is NOX-limited. For example, reducing
the concentration of VOCs from 1.2 ppm to 0.8 ppm has virtually no effect
on the ozone concentration, which remains at about 160 ppb since the curve
in this region is almost linear and runs parallel to the horizontal axis. How-
ever, a reduction of the NOX level from about 0.03 ppm at point A to a lit-
tle less than half this amount, which corresponds to dropping down to the
curve directly below it in the figure, cuts the predicted ozone level in half,
from 160 ppb to 80 ppb. Chemically, NOX-limited conditions occur when,
due to the high concentration of VOC reactants, an abundance of peroxy
free radicals HOO and ROO are produced, which quickly oxidize NO emis-
sions to NO2:
HOO NO 9: OH NO2
The nitrogen dioxide then photochemically decomposes to produce the free

oxygen atoms that react with O2 to produce ozone, as previously discussed
(see Figure 3-3).
In the portion of the VOC-limited region that lies to the left of the diag-
onal dashed line of Figure 3-6, there is a large excess of NOX; under such
conditions, the OH radical tends to react with NO2, so less of it is available

to initiate the reaction of more VOCs:
OH NO2 9: HNO3
Consequently, lowering the NOX concentration actually produces more
ozone, not less, since more OH is available to react with the VOCs,
although production of other smog reaction products such as nitric acid is
thereby reduced. Thus, for example, when the VOC concentration is about
0.5 ppm, lowering the NOX concentration from 0.21 ppm—corresponding
to point B on Figure 3-6—even by two-thirds of this amount is predicted to
increase the ozone level slightly beyond 160 ppb; further reductions do not
begin to decrease ozone until NOX reaches about 0.05 ppm. In situations
where VOCs are relatively plentiful, that is, to the right side of the dashed
line in Figure 3-6, reducing NOX also reduces ozone. Thus, when the VOC
level is 0.5 ppm, the ozone concentration falls back to 160 ppb when the
NOX is reduced to 0.04 ppm (point C) and declines more with further
decreases of NOX.
P R O B L E M 3-2
Using Figure 3-6 and assuming a NOX concentration of 0.20 ppm, estimate
the effect on ozone levels of reducing the VOC concentration from 0.5 to
0.4 ppm. Do your results support the characterization of that zone of the
graph as VOC-limited?
P R O B L E M 3-3
Using Figure 3-6, again with an initial VOC concentration of 0.50 ppm, esti-
mate the effect on ozone levels of lowering the NOX concentration from 0.20
to 0.08 ppm. Explain your results in terms of the chemistry discussed above.
Some urban areas such as Atlanta, Georgia, and others located in the
southern United States include or border upon heavily wooded areas whose
trees emit enough reactive hydrocarbons to sustain smog and ozone produc-
tion, even when the concentration of anthropogenic hydrocarbons, i.e.,
those that result from human activities, is low. Deciduous trees and shrubs
emit the gas isoprene, whereas conifers emit pinene and limonene; all three
hydrocarbons contain CRC bonds. The blue hazes that are observed over
forested areas such as the Great Smoky Mountains in North Carolina and the
Blue Mountains in Australia result from the reaction of such natural hydro-
carbons in sunlight to produce carboxylic acids that condense to form sus-
pended particles of the size that scatter sunlight and thereby produce a haze.
Some of the ozone molecules present above the forests react with the CRC
bond in the natural hydrocarbons to first produce aldehydes, which are then
further oxidized in air to the corresponding carboxylic acids. Eventually, the
acids in the aerosol are attacked by hydroxyl radicals, which initiate their
decomposition, if the haze is not rained out of the air beforehand.
In urban atmospheres, the concentration of these natural reactive hydro-
carbons normally is much less than that of the anthropogenic hydrocarbons,
and it is not until the latter are reduced substantially that the influence of
these natural substances becomes noticeable. In areas affected by the pres-
ence of vegetation, then, only the reduction of emissions of nitrogen oxides
will reduce photochemical smog production substantially. As an air mass
moves from an urban area to a rural one downwind, it often changes from
being VOC-limited to being NOX-limited, since there are few sources of nitro-
gen oxides, but often substantial sources of reactive VOCs, outside cities and
since the reactions that consume nitrogen oxides occur more quickly than do
those that consume VOCs.
Although hydrocarbons with CRC bonds and aldehydes are the most
reactive types in photochemical smog processes, other VOCs play a signifi-
cant role after the first few hours of a smog episode have passed and the con-
centration of free radicals has risen. For this reason, control of emissions of all
VOCs is required in areas with serious photochemical smog problems. Gaso-
line, which is a complex mixture of hydrocarbons, is now formulated in order
to reduce its evaporation, since gasoline vapor has been found to contribute
significantly to atmospheric concentrations of hydrocarbons. The control of
VOCs in air is discussed in more detail in Chapter 16. New regulations in
California (with Los Angeles especially in mind) limit the use of hydrocarbon-
containing products such as barbecue-grill starter fluid, household aerosol
sprays, and oil-based paints that consist partially of a hydrocarbon solvent
that evaporates into the air as the paint dries. The air quality in this region
has improved because of current emission controls, but the increase in vehicle-
miles driven and the hydrocarbon emissions from nontransportation sources
such as solvents have thus far prevented a more complete solution. Research
has also indicated that any substantial increase in the emissions of methane
to the atmosphere could prolong and intensify the periods of high ozone in
the United States, even though CH4 is usually considered to be a rather unre-
active VOC.
Technological Control of Emissions

Catalytic Converters
Over the last decades, automobile manufacturers have employed several
strategies to decrease VOC and NOX emissions from their vehicles and
thereby meet governmental standards. One early technique that had some
success for NOX control was to lower the temperature of the combustion
flame and thereby decrease the rate of creation of thermal nitric. The tem-
perature lowering was achieved by recirculating a fraction of the engine
emissions back through the flame, which presumably lowered the flame tem-
perature and hence the production of thermal NO by lowering the concentra-
tion of oxygen in combustion.
In recent decades, more complete control of NOX emissions from gasoline-
powered cars and trucks has been attempted using catalytic converters
placed just ahead of the mufflers in the vehicle’s exhaust system. The original
two-way converters controlled only carbon-containing gases, including car-
bon monoxide, CO, by completing their combustion to carbon dioxide.
However, by use of a surface impregnated with a platinum–rhodium catalyst,
the modern three-way converter changes nitrogen oxides back to elemental
nitrogen and oxygen using unburned hydrocarbons and the combustion
intermediates CO and H2 as reducing agents:
2 NO 9: N2 O2 overall
via, for example,
2 NO 2 H2 9: N2 2 H2O
P R O B L E M 3-4
Write and balance reactions in which NO is converted to N2 by (a) CO and
(b) C6H14. [Hint: The other reaction product is CO2, plus H2O in the latter case.]
The carbon-containing gases in the exhaust are catalytically oxidized

almost completely to CO2 and water by the oxygen that is present:
2 CO O2 9: 2 CO2
CnHm (n m/4) O2 9: n CO2 m/2 H2O
CH2O O2 9: CO2 H2O
The catalyst is dispersed as very tiny crystallites, initially less than 10 nm

in size. An oxygen sensor in the vehicle’s exhaust system is monitored by a
computer chip that controls the intake air/fuel ratio of the engine to the stoi-
chiometric amount required by the fuel in order to ensure a high level of con-
version of the pollutants. The whole process is illustrated in Figure 3-7a. If the
air/fuel mix is not very close to the stoichiometric ratio, the warmed catalyst
will not be effective for reduction (if there is too much air), causing nitrogen
oxides to be emitted into the air, or for oxidation (if there is too little air),
causing CO and hydrocarbons to be emitted, as illustrated in Figure 3-7b.
(a) (b)
100
Catalytic 90
converter Hydrocarbons
Exhaust from 80
Conversion (percent)
motor
70
Catalytic converter
60
Muffler 50
Tailpipe 40
Exhaust 30
Platinum to tailpipe CO NOX
20
Rhodium 10
Porous
ceramic
0
coating <1 Rich 1.0 Lean >1
(excess fuel) (excess air)
Air/fuel ratio
FIGURE 3-7 (a) Modern catalytic converter for automobiles, with its position in the exhaust
system indicated. [Source: L. A. Bloomfield, “Catalytic Converter,” Scientific American (February 2000):
108.] (b) Efficiency in conversion of catalytic converter versus air/fuel ratio. [Source: B. Harrison,
“Emission Control,” Education in Chemistry 37 (2000): 127.]
reduction
N2 NO
catalytic
converter
processes
CO
oxidation
CnHm CO2 H2O
CH2O
Some progress has been reported recently in the use of less valuable met-
als, such as copper and chromium, instead of the expensive platinum-group
metals as catalysts in catalytic converters. Although the metals are recycled
from old converters, a portion is inevitably lost in the process. Recently, sci-
entists have become concerned about the environmental problem of widely
broadcasting the tiny particles of platinum, palladium, and rhodium that are
lost from the converters themselves during their operation.
The catalyst that reduces nitric oxide to nitrogen also reduces sulfur
dioxide, SO2, to hydrogen sulfide, H2S. The emitted gases include reduced
sulfur compounds such as H2S, which often give vehicle emissions their char-
acteristic odor of rotten eggs. In addition, the small amounts of sulfur-containing
molecules in gasoline—and diesel fuel—can partially deactivate catalytic con-

verters if sulfate particles produced during the gasoline’s combustion become
attached to and thereby cover the active sites of the catalyst metal. The max-
imum annual average sulfur levels in gasoline, amounting to several hundred
parts per million in the past, have recently been reduced to 30 ppm in both the
United States and Canada, and to 50 ppm in the European Union. The sulfur
is removed during refining, usually by hydrodesulfurization, itself a catalytic
process, which reacts organic sulfur-containing molecules in the gasoline with
hydrogen gas, H2, to produce hydrogen sulfide, H2S, which is then removed.
Alternatively, the sulfur-containing molecules may be removed from the fuel
by absorbing them during the refining process.
In the first few minutes after a vehicle’s engine has been started up, the
catalysts are cold, so the converters cannot operate effectively and there
are bursts of emissions from the tailpipe. Indeed, approximately 80% of all
the emissions from converter-equipped cars are produced in the first few min-
utes after starting. Once an engine has warmed up and the catalysts have
been heated to about 300°C by engine exhaust, three-way catalysts convert
80–90% of the hydrocarbons, CO, and NOX to innocuous substances before
the exhaust gases are released into the atmosphere. However, fuel-rich mix-
tures are fed to the engine in the first minute or so after the vehicle engine is
started, and also when high acceleration occurs, so carbon monoxide and
unburned hydrocarbons are emitted directly into the air under these oxygen-
starved conditions.
Research and development is underway to develop catalytic converters
that would convert start-up emissions so that these are not released into the
air. Various approaches being investigated include
• devising a converter that will operate at lower temperatures or that can
be preheated so it begins to operate immediately,
• storing pollutants until the engine and converter are heated, and
• recirculating engine exhaust through the engine until the reactions are
more complete.
Older cars (with no converters or just two-way converters) still on the road
continue to pollute the atmosphere with nitrogen oxides even during their
normal operation.
The maximum amounts of emissions that can legally be released from
light-duty motor vehicles such as cars have gradually been decreased in order
to improve air quality. Some governments have recently instituted manda-
tory inspections of exhaust systems to ensure that they continue to operate
properly.
Vehicles whose catalytic converters have been damaged or tampered
with produce most of the emissions: Typically, 50% of the hydrocarbons and
carbon monoxide are released from 10% of the cars on the road. For example,
0.1
0.075
Fraction of total CO
0.05
0.025
0.0
’71 ’72 ’73 ’74 ’75 ’76 ’77 ’78 ’79 ’80 ’81 ’82 ’83 ’84 ’85 ’86 ’87 ’88 ’89 ’90 ’91 ’92 ’93 ’94 ’95 ’96 ’97
Model year
FIGURE 3-8 Fleet-weighted CO contribution of vehicles by model year. [Source: G. A. Bishop

et al., “Drive-By Motor Vehicle Emissions: Immediate Feedback in Reducing Air Pollution,” Environ. Sci.
Technol. 34 (2000): 1110.]
a recent study about soot emissions from cars in the Netherlands found that
5% of vehicles accounted for 43% of pollution. A mid-1990s survey of carbon
monoxide emitted by passing traffic in Denver, Colorado, produced the
results shown in Figure 3-8. The great majority of Denver vehicles of ages up
to about 12 years were rated “good” in terms of their control of tailpipe emis-
sions. Most of the carbon monoxide came from cars 6–12 years old because they
were so numerous and because of the presence in that fleet of cars with “poor”
or “fair” emission levels.
The control over the past half-century of carbon monoxide levels in
urban areas of developed countries has been one of the real success stories in
environmental management. In the United States, for example, the average
CO concentration declined by two-thirds in the 1983–2002 period alone.
Most of the reduction has resulted from the use of catalytic converters on vehi-
cles, from the ever tightening regulations on vehicular emissions, and from the
natural continuing increase in the fraction of vehicles built after standards had
been tightened. The introduction of oxygenated substances, which are hydro-
carbons in which some of the atoms have been replaced by oxygen, into
American gasoline has also reduced CO emissions from vehicles (as will be
discussed further in Chapter 8). Average new-vehicle emissions before any
emission controls were introduced in the United States were about 38 g
CO/km, compared to the present standard of 1.5 g/km. Generally speaking,
carbon monoxide emissions from vehicles are greatest from cold engines (and
cold catalytic converters) and when the engine has an increased load due to
rapidly accelerating or climbing a hill, since under these conditions, a rich fuel
mix supplies insufficient oxygen to completely oxidize the gasoline.
There are some cities in developed countries that are still vulnerable to
CO concentration excesses in winter due to meteorological and topological
conditions. The temperature inversions in Fairbanks, Alaska, for example,
produce several days each winter with high carbon monoxide levels. People
such as traffic police who work outdoors in areas of high vehicular traffic can
be exposed to elevated CO levels for long periods.
In the past, emission standards were applied only to passenger vehicles.
However, starting in 2004, new U.S. regulations required for the first time
that gasoline-powered sport-utility vehicles (SUVs)—which now account
for about half of new-vehicle sales—and light trucks also meet emission
standards.
Motorcycles and the three-wheel tuk-tuk taxis common in Asia are
gasoline-powered, and their emissions, especially of CO and unburned hydro-
carbons, make substantial contributions to air pollution. In a recent study in
Switzerland, scooters and motorcycles (some fitted with catalytic converters)
were found to emit more CO and hydrocarbons in urban driving, and signifi-
cantly more NOX on the highway per kilometer traveled, than did cars.
Most trucks and buses are powered by diesel engines, as are many cars in
Europe and elsewhere outside North America. The catalytic converters used on
vehicles with diesel engines in the past were much less effective than those on
gasoline-powered vehicles. They typically removed only about half the gaseous
hydrocarbon emissions, compared to 80–90% achieved for gasoline engine
emissions. This difference is due to the less active catalyst formulations that
had to be used with diesels because of the high sulfur content of diesel fuel; more
active catalysts would have oxidized the sulfur dioxide gas to sulfate particles,
which would cover the catalyst surface and render it ineffective. Much more
effective catalytic converters are now being installed on diesel equipment for
use with low-sulfur fuel. Also, the loss of engine exhaust gases and particles to
the air—including that inside the vehicle—through crankcase emissions is
being eliminated by rerouting the emissions back into the engine.
Catalytic converters used for diesel engines did not convert NOX since
diesel engines are operated “fuel lean,” i.e., with excess oxygen present, and
hence the required chemically reducing conditions did not exist. However,
NOX emissions from diesels are inherently lower than from gasoline vehicles
since their operating temperature is significantly lower and consequently less
thermal NO is formed. Lowering the engine operating temperature even
further, by recirculating some of the exhaust gases through the engine, cuts
back the amount of NOX produced even more, as was also done with automo-
biles, as mentioned above. New emission regulations in North America that
take effect in the mid- and late-2000s demand substantial reductions in NOX
emissions from diesel-powered vehicles. The U.S. Environmental Protection
Agency (EPA) has recently proposed that train locomotives and ships powered
by diesel should also be forced to substantially reduce their emission of nitro-

gen oxides. In one scheme for NOX removal from diesel exhaust, the gas is
temporarily stored on an adsorber present in the converter. Periodically,
diesel fuel is injected into the stored NOX, creating reducing conditions and
promoting the reaction described above for gasoline vehicles, namely, the
catalytic reduction of NOX to N2.
In addition to CO, hydrocarbon, NOX, and SO2 gases, diesel engine
exhaust also includes significant quantities of solid and liquid particles. The
liquid consists of unburned fuel and lubricating oil, plus some sulfuric acid
produced from sulfur in the fuel. The catalytic converters formerly used on
diesel engine vehicles were designed to oxidize the carbon-containing gases
and liquids but without oxidizing the SO2 further to sulfuric acid and sulfates.
Diesel fuel intended for new on-road vehicles in the United States has
recently had its maximum allowed sulfur level dropped from 500 ppm to
15 ppm; and the level has dropped to 50 ppm in the European Union. Low-
ering the sulfur level in diesel fuel will also reduce particle emissions to some
extent. Ironically, some of the soot carbon reacts with nitrogen dioxide in the
exhaust gas to oxidize it:
C(s) NO2 9: CO NO
However, a filter—sometimes known as a particle trap—is required to achieve
a suitable reduction in diesel exhaust particles. The traps can physically
remove up to 90% of small particle emissions, thus preventing them from
escaping into the air from the exhaust system of light-duty diesel vehicles. In
order to prevent a buildup of solids, which would restrict engine exhaust flow
or melt the trap, the system is designed so that the soot will ignite and burn
away once a temperature of at least 500°C is attained. Alternatively, tiny
amounts of a metal catalyst compound containing iron or copper are added to
lower the temperature at which ignition will occur and assure more continu-
ous regeneration of the filter. Eventually the filter requires cleaning since
nonorganic components of the exhaust build up over time.
Scientists and engineers are currently developing a new type of internal
combustion engine that combines the best aspects of gasoline and diesel tech-
nologies. In the homogeneous charge compression ignition (HCCI) engine, the
fuel and the air are well mixed before ignition, thereby preventing the forma-
tion of soot particles that occurs in diesel engines. High compression of the
air/fuel mix allows combustion to begin at many locations in the cylinder and
produces a much greater efficiency than in gasoline engines, thereby reducing
CO2 emissions. Since the engine is run with an even larger excess of air than
in a diesel, and no “hot spots” occur where combustion temperatures are high,
much smaller amounts of NOX than normal are produced.
Eventually, vehicles using internal combustion may well be replaced by
emission-free ones powered by fuel cells. Such a prospect is discussed in
Chapter 8 when we consider various alternative fuels.
Control of Nitric Oxide Emissions from Power Plants

In the United States, approximately equal amounts of NOX are emitted cur-
rently from vehicles and from electric power plants; taken together they con-
stitute the majority of the anthropogenic sources of these gases. In this
section, we investigate the processes that are in use to decrease the quantity
of nitrogen oxides emitted into the air by power plants.
• To reduce their NOX production, some power plants use special burners
designed to lower the temperature of the flame. Alternatively, the recircula-
tion of a small fraction of the exhaust gases through the combustion zone has
the same effect, as previously discussed for vehicles.
• Nitric oxide formation in power plants can also be greatly reduced by hav-
ing the combustion of the fuel occur in stages. In the first, high-temperature
stage, no excess oxygen is allowed to be present, thus limiting its ability to
react with N2. In the second stage, additional oxygen is supplied to complete
the fuel’s combustion but under lower temperature conditions, so that again
little NO is produced.
• Other power plants, especially those in Japan and Europe, have been fit-
ted with large-scale versions of catalytic converters that change NOX back to
N2 before the release of stack gases into air. The reduction of NOX to N2 in
these selective catalytic reduction systems is accomplished to 80–95% com-
pletion by adding ammonia, NH3, to the cooled gas stream. This highly
reduced compound of nitrogen combines with the partially oxidized com-
pound NO to produce N2 gas in the presence of oxygen:
4 NH3 4 NO O2 9: 4 N2 6 H2O
However, tight control is needed to regulate the addition of ammonia in

order to prevent its inadvertent oxidation to NOX. The same reaction can
be accomplished without expensive catalysts, though with much less
efficient nitric oxide removal, by using the uncooled gases at about 900°C.
The catalytic process occurs at 250°C to 500°C, depending upon the cata-
lyst used.
• The wet scrubbing of exhaust gases by an aqueous solution can also be
used to prevent NOX from being emitted into outside air. Since NO itself is
rather insoluble in water and in typical aqueous solutions, half or more of the
NOX must be in the form of the much more soluble NO2 for such techniques
to be effective. Solutions of sodium hydroxide, NaOH, react with equimolar
amounts of NO and NO2 to produce an aqueous solution of sodium nitrite,
NaNO2:
NO NO2 2 NaOH 9: 2 NaNO2 H2O

P R O B L E M 3-5
Deduce the balanced reaction in which ammonia reacts with nitrogen diox-
ide to produce molecular nitrogen and water. Using the balanced equation,
calculate the mass of ammonia that is required to react with 1000 L of air at
27°C, 1 atm pressure, containing 10 ppm of NO2. [Hint: Recall from introduc-
tory chemistry that PV nRT and that a balanced equation indicates the number
of moles of the substances that react with each other.]
P R O B L E M 3-6
In a related technology, reduced nitrogen in the form of the compound urea,
CO(NH2)2, is injected directly into the combustion flame to combine there,
rather than later in the presence of a catalyst, with NO to produce N2.
Deduce the balanced equation that converts urea and nitric oxide into N2,
CO2, and water.
Future Reductions in Smog-Producing Emissions

Although direct emissions of five (CO, VOCs, SO2, particulate matter, and
lead) of the six major air pollutants in the United States fell significantly
between 1970 and 2000, emissions of NOX grew by 20%, with half that
increase occurring during the 1990s. Since energy consumption grew 45%
and vehicle distance traveled grew 143% in that period, restrictions on nitro-
gen oxide emissions have had some success in controlling some of the growth
in this pollutant, but not enough to prevent an overall increase. NO emis-
sions from electric power plants, their other major source, have recently been
falling somewhat.
As a consequence of the increase in overall NO emissions, ground-
level ozone concentrations increased in the southern (especially around
Houston) and northcentral regions of the United States in the 1990s. The
latter effect can be seen in Figure 3-5a, where high ozone levels center
around New York–Boston and a few midwestern sites, and somewhat lower
levels cover most of the East Coast and the Midwest, extending into southern
Ontario. High ozone levels have been a problem in southern California for
many decades.
To help reduce the incidence of summertime smog in southcentral
Canada and the northeastern United States, the two nations have signed an
annex to their Air Quality Accord. The United States committed to reduce
NOX emissions originating from northern and northeastern states by 35%
by 2007 and also to reduce VOC emissions during summer months, when
most smog forms in this region. Canada agreed to reduce its NOX emissions
from power plants in southern Ontario by 50% by the same date. The drastic
lowering of the allowed sulfur levels in gasoline should assist in the reduction
of NOX from vehicles. Emission standards for SUVs, trucks, and buses are
also being tightened to bring them more in line with those for regular
automobiles.
The Gothenburg Protocol, which controls the release of many pollutants
in Europe, is expected to reduce NOX emissions there by more than 40% by
2010, compared to 1990 levels; a 30% reduction had already been achieved
by 2000. Great Britain—which saw its emissions decline by the late 1990s by
almost 40% compared to their peak in the late 1980s—will have to reduce its
emissions by another third from 1998 levels by 2010 in order to meet these
regulations. European VOC emissions are due to drop by 40% according to
the protocol.
The trends in anthropogenic NOX emissions into the air over North
America, Europe (including Russia and the Near and Middle East), and Asia
(east, southeast, and south) in the past few decades are shown in Figure 3-9.
As discussed above, European contributions have fallen, North American
emissions displayed growth in some periods but declined in others, remaining
about constant overall, and those from Asia have risen from relatively small
to largest of all. Consistent with these trends, a comparison of measurements
from space of tropospheric NO2 levels in 2002 compared to those in 1996
show significant reductions over much of Europe, declines over the Ohio Valley
(where emissions had dropped 40% by 2006, compared to 1999 levels), but
increases in the northeastern states and in southern Ontario, and a large
increase over industrial areas of China.
40,000
Anthropogenic NOX emissions (kt/year)
35,000
30,000
North America
25,000
Europe
20,000
15,000
Asia
FIGURE 3-9 10,000

Anthropogenic NOX
atmospheric emissions. 5,000
[Source: H. Akimoto, “Global
1970 1975 1980 1985 1990 1995 2000
Air Quality and Pollution,” Year
Science 302 (2003): 1716.]
Green Chemistry: The Replacement of Organic

Solvents with Supercritical and Liquid Carbon
Dioxide; Development of Surfactants for
This Compound
In addition to their role in paints, organic solvents are used in many different
products and processes in both commercial and household applications. It is
estimated that over 15 billion kilograms of organic solvents are used world-
wide each year in such areas as the electronics, cleaning, automotive, chemi-
cal, mining, food, and paper industries. These liquids include not only
hydrocarbon solvents but also halogenated solvents. Both of these types of
solvents contribute not only to air pollution as VOCs but also to water pollu-
tion (Chapter 14). Some halogenated solvents contribute to the depletion of
the ozone layer, as seen in Chapter 2. Discovering solvents with less environ-
mental impact and even designing processes that use no solvents at all are the
subjects of many green chemistry initiatives.
Carbon dioxide, CO2, is one solvent that is receiving considerable atten-
tion as a replacement for traditional organic solvents. Although carbon diox-
ide is a gas at room temperature and pressure, it can be liquefied easily by the
application of pressure. In addition to liquid carbon dioxide, there is consider-
able interest in supercritical carbon dioxide (a discussion of supercritical fluids
can be found in Chapter 16) as a solvent in the electronics industry, as discussed
in the green chemistry section of Chapter 6. The decaffeination of coffee and
tea with carbon dioxide is a well-known application of this solvent.
Liquid carbon dioxide is attractive as a solvent due to its low viscosity
and polarity and its wetting ability. Because of its low polarity, carbon dioxide
is able to dissolve many small organic molecules. However, larger molecules
including oils, polymers, waxes, greases, and proteins are generally insoluble
in it. To increase the solubility of compounds in water, surfactants such as
soaps and detergents have been developed which allow this very polar solvent
to dissolve less polar materials such as oils and grease. In an analogous fash-
ion, surfactants for carbon dioxide have been developed that increase the
range of materials that will dissolve in it.
Joseph DeSimone, of the University of North Carolina and North Carolina
State University, earned a Presidential Green Chemistry Challenge Award in
1997 for his preparation and development of polymeric surfactants for carbon
dioxide. DeSimone is currently the director of the National Science Founda-
tion Science and Technology Center for Environmentally Responsible Sol-
vents and Processes. This center focuses on discovering ways to replace
conventional organic solvents and water with carbon dioxide in a multitude
of processes. An example of a surfactant developed by DeSimone is the block
copolymer shown in Figure 3-10a. This molecule has nonpolar regions, which
are CO2-philic, and polar regions, which are CO2-phobic. When dissolved in
(a) carbon dioxide, the CO2-philic regions orient

999 CH2 9 CH 999 CH2 9 CH 999 themselves to interact with the surrounding
carbon dioxide solvent, while the CO2-phobic
n C"O m regions aggregate with one another. The over-
all result is the formation of a structure know as
O CH2(CF2)6CF3
a micelle (Figure 3-10b). Polar substances that
normally do not dissolve in carbon dioxide
CO2 -phobic CO2 -philic
will dissolve in the center polar region of the
chain segment chain segment
micelle.
DeSimone was one of the founders of a
(b)
dry-cleaning chain that uses liquid carbon
Carbon dioxide solvent dioxide, along with surfactants that he devel-
oped, to clean clothes. The spent liquid car-
bon dioxide is drained from the clothes after
the wash cycle (in much the same way as the
wash water in our washing machines at home
is drained off after the wash cycle), and the
CO2-phobic carbon dioxide is allowed to evaporate by sim-
chain segments
ply reducing the pressure. The carbon dioxide
vapors are then captured, liquefied by increas-
CO2-philic ing the pressure, and reused for another wash.
chain segments Carbon dioxide is plentiful and inexpensive,
since it can be recovered as a by-product from
natural gas wells or ammonia production. Cap-
FIGURE 3-10 (a) A copolymer surfactant for carbon dioxide.
(b) A micelle in liquid carbon dioxide. [Source: M. C. Cann and
ture of carbon dioxide from these processes puts
M. E. Connelly, Real-World Cases in Green Chemistry (Washington, DC: to good use this compound which would nor-
American Chemical Society, 2000).] mally be released to the atmosphere and con-
tribute to global warming (see Chapter 6). By
contrast, most dry cleaners in North America
presently use perchloroethylene, Cl2CRCCl2, known as PERC, as the solvent.
PERC is a VOC, since it has a high vapor pressure and readily escapes into
the troposphere if not carefully controlled. PERC is also a groundwater con-
taminant (see Chapter 14) and is a suspected human carcinogen.
Green Chemistry: Using Ionic Liquids to Replace

Organic Solvents; Cellulose, a Naturally
Occurring Polymer Replacement for
Petroleum-Derived Polymers
Cellulose (Figure 3-11) is a polymer of glucose that makes up about 40% of
all organic matter on Earth. About 700 billion tonnes of cellulose exist on
Earth, with another 40 billion tonnes produced each year as the major com-
ponent of biomass by plants from atmospheric carbon dioxide and water via
HO
OH
H O
H
OH H
H
H OH
HO
O
H O
H
OH H
H
HO H OH
O
H O
H
OH H
H
H OH
n
HO
O
H O
H
OH H
HO H FIGURE 3-11 Structure of
H OH cellulose.
photosynthesis. This removal of carbon dioxide from the atmosphere helps

to mitigate some of the global warming caused by anthropogenic emissions
of this gas.
Many polymers produced from crude oil are ubiquitous in our everyday
lives, including polyethylene terephthalate (PET), which is found in bever-
age bottles and polyester clothing; polyethylene, which is employed in mak-
ing plastic bags and milk jugs; polyvinyl chloride, which is found as plastic
pipes and shower curtains; and polystyrene, which we discussed in the green
chemistry section in Chapter 2. Hundreds of million of kilograms of these
petrochemical-based polymers are produced each year, requiring as raw mate-
rial approximately 700 million barrels of crude oil. As the price of conven-
tional crude oil increases and the supply declines, a major focus of green
chemistry is the production of organic chemicals, including polymers, from
biomass (see the green chemistry section in Chapter 7). An even more
intriguing opportunity is to use naturally occurring polymers such as cellulose
to replace the polymers synthesized from crude oil.
The use of cellulose is severely limited by its insolubility in water and
in traditional organic solvents. The strong intra- and inter-chain hydrogen
bonding between the numerous hydroxyl

N N Cl
groups on the cellulose polymer are
likely the reason for this insolubility,
which results in very poor processability
for cellulose. Consequently, only about
N AlCl4 0.1 billion tonne of cellulose has been
used annually as a feedstock for further
processing.
In the previous green chemistry sec-
O tion, the replacement of traditional
O organic solvents with supercritical and
H3C(H2C)12 P liquid carbon dioxide was discussed. A
very interesting and relatively unknown
P (CH2)5CH3 group of compounds that are of growing
interest as replacements for traditional
H3C(H2C)5 (CH2)5CH3 organic solvents are called room-tempera-
ture ionic liquids, or just ionic liquids (ILs).
Most ionic compounds have characteris-
tically high melting points due to their
strong network of ionic bonding. For
F3C example, sodium chloride (table salt) has
CF2
a melting point of 801°C. In contrast, a
F2C few ionic compounds have melting points
N CF2 below or moderately above (100°C)
room temperature; such compounds are
O S O known as (room-temperature) ionic liq-
uids. ILs are generally composed of bulky
O ions that often have dispersed rather
than localized charges and large nonpolar
groups (Figure 3-12). As a consequence,
FIGURE 3-12 Ion pairs in
four typical ionic liquids.
their oppositely charged ions have only weak attractive interactions with one
another, which results in the low melting points of these compounds.
One very beneficial characteristic of ILs is their very low vapor pressure.
This is in contrast to most organic solvents, which, because of their signifi-
cant vapor pressures, are VOCs and contribute to tropospheric pollution.
Because ILs are ionic, they are nonvolatile and thus their potential to replace
VOCs is of significant interest. Ionic liquids may also be purified and recy-
cled, thereby adding to the green characteristics of these solvents. In addi-
tion, they are nonflammable, and many are stable up to 300°C, making them
attractive for reactions and processes that require high temperatures.
Another strong interest of the green chemistry community is the use of
microwave ovens to facilitate chemical processes and reactions. Conventional
heat sources—such as heating mantles, Bunsen burners, and oil baths—heat
materials from the outside in, transferring energy (in turn) from the heat
source to the bottom of the reaction vessel, to the solvent inside the vessel,
and finally to the dissolved reactants. In each step, heat energy is lost to the
surroundings as it is transferred. A microwave-absorbing reactant or solvent,
however, can be targeted by microwaves and therefore can be directly heated
by irradiation in a microwave oven or reactor. Thus with microwave heating,
the contents may be heated directly without heating the vessel. Most people
have experienced this phenomenon when heating a cup of water in a house-
hold microwave oven. The water heats quite quickly while the cup remains
relatively cool. Chemists have found that many reactions and processes can
be accelerated in a microwave oven, whose heating efficiency has the potential
to reduce energy requirements.
In order to effectively heat via a microwave source, a substance must be
polar and/or ionic. ILs heat up very quickly in a microwave since by nature
they are ionic. They can reach temperatures as high as 300°C in 15 seconds
of microwave heating.
Robin Rogers and his group at the University of Alabama won a Presi-
dential Green Chemistry Challenge Award in 2005 for their discovery that
certain ILs readily dissolve cellulose when heated in a microwave oven. The
process they developed involves the use of gentle, pulsed microwave heating
in a domestic microwave oven to expedite the dissolution of cellulose in ILs.
Their studies indicate that with the IL 1-butyl-3-methylimidazolium chlo-
ride, they can produce solutions with up to 25% (by mass) cellulose.
H3C
N N
CH3 Cl
There is evidence that the chloride ion in this compound disrupts the
internal hydrogen bonding in the cellulose, thereby leading to dissolution. The
addition of small amounts of water solvates the chloride ions, allowing the
hydrogen bonding of the cellulose to resume. The cellulose precipitates from
the solution and can then be deposited as films, membranes, and fibers.
By dispersing additives in the IL either before or after the dissolution of
cellulose, composite or encapsulated cellulose-based materials can be formed
when the polymer is regenerated. For example, laccase, an enzyme found in
fungi that degrades polyphenolic compounds, has been encapsulated in a
cellulose support without loss of its activity. The enzyme, when supported on
a cellulose film, can be immersed in an aqueous reaction environment and
easily removed at the end of the reaction by removing the film, which can
then be reused.
The Rogers group has also successfully suspended many other materials
in cellulose. These include dyes that can be used to detect metals, such as
mercury, and magnetite (Fe3O4) that produces a composite with uniform
magnetic properties. Using this method, cellulose can be combined with
other polymers to produce blends. When mixed with polypropylene, a com-
posite that has excellent tear properties is formed. The use of this material for
packaging offers significant promise. Encapsulation of medically active com-
pounds along with magnetic materials has the potential to produce microcap-
sules that can be directed to specific parts of the body. In addition, titanium
dioxide infusion into cellulose fibers can produce clothing and bedding with
antibacterial properties. The development of cellulose-based materials has
the potential to produce new materials with novel characteristics that require
less use of petroleum than conventional polymers.
Sulfur Dioxide and Hydrogen Sulfide Sources

and Abatement
On a global scale, most SO2 is produced by volcanoes and by the oxidation of
sulfur gases produced by the decomposition of plants. Because this natural
sulfur dioxide is mainly emitted high into the atmosphere or far from popu-
lated centers, the background concentration of the gas in clean air is quite
small, about 1 ppb. However, a sizable additional amount of sulfur dioxide is
emitted into ground-level air, particularly over land masses in the Northern
Hemisphere, due to industrial activities. The main anthropogenic source of
SO2 is the combustion of coal, a solid that, depending on the geographic area
from which it is mined, contains 1 to 6% sulfur. In most countries, including
the United States, the major use of coal is to generate electricity. Usually half
or more of the sulfur is trapped as inclusions in the mineral content of the
coal. If the coal is pulverized before combustion, this type of sulfur can be
mechanically removed, as discussed below. The rest of the sulfur, which
usually amounts to about 1% of the coal’s mass, is bonded in the complex
organic structure of the solid and cannot be removed without expensive
processing that breaks covalent bonds.
Sulfur occurs to the extent of a few percent in crude oil (with higher con-
centrations in tar sands and shale oil), but it is reduced to the level of a few
hundred ppm or less in products such as gasoline. Sulfur dioxide is emitted
into air directly as SO2 or indirectly as H2S by the petroleum industry when
oil is refined and natural gas is cleaned before delivery. Indeed, the predomi-
nant component in natural gas wells is sometimes H2S rather than CH4! The
substantial amounts of hydrogen sulfide obtained from its removal from oil
and natural gas are often converted to solid, elemental sulfur, an environmen-
tally benign substance, using the gas-phase process called the Claus reaction:
2 H2S SO2 9: 3 S 2 H2O

One-third of the molar amount of hydrogen sulfide extracted from the fossil
fuel is first combusted to sulfur dioxide to provide the other reactant for this
process. Huge amounts of elemental sulfur are produced by sulfur removal,
especially from natural gas. Notice the analogy between the Claus reaction
and the selective catalytic reduction process for nitric oxide control: They
both involve the reaction together of oxidized and reduced forms of an ele-
ment (N or S) to form the innocuous elemental form.
It is very important to remove hydrogen sulfide from gases before their
dispersal in air because it is a highly poisonous substance, more so than sulfur
dioxide. The concentration of H2S sometimes becomes elevated in the area
surrounding natural gas wells during flaring—the burning off of gas that can-
not be immediately captured. Flaring burns only about 60% of the hydrogen
sulfide content of the gas, so the remainder becomes dispersed into the sur-
rounding air. Hydrogen sulfide is also a common pollutant in the air emissions
from pulp and paper mills.
In addition to H2S, several other smelly gases containing sulfur in a
highly reduced state are emitted as air pollutants in petrochemical processes;
these include CH3SH, (CH3)2S, and CH3SSCH3. The term total reduced
sulfur is used to refer to the total concentration of sulfur from H2S and these
three compounds. (The word reduced is used here to denote not a decrease in
sulfur emissions but rather the oxidation state of the sulfur.)
Large point sources—individual sites that emit large amounts of a
pollutant—of SO2 are also associated with the nonferrous smelting (i.e., the
conversion of ores to free metals) industry. Many valuable and useful metals,
such as copper and nickel, occur in nature as ores containing the sulfide ion,
S2. In the first stage of their conversion to the free metals they were usually
“roasted” in air to remove the sulfur, which was converted to SO2 and was tra-
ditionally released into the air. For example,
2 NiS(s) 3 O2(g) 9: 2 NiO(s) 2 SO2(g)
Ores such as copper sulfide can be smelted in a process that uses pure oxygen
forced into the smelting chamber, and the very concentrated sulfur dioxide
that is obtained from the reaction can be readily extracted, liquefied, and sold
as a by-product. On the other hand, the SO2 concentration in the waste gases
from conventional roasting processes (such as that used for nickel) is high.
Consequently, it is feasible to pass the gas over an oxidation catalyst that con-
verts much of the SO2 to sulfur trioxide, to which water can be added to pro-
duce commercial concentrated sulfuric acid.
2 SO2(g) O2(g) 9: 2 SO3(g)

SO3(g) H2O(aq) 9: H2SO4(aq)
The latter reaction (which represents only initial reactants and end-product)
is in fact accomplished in two steps (not shown) in order to ensure that none
of the substances escape into the environment: First the trioxide is combined
with sulfuric acid, then water is added to the resulting solution.
The Oxidation of Sulfur Dioxide in Suspended

Water Droplets
Although some sulfur dioxide in air is oxidized by gas-phase reactions, most
of it is converted to sulfuric acid after it has dissolved in tiny suspended water
droplets present in clouds, mists, etc. The uncatalyzed oxidation of dissolved
SO2 by dissolved oxygen proceeds at a very slow rate unless a catalyst such as
Fe3 or the ions of other transition metals are also present in the droplets.
The most important oxidizing agents in the droplets, though present only in
tiny concentrations, are the dissolved atmospheric gases ozone and hydrogen
peroxide, H2O2. The concentration of these two pollutants is much greater in
air masses undergoing photochemical smog than in clean air.
In general, the concentration of a dissolved gas in the liquid phase can be
determined by considering the equilibrium between its two forms. Thus for
hydrogen peroxide, we have
H2O2(g) Δ H2O2(aq)
The useful form of the equilibrium constant for such processes is the Henry’s
law constant, KH, which is equal to the concentration of the dissolved species
divided by the partial pressure of the gas. For the above reaction, we have
[H2O2]
KH
PH2O2
If the concentration is expressed as a molarity, and the unit of pressure is
atmospheres, from experimental data
KH 7.4 104 M atm1
Using this information, we can determine the molarity of H2O2 in

a raindrop for typical clean-air conditions of 0.1 ppb, i.e., equivalent to
0.1 109 atm.
[H2O2] KH PH2O2
7.4 104 M atm1 0.1 109 atm
7.4 106 M
Although a concentration of 7.4 ␮M seems tiny by comparison to values

routinely encountered in laboratories, it is sufficient to oxidize dissolved SO2
at an appreciable rate. The hydrogen peroxide concentration in smoggy
air is an order of magnitude or more larger than in clean air, so its concen-
tration in water droplets rises accordingly, as does the rate of oxidation of
sulfur dioxide. (Recently it has been discovered that, for unknown reasons,
hydrogen peroxide levels in suspended aerosol droplets in the air at several
California locations are orders of magnitude larger even than predicted by
Henry’s law.)
The calculation of the solubility of SO2 in raindrops is more complicated,
since in the aqueous phase it exists as sulfurous acid, H2SO3:
SO2(g) H2O(aq) Δ H2SO3(aq)
The Henry’s law expression does not include the concentration of the sol-
vent, water:
KH [H2SO3]/PSO2
Since KH 1.0 M atm1 for SO2, and since its concentration in a typical
sample of air is about 0.1 ppm, i.e., equivalent to 0.1 106 atm, the equilib-
rium concentration of sulfurous acid is
[H2SO3] KH PSO2
1.0 M atm1 0.1 106 atm

1.0 107 M
This value of about 107 M for the equilibrium concentration of H2SO3 is
deceptive since it by no means represents all
the sulfur dioxide that dissolves in a water
droplet (see Figure 3-13). Sulfurous acid is a Water Droplet
weak acid whose ionization to the bisulfite
ion, HSO3, must also be considered in cal- O3
culating the solubility of sulfur dioxide:
H2SO3 Δ H HSO3
HSO4–
The acid dissociation (or ionization) con-
HSO3– + H+
stant Ka for H2SO3 is equal to 1.7 102, SO2 H2SO3
where Ka is related to concentrations by

the expression
[H+] [HSO3-]
Ka
[H2SO3]
H2O2
The concentrations in such expressions are
equilibrium values. Since the equilibrium
molarity of H2SO3 is determined in the FIGURE 3-13 Dissolution of atmospheric gases SO2, O3, and H2O2
raindrop by its interchange with SO2 in into a water droplet and their subsequent reactions.
air, we can substitute that known value into the Ka expression:

[H + ] [HSO3-]
Ka
1.0 * 10-7
Rearranging the equation to solve for the ion concentrations, which from
stoichiometry are equal in value, we obtain
[HSO3]2 1.7 102 M 1.0 107 M
and hence
[HSO3] 4 105 M
Thus the equilibrium ratio of bisulfite ion to sulfurous acid in water is about
400 : 1. Consequently, the total dissolved sulfur dioxide is about 4 105 M,
rather than just the 1 107 M that represents the contribution from the un-
ionized acid.
Since the concentration of hydrogen ion produced by the reaction is also
4 105 M, the pH of such raindrops is 4.4. Rain does not become much
more acidic than this if no strong acids are dissolved in the droplets.
P R O B L E M 3-7
Bisulfite ion can act as a weak acid and ionize further:
HSO3 Δ H SO32
Given that Ka for HSO3 is 1.2 107, calculate the concentration of SO32
that is present in the raindrops of pH 4.4 discussed above. [Hint: The concen-
trations of bisulfite and hydrogen ion will be very close to their previously established
values.]
P R O B L E M 3-8
Calculate the pH of rainwater in equilibrium with SO2 in a polluted air mass for
which the sulfur dioxide concentration is 1.0 ppm. [Hint: Recall the relationship
between partial pressure and ppm concentration discussed earlier in the chapter.]
P R O B L E M 3-9
Calculate the concentration of SO2 that must be reached in polluted air if the
dissolved gas is to produce a pH of 4.0 in raindrops without any oxidation of
the sulfur.
P R O B L E M 3-10
CO2 dissolves in water to produce H2CO3 in the same way that SO2 produces
H2SO3. (a) Confirm by calculation that the pH of CO2-saturated water at
25°C is 5.6, given that the CO2 concentration in air is 365 ppm. For carbon
dioxide, the Henry’s law constant KH 3.4 102 M atm1 at 25°C. The Ka
for carbonic acid, H2CO3, is 4.5 107. (b) Recalculate the pH for a carbon
dioxide concentration of 560 ppm, i.e., double that of the preindustrial age.
Clean Coal: Reducing Sulfur Dioxide Emissions

from Power Plants
When the sulfur dioxide present in exhaust gases is dilute, as in the case of
power-plant emissions, its extraction by oxidation is not feasible. Instead, the
SO2 gas is removed by an acid–base reaction between it and calcium carbonate
(limestone), CaCO3, or calcium oxide (lime), CaO, in the form of wet, crushed
solid. The emitted gases are either passed through a slurry of the wet solid or are
bombarded by jets of the slurry. In some applications, fine grains of calcium
oxide, rather than a slurry of calcium carbonate, are used to trap the sulfur diox-
ide from the emission gases. Up to 90% of the gas can be removed by such
scrubber processes, more formally known as flue-gas desulfurization. In some
operations, notably in Japan and Germany, the product is fully oxidized by reac-
tion with air, and the resulting calcium sulfate, CaSO4, is dewatered and sold
as gypsum. Usually the product, a mixture of calcium sulfite, CaSO3, and cal-
cium sulfate, is a slurry—or a dry solid if granular calcium oxide was used—and
is buried in a landfill. The reactions with calcium carbonate are
CaCO3 SO2 9: CaSO3 CO2
2 CaSO3 O2 9: 2 CaSO4
Alternatively, the sulfur dioxide can be captured by use of slurries of sodium
sulfite or magnesium oxide or amine salts, and these reactant compounds
and concentrated SO2 gas are later regenerated by thermally decomposing
the product.
Recently, clean coal technologies have been developed to use coal in
ways that are cleaner and often more energy efficient than those employed
in the past. In the various technologies, the cleaning can occur precombus-
tion, during combustion, postcombustion, or by conversion of the coal to
another fuel.
In precombustion cleaning, the coal has the sulfur associated with its
mineral content—usually pyritic sulfur, FeS2—removed so it cannot subse-
quently produce sulfur dioxide. The coal first is ground to a very small parti-
cle size, effectively into separate mineral particles and carbon particles. Since
they have different densities, the two types of particles can be separated by
mixing the pulverized solid in a liquid of intermediate density and allowing
the fuel portion to rise to the top, where it can be skimmed off. As an alter-
native to such physical cleaning, biological or chemical methods can be
employed. For example, bacteria cultured to eat the organic sulfur in coal can
be utilized. Chemically, the sulfur can be leached from coal with a hot sodium
or potassium caustic solution.
In combustion cleaning, the combustion conditions can be modified to

reduce the formation of pollutants, and/or pollutant-absorbing substances
can be injected into the fuel to capture pollutants as they form. In fluidized-bed
combustion, pulverized coal and limestone are mixed and then suspended on
jets of air (fluidized) in the combustion chamber. Virtually all the sulfur diox-
ide is thereby captured in solid form as calcium sulfite and sulfate before the
gas can escape. This procedure allows for much-reduced combustion temper-
atures and therefore also greatly reduces the amount of nitrogen oxides that
are formed and released.
Some of the advanced techniques used in postcombustion cleaning—such
as the use of granular calcium oxide or sodium sulfite solutions—have already
been described. In the SNOX process developed in Europe, cooled flue gases are
mixed with ammonia gas to remove the nitric oxide by its catalytic reduction
to molecular nitrogen (by the reaction discussed previously). The resulting gas
is reheated and the sulfur dioxide oxidized catalytically to sulfur trioxide, which
is then hydrated by water to sulfuric acid, condensed, and removed.
In the conversion of coal to other fuels, it is first gasified by reaction with
steam, as will be described in Chapter 8. The gas mixture is cleaned of pollu-
tants, and the purified gas is then burned in a gas turbine that generates elec-
tricity. The waste heat of the combustion gases is used to produce steam for a
conventional turbine and thus to generate more electricity. Alternatively, the
gasified coal can be converted into liquid fuels suitable for vehicular use.
Sulfur dioxide emissions from power plants can also be minimized by
burning oil, natural gas, or low-sulfur coal as the fuel, though these fuels usu-
ally are more expensive than high-sulfur coal.
P R O B L E M 3-11
What mass of calcium carbonate is required to react with the sulfur dioxide
that is produced by burning one tonne (1000 kg) of coal that contains 5.0%
sulfur by mass?
P R O B L E M 3-12
Write the balanced reaction whereby sodium hydroxide can be used to scrub
sulfur dioxide from exhaust gases by a reaction that produces water and
sodium sulfite, Na2SO3. What substance would you have to react with this
solution to produce calcium sulfite and regenerate the sodium hydroxide?
Write the balanced equation for the latter process, and deduce the net reac-
tion for the cycle.
The alternative to sulfur dioxide control—to simply allow the pollutant

gas to be emitted into the air—can cause devastation by SO2 to the plant life
in the surrounding area unless extremely high smokestacks are used. The
tallest such stacks in the world are located at Sudbury, Ontario, and reach
400 meters. However, using tall stacks simply solves a local SO2 problem at
the expense of creating a problem downwind. For example, emissions from
mainland North America can sometimes be detected in Greenland.
Because of federal regulations, the amount of sulfur dioxide emitted into
the air in North America has fallen substantially—by about 38% from the
peak levels (in 1973) by 1998 in the United States and by 45% in Canada by
2000. The 1991 Air Quality Accord between the United States and Canada
required both countries to substantially reduce their sulfur dioxide emissions
beyond those of previous laws and agreements. Such emissions in the United
States are restricted in accordance with the Clean Air Act, especially the
1990 amendments to it. The average concentration of sulfur dioxide in air in
the United States fell by 43%, from 13.2 ppb to 7.5 ppb, from 1975 to 1991.
Whereas Phase I (1995 deadline) of the Clean Air Act imposed controls on
only the largest coal-fired plants, Phase II, which began in 2000, imposes
more stringent requirements and applies to almost all plants. There is an SO2
tonnage limit for each power plant that emits this gas, based upon the power
it produces, and a cap on overall national emissions as well. By 2010, the SO2
emissions from these power plants should have been reduced by 50% com-
pared to 1980 levels.
The reductions in sulfur dioxide emissions by power plants in the U.S.
Midwest have been achieved at lower-than-expected cost, due in part to the
availability of cheap, low-sulfur coal (1% S, versus more than 3% S in the
high-sulfur coal used previously) and inexpensive scrubbers, and in part to
the implementation of a system of tradable emission permits. This permit sys-
tem, in operation since the early 1980s, allows industries to buy emission
allowances if they need to exceed their allowed levels or to sell excess
allowances on the open market (through the Chicago Board of Trade) if they
do not need their whole allowance. A similar program has been started for
nitrogen oxide emissions.
The European Union issued a directive in 1988 specifying reductions
from large power plants of 50–70% of SO2 emissions from 1980 levels by
2003. The decline in SO2 emissions in Great Britain from 1970 to 1998
amounted to 75%. This cutback was achieved mainly by switching from coal
to natural gas in power stations and by the use of low-sulfur coal and the
scrubbing of emissions in facilities where coal is still burned. According to
the 1999 Gothenburg Protocol, Europe’s sulfur dioxide emissions are to be cut
beyond 1990 levels by another 63% by 2020.
Global SO2 emissions are predicted to keep rising until about 2020, due
mainly to increased releases from Asia. China has become the world leader in
emitting sulfur dioxide. Because of its rapid economic expansion, the growth
in the burning of coal—which supplies about two-thirds of China’s energy—
has recently been about 20% per year. As a consequence, its SO2 emissions
have risen rapidly—its 2005 emissions were 27% higher than those in 2000.
Because it has closed many small coal-fired power plants and either cleans the
coal before combustion or scrubs emission gases, China’s sulfur dioxide emis-
sions are predicted to level off by about 2010. However, the quantity of nitric
acid (from NOX emissions) in its acid rain is predicted to increase due to the
rapid rise in domestic vehicle ownership.
Japan initiated tight controls on SO2 emissions in the 1970s, and by 1980
its power plants had almost eliminated such emissions by the widespread
installation of scrubbers. The high rate of SO2 emissions from the former
Soviet bloc has declined in recent decades, due more to economic problems
than to intentional controls, though in places emissions continue to make
acidification a problem.
Particulates in Air Pollution

The black smoke released into the air by a diesel truck is often the most
obvious form of pollution that we routinely encounter. The smoke is
composed largely of particulate matter. Particulates are tiny solid or liquid
particles—other than those of pure water—that are temporarily suspended
in air and that are usually individually invisible to the naked eye. Collec-
tively, however, such particles often form a haze that restricts visibility.
Indeed, on many summer days the sky over North American and European
cities is milky white rather than blue. More importantly, breathing air that
contains particulates is known to be hazardous to human health. In the
material that follows, we investigate the wide range of sizes of the suspended
particles and their origins.
The particles that are suspended in a given mass of air are neither all of
the same size or shape nor do they all have the same chemical composition.
The smallest suspended particles are about 0.002 ␮m (i.e., 2 nm) in their
dimensions; by contrast, the length of typical gaseous molecules is 0.0001 to
0.001 ␮m (0.1 to 1 nm). The upper limit for suspended particles corresponds
to dimensions of about 100 ␮m (i.e., 0.1 mm). When atmospheric water
droplets coalesce to form particles bigger than this, they are raindrops and fall
out of the air so quickly they are not considered to be “suspended.” The
ranges of particle sizes for common types of suspended particulates is illus-
trated in Figure 3-14.
Although few of the particles suspended in air are exactly spherical in
shape, it is convenient and conventional to speak of all particles as if they
were so. Indeed, the diameter of particulates is their most important property.
Qualitatively, individual particles are classified as coarse or as fine depending
upon whether their diameters are greater or less than 2.5 ␮m, respectively.
(About 100 million particles of diameter 2.5 ␮m would be required to cover
the surface of a small coin.)
There are many common names for atmospheric particles: dust and soot
refer to solids, whereas mist and fog refer to liquids, the latter denoting a high
Coarse particles Fine particles
Rain Mist/Fog/Clouds Smog
Coal dust Tobacco

smoke
Atmospheric dust
Foundry dust
Agriculture Oil
sprays smoke
Pollen
Bacteria Viruses FIGURE 3-14 Sizes of
common airborne fine and
100,000 10,000 1,000 100 10 1 10–1 10–2 10–3 10–4 coarse particulates. [Source:
1,000,000 Adapted from J. G. Henry and
(1 mm) (1 nm)
(1 m) G. W. Heinke, Environmental
Science and Engineering (Upper
Particle diameter in micrometers ( μm) Saddle River, NJ: Prentice Hall,
1989).]
concentration of water droplets. An aerosol is a collection of particulates,

whether solid particles or liquid droplets, dispersed in air. A true aerosol (as
opposed to, say, the fairly large droplets from a hairspray dispenser) has very
small particles: Their diameters are less than 100 ␮m.
Intuitively, one might think that all particles should settle out under the
influence of gravity and be deposited onto the Earth’s surface rapidly, but this
is not true for the smaller ones. According to Stokes’ law, the rate, in distance
per second, at which particles settle increases with the square of their diameter.
In other words, a particle half the diameter of another falls four times more
slowly. The small ones fall so slowly they are suspended almost indefinitely in
air (unless they stick to some object they encounter). As we shall see later,
the very small ones aggregate to form larger ones, usually still in the fine size
category. Fine particulates usually remain airborne for days or weeks, whereas
coarse particulates settle out fairly rapidly. In addition to this sedimentation
process, particles also are commonly removed naturally from air by their
incorporation into falling raindrops.
Sources of Coarse Particles

The primary-versus-secondary distinction made between atmospheric gaseous
pollutants is also applied to suspended particles. Most coarse particles are pri-
mary, although they often begin their existence as even coarser matter, since
they originate chiefly from the disintegration of larger pieces of matter. Miner-
als constitute one important type of the coarse particulates in air. Because many
of the large particles in atmospheric dust, particularly in rural areas, originate as
soil or rock, their elemental composition is similar to that of the Earth’s crust,
namely high concentrations of Al, Ca, Si, and O in the form of aluminum sili-
cates (see Chapter 16), some of which also contain the calcium ion.
Wind storms in deserts sweep large amounts of fine sand into the air. Dust
storms in Asia, whose effects reach as far away as North America, are increas-
ing due to the continuing transformation of fertile land into desert as a con-
sequence of global warming, deforestation, and overgrazing. The wind
generates coarse particles by the mechanical disintegration of leaf litter.
Pollen released from plants also consists of coarse, primary particles. Wildfires
and volcanic eruptions generate both fine and coarse particulate matter. Near
and above oceans, the concentration of solid NaCl is very high, since sea
spray leaves sodium chloride particles airborne when the water evaporates.
Indeed, sea salt aerosols are by far the largest mass of primary particles in air,
followed by soil dusts and debris from natural fires.
Although most coarse particulates originate with natural sources, human
activities such as stone crushing in quarries and land cultivation result in parti-
cles of rock and topsoil being picked up by the wind. Coarse particles in many
areas are basic, reflecting the calcium carbonate and other such salts in soils.
Sources of Fine Particles

Primary fine particles of anthropogenic origin include ones generated by the
wearing of tires and vehicle brakes as well as the dust from metal smelting.
The incomplete combustion of carbon-based fuels such as coal, oil, gasoline,
and diesel fuel produces many fine soot particles, which are mainly crystallites
(miniature crystals) of carbon. Consequently, one of the main sources of
carbon-based primary atmospheric particulates, both fine and coarse, is the
exhaust from vehicles, especially those having diesel engines. About half the
organic content from heavy-duty diesel vehicles is elemental carbon; one can
easily observe this soot as the black smoke that emanates from such equip-
ment. Most carbon-containing emissions from gasoline-powered engines are
composed of organic compounds rather than elemental carbon.
Whereas coarse particles result mainly from the breakup of larger ones,
fine particles are formed mainly by chemical reactions between gases and by
the coagulation of even smaller species including molecules in the vapor state,
so they are mainly secondary particles. Although most of the atmospheric
mass of fine particles arises from natural sources, that over urban areas often
has mainly an anthropogenic origin.
The average organic content of fine particles is generally greater than
that for coarse ones. In areas such as Los Angeles, up to half the organic com-
pounds in the particulate phase are formed from the reaction of VOCs and
nitrogen oxides in the photochemical smog reaction; these compounds corre-
spond to partially oxidized hydrocarbons that have incorporated oxygen to
form carboxylic acids, etc. and nitrogen to form nitro groups, etc. Aromatic
hydrocarbons with at least seven carbon atoms (e.g., toluene) that enter the
air of such cities from the evaporation of gasoline also form aerosols. Hydro-
carbons having fewer than seven carbons give oxidation products with sub-
stantial vapor pressures and therefore remain in the gas phase.
The other important fine particles suspended in the atmosphere consist
predominantly of inorganic compounds of sulfur and of nitrogen. Much of the
natural sulfur in air originates as dimethyl sulfide, (CH3)2S, emitted from the
oceans. A by-product of its oxidation in air is carbonyl sulfide, COS, a long-
lived trace atmospheric component that also results from the atmospheric
oxidation of carbon disulfide, CS2, and from direct emissions from oceans and
biomass. Some of the COS makes its way into the stratosphere, where it is
oxidized and produces the natural sulfate aerosol found at those altitudes.
Both dimethyl sulfide and hydrogen sulfide are oxidized in air mainly to sul-
fur dioxide, SO2. Sulfur dioxide gas also is emitted directly in large quantities
both by natural sources such as volcanoes and as pollution from power plants
and smelters. It becomes oxidized over a period of hours or days to sulfuric
acid and sulfates in air. Sulfuric acid, H2SO4, itself travels in air not as a gas
but as an aerosol of fine droplets, since it has such a great affinity for water
molecules. A huge volcanic eruption in Iceland in 1783 produced enough
sulfuric acid particles to blanket Europe in a “great dry fog” for the entire sum-
mer, killing many people. In Iceland itself, fluoride emitted from the volcano
was a worse problem since it proved fatal to crops, livestock, and people.
Another natural source of atmospheric particles has been discovered.
Alkyl iodine compounds such as CH2I2 are emitted by seaweed into the air
above coastal regions. Absorption of the ultraviolet component of light is suf-
ficient to detach iodine atoms from such gaseous molecules. In subsequent
reactions analogous to those of chlorine in the stratosphere, the iodine atoms
react with ozone to form iodine monoxide, IO, which in turn dimerizes to form
I2O2. The dimer and other iodine–oxygen compounds condense to form fine
particles.
P R O B L E M 3-13
By analogy with the reactions of atomic chlorine discussed in Chapter 2,
write balanced equations for the reaction of atomic iodine with ozone and for
the dimerization of IO.
Fine particles in many areas are acidic, due to their content of sulfuric
and nitric acids. The nitric acid is the end-product of the oxidation of nitrogen-
containing atmospheric gases such as NH3, NO, and NO2. Because HNO3
has a much higher vapor pressure than does H2SO4, there is less condensation
of nitric acid onto preexisting particles than occurs with H2SO4.
Both sulfuric and nitric acids in tropospheric air often eventually
encounter ammonia gas that is released as a result of biological decay processes
occurring at ground level. The acids undergo an acid–base reaction with the
ammonia, which transforms them into the soluble salts ammonium sulfate,
(NH4)2SO4, and ammonium nitrate, NH4NO3. Since sulfuric acid contains
two hydrogen ions, the neutralization reaction occurs in two stages, the first
producing ammonium bisulfate, NH4HSO4:
H2SO4(aq) NH3(g) 9: NH4HSO4(aq)
NH4HSO4(aq) NH3(g) 9: (NH4)2SO4(aq)
The ammonia that results from animal urine originates in the liquid as urea,
CO(NH2)2, which subsequently hydrolyzes:
CO(NH2)2 H2O 9: 2 NH3 CO2
The neutralization of acidity by ammonia gas released into the air from live-
stock and from the use of fertilizers, and by carbonate ion suspended in air from
the dust raised by farming activities, is the main reason why precipitation over
the central United States is not particularly acidic, and similarly for regions of
China. However, some acidification results from the ionization of the ammo-
nium ion, NH4, a weak acid, that is produced by ammonia neutralization:
NH4 Δ NH3 H
Although the nitrate and sulfate salts initially are formed from acids in
aqueous particles, evaporation of the water can result in the production of
solid particles. The predominant ions in fine particles are the anions sulfate,
SO42; bisulfate, HSO4; and nitrate, NO3; and the cations ammonium,
NH4; and hydrogen ion, H. Aerosols dominated by oxidized sulfur com-
pounds are called sulfate aerosols.
(NH4)2SO4 NH3
NH4
NH3 NH4NO3 NH4HSO4
NO3 2
SO4
HNO3 NH3
H
HSO4 H2SO4
sulfate
aerosol
particle
On the west coast of North America, nitrate rather than sulfate is the
predominant anion because more pollution results initially from nitrogen
oxides than from sulfur dioxide, since coal mined in the western United
States tends to be low in sulfur. In Great Britain, most of the fine particles in
the winter months originate as soot from car exhaust and pollution from
industry, whereas in the summer they arise from the oxidation of sulfur and
nitrogen oxides.
If there is substantial ammonia gas in the air, nitric acid will react with it
to form ammonium nitrate solid in the particulate phase. Recent simulations
of smog formation in southern California indicate that although reductions
in VOC concentrations without any change in NOX would reduce ozone for-
mation, the production of nitrate-based particulates would actually increase
because more nitrogen dioxide would then react to produce nitric acid and
then nitrate ion. The simultaneous control of ozone and particulates presents
regulators with a formidable challenge!
In summary, coarse particles are usually either soot or inorganic (soil-
like) in nature, whereas fine ones are mainly either soot, or sulfate or nitrate
aerosols. Fine particles are usually acidic due to the presence of unneutralized
acids, whereas coarse ones are usually basic because of their soil content.
Air Quality Indices and Size Characteristics

for Particulate Matter
As we shall see in subsequent sections, the effect of particles suspended in air
upon human health depends significantly upon the size of the particles
involved. In the material that follows, we investigate the pollution indices
used by governmental agencies to characterize the level of particulate air pol-
lution present in an air sample as well as the effect of particle size on visibil-
ity through air masses.
The PM Indices
When air quality is monitored, the most common measure of the concentra-
tion of suspended particles is the PM index, which is the amount of particulate
matter that is present in a given volume. Since the matter involved usually is
not homogeneous, no molar mass for it can be quoted and thus concentrations
are given in terms of the mass, rather than the number of moles, of particles.
The usual units are micrograms of particulate matter per cubic meter of air, i.e.,
␮g/m3. Because smaller mass particles have a greater detrimental effect on
human health than do larger ones, as we shall see later in this chapter, usually
only those having a specified diameter or smaller are collected and reported.
This cut-off diameter, in ␮m, is listed as the subscript to PM.
In recent years, government agencies in many countries, including the
United States and Canada, have monitored PM10, i.e., the total concentra-
tion of all particles having diameters less than 10 ␮m, which corresponds to
all of the fine-particle range plus the smallest members of the coarse range.
These are called inhalable particles since they can be breathed into the lungs.
A typical value for PM10 in an urban setting is 20–30 ␮g/m3. Increasingly,
regulators are using the PM2.5 index, i.e., one that includes all and only fine
particles, which are also called respirable particles. The respirable range
includes only particles that can penetrate deep into the lungs, where there are
no natural mechanisms such as the cilia that line the walls of bronchial tubes
to catch particles and move them up and out. Urban PM2.5 values are usually
in the 10–20 ␮g/m3 range in North America, though background concen-
trations are only 1–5 ␮g/m3. The new term ultrafine is applied to particles
with very small diameters, usually taken to be less than 0.1 ␮m. Most ultra-
fine particles are anthropogenic in origin. In the past, the total suspended
particulates, abbreviated TSP, which is the concentration of all particulates
suspended in air, was often reported instead of a PM index.
The 1987 U.S. Air Quality Standards called for a maximum 24-hour
PM10 level of 150 ␮g/m3 and a maximum annual average of 50 ␮g/m3. The
United Kingdom has instituted a 24-hour PM10 standard of 50 ␮g/m3 that
cannot legally be exceeded on more than four days each year. In 1997, the
U.S. EPA decided to regulate PM2.5 levels—to an average of no more than
15 ␮g/m3 annually and 65 ␮g/m3 daily. The EPA estimated that the new par-
ticulate standards could prevent 15,000 premature deaths, as well as 250,000
person-days of aggravated asthma, annually. Indeed, PM2.5 levels in the
United States in 2003 were the lowest since 1999 at least, when they were
first monitored by the EPA. Although 30 states met the new PM2.5 standard
in 2003, the other 20—mostly along the East Coast—did not. In 2006, the
EPA proposed to lower the daily PM2.5 level to 35 ␮g/m3, which would fur-
ther reduce death rates from particulate exposure by 22%. The corresponding
Canadian standard is 30 ␮g/m3, to be achieved by 2010. The European
Union has proposed that its member states reduce their PM2.5 levels by 20%
between 2010 and 2020, with a cap of 25 ␮g/m3.
P R O B L E M 3-14
What would be the correct PM symbol for an index that included only ultra-
fine particles? What would be the PM symbol for the TSP index? Numeri-
cally, would the value for the ultrafine component of a given air mass be larger
or smaller than its TSP?
As discussed in detail in Box 3-2, the distribution of particles is suspended

in air peaks in the micrometer region because smaller ones coagulate to form
particles of this size and further growth is slow, and because much larger ones
rapidly settle out. The large increase in surface area that occurs when a large
particle is split into smaller ones is explored in Problem 3-15.
BOX 3-2 Distribution of Particle Sizes in an Urban

Air Sample
ecause particles suspended in the atmos- bution is probably the sum of several symmetri-
B phere have different origins and composi-
tions, and were formed and interacted with
cal (bell-shaped) distributions having peaks at
different diameters. The particles of the distri-
each other over a period of time in haphazard bution with the smallest diameter (0.01 ␮m)
ways, there is a wide distribution of particle are formed by the condensation of vapors of
sizes present in any air mass. pollutants formed by chemical reactions, such
One way of looking at the distribution of as the sulfuric acid formed by the oxidation of
sizes is to plot the number of particles having a gaseous sulfur dioxide and the soot particles
given diameter against the diameter; this is formed by combustion. The coagulation of
done in the solid curve of Figure 1 for a typical such particles into larger ones (which can
urban air sample. Notice that logarithmic occur in minutes) and the deposition of gas
scales were used in plotting both axes, in order molecules onto them result in the distribution
that the details of the distribution for particles having its peak at about 0.1 ␮m. Particles of
of many sizes can be seen clearly. The peak in this size also are created when water in aqueous
the distribution occurs at about 0.01 ␮m and droplets containing dissolved solids evaporates.
has a shoulder at about 0.1 ␮m. The net distri- Growth beyond this size is slow because the
Number
Surface area
Mass
Log quantity
FIGURE 1 Distribution of
0.001 0.01 0.1 1 10 100
particles by size in a typical
Log particle diameter (␮m) urban environment. [Source:
G. Oberdorster and M. J. Utell,
Nano Ultrafine Fine Coarse Environmental Health Perspectives
110 (2002): A440.]
BOX 3-2 Distribution of Particle Sizes in an Urban

Air Sample (continued)
larger the particle, the slower it moves, and (or volume) of a particle is proportional to the
thus the less likely it is to encounter and coag- cube of its diameter d (since for a sphere volume
ulate with particles of comparable size. Growth is proportional to the cube of the radius), so the
by condensation of gases is also slow for larger height of the curve at any diameter of the distri-
particles since their surface-to-mass ratio is bution in the longer-dashed curve in Figure 1
smaller than for small particles. corresponds to the value for the number distri-
The particles associated with the tail of bution for this air mass times d3. Consequently,
the distribution, at almost 1 ␮m, are mainly soot in the mass distribution, the peak heights for
or consist of material produced by mechanical larger particles are emphasized more than are
disintegration of soil particles, etc. There are those for smaller ones, and the whole distribu-
few particles of mass larger than a few microns tion appears to shift to larger diameters. Two
in diameter because they quickly settle out of symmetrical distribution curves, one centered in
the air, although large particles that have set- the fine region at about 0.3 ␮m and the other in
tled on roadways often are resuspended tem- the coarse region at about 7 ␮m, appear to be
porarily by the action of vehicular traffic. superimposed to produce the final bimodal distri-
The plots of particle numbers can be mis- bution. Notice that the total mass of the coarse-
leading for some purposes because tiny particles particle range (i.e., the sum of the area under
of very small mass and surface area dominate the the longer-dashed curve for d 2.5 ␮m) in Fig-
samples and thus the distributions. One alterna- ure 1 is greater than that for the fine region; this
tive way to represent the data in a more mean- ratio is even larger for clean, rural air masses.
ingful way is to plot the total mass of all particles The function representing the distribu-
of a given size in an air sample against the diam- tion of surface area versus size is the shorter-
eter to see how mass is distributed among the dashed curve in Figure 1. The points on it are
different sizes. This type of plot is shown by the proportional to those for the number distribu-
longer-dashed curve in Figure 1. The distribution tion times d2, rather than d3, since surface area
function for mass is displaced to larger diameters is proportional to the square of the radius or
compared to that for particle numbers: The mass diameter of the particle.
P R O B L E M 3-15
Let k be a given measure of length; then suppose a cubic particle of dimension
3k 3k 3k is split up into 27 particles with size k k k. Calculate the rel-
ative increase in surface area when this occurs by comparing the surface area
(length times width) of the six faces of the larger cube to the sum of all those
of the smaller ones. From your answer, deduce whether the total surface area
of a given mass of atmospheric particles is larger or smaller when it occurs as a
large number of small particles rather than a small number of large ones.
Review Questions
1. In the “micrograms per cubic meter” concentra- 9. What species are included in the air pollution
tion scale, to what substances do micrograms and index called total reduced sulfur?
cubic meters refer?
10. Describe the various strategies used to produce
2. In general terms, what is meant by photochemical clean coal.
smog? What are the initial reactants in the process?
11. Deduce the balanced reaction corresponding to
Why is sunlight required?
the capture of sulfur dioxide gas by aqueous sodium
3. What is meant by a primary pollutant and by a sulfite and water to produce calcium bisulfite.
secondary pollutant? Give examples.
12. What is the difference between dry and wet
4. What is the chemical reaction by which thermal deposition?
NO is produced? From which two sources does most
13. Define the term aerosol, and differentiate between
urban NO arise? What is meant by the term NOX?
coarse and fine particulates. What are the usual origins
5. Describe the strategies by which reduction of of these two types of atmospheric particles?
urban ozone levels have been attempted. What
14. What are the usual chemical components of a
difficulties have been encountered in these efforts?
sulfate aerosol?
6. Describe the operation of the three-way
15. Write a balanced equation illustrating the
catalyst in transforming emissions released by an
reactions that occur between one molecule of
automobile engine. Does the catalyst operate
ammonia with (a) one molecule of nitric acid and
when the engine is cold? Why is it important for
with (b) one molecule of sulfuric acid.
converters that the level of sulfur in gasoline be
minimized? 16. What are the usual concentration units for sus-
pended particulates? What would the designation
7. Describe the reaction used in the selective cat-
PM40 mean? What do the terms respirable and ultra-
alytic reduction of nitrogen oxides.
fine mean?
8. What are the main anthropogenic sources of sul-
17. What is the two-step mechanism by which the
fur dioxide? Describe the strategies by which these
hydroxyl free radical is produced in clean air?
emissions can be reduced. What is the Claus reaction?

See the discussion of focus areas and the principles (b) Would these same environmental problems or
of green chemistry in the Introduction before worker hazards be eliminated by the use of PERC?
attempting these questions. (c) By the use of carbon dioxide?
1. PERC replaced gasoline and kerosene in the 2. The development of surfactants for carbon diox-
dry-cleaning process. ide by Joseph DeSimone won a Presidential Green
(a) Describe any environmental problems or Chemistry Challenge Award.
worker hazards that would be associated with these (a) Into which of the three focus areas for these
solvents. awards does this award best fit?
(b) List two of the twelve principles of green chem- in weak interactions between the oppositely
istry that are addressed by the green chemistry charged ions.
developed by DeSimone.
4. The discovery of the dissolution of cellulose
3. The ions in ionic liquids (ILs) have weak with ionic liquids and the formation of various cel-
ionic attractions for one another. This weak lulose composites by Robin Rogers won a Presiden-
interaction is due to one or more factors tial Green Chemistry Challenge Award.
including (a) Into which of the three focus areas for these
• the presence of bulky nonpolar groups that pre- awards does this award best fit?
vent the close interaction of the charged regions of (b) The use of an abundant and naturally occurring
the ions, and polymer, a microwave heat source, and ionic liquids
are three important green chemistry aspects of this
• delocalized and/or dispersed charges resulting in
study. For each of these aspects, list at least two of
low charge density.
the twelve principles of green chemistry that are
Inspect the ILs in Figure 3-12 and discuss the addressed in this study.
structural features of these compounds that result
Additional Problems
1. The rate constant for the oxidation of nitric of CO fixed at 20 ppm. Consult your introductory
oxide by ozone is 2 1014 molecule1 cm3 sec1, chemistry textbook to find the relationship between the
whereas that for the competing reaction in which it half-life of a substance and the rate constant for its
is oxidized by oxygen, that is, first-order decay.]
2 NO O2 9: 2 NO2 3. In the overall reaction that produces nitric

oxide from N2 and O2, the slow step in the mecha-
is 2 1038 molecule2 cm6 sec1. For typical con- nism is the reaction between atomic oxygen and
centrations encountered in morning smog episodes, molecular nitrogen to produce nitric oxide and
namely 40 ppb for ozone and 80 ppb for nitric atomic nitrogen.
oxide, deduce the rates of these two reactions and (a) Write out the chemical equation for the slow
decide which one is the dominant process. step and the rate law equation for it.
2. In a particular air mass, the concentration of (b) Given that its rate constant at 800°C is 9.7
OH was found to be 8.7 106 molecules cm3, and 1010 L mol1 sec1, and that its activation energy is
that of carbon monoxide was 20 ppm. 315 kJ mol1, calculate the amount by which the
(a) Calculate the rate of the reaction of OH with rate constant increases if the temperature is raised
atmospheric CO at 30°C, given that the rate con- to 1100°C.
stant for the process is 5 1013 e300/T 4. At combustion temperatures, the equilibrium
molecule1 cm3 sec1. constant for the reaction of N2 with O2 is about
(b) Estimate the half-life of OH molecules in air at 1014. Calculate the concentration of nitric oxide
30°C, assuming that their lifetime is determined that is in equilibrium with atmospheric levels of
by their reaction with CO. [Hint: Re-express the nitrogen and oxygen. Repeat the calculation for
rate law as a pseudo-first-order process with the level normal atmospheric temperatures, at which the
equilibrium constant is about 1030. Given that acid, and then titrating the acid. Calculate the
the concentration of NO that exits from the mass percentage of sulfur in a sample if the gas from
combustion zone in a vehicle is much higher a 8.05-g sample required 44.1 mL of 0.114 M
than this latter equilibrium value, what does that NaOH in the titration of the diprotic acid.
imply about equilibrium in the reaction mixture? 8. Calculate the volume, at 20°C and 1.00 atm,
[Hint: Use the stoichiometry of the reaction to reduce of SO2 produced by the conventional roasting of
the number of unknowns in the expression for K.] 1.00 tonnes (10,000 kg) of nickel sulfide ore, NiS.
5. The concentration of ozone in ground-level air What mass of pure sulfuric acid could be produced
can be determined by allowing the gas to react with from this amount of SO2?
an aqueous solution of potassium iodide, KI, in a 9. The settling rate of particulates in air is directly
redox reaction that produces molecular iodine, proportional to the squares of their diameters
molecular oxygen, and potassium hydroxide. (Stokes’ law), provided that their densities are
(a) Deduce the balanced reaction for the overall equal. If emitted particulates with a given diameter
process. are found to settle out after two days, how long
(b) Determine the ozone concentration, in ppb, in would it take particulates of the same material with
a 10.0-L sample of outdoor air if it required 17.0 ␮g half the diameter to settle out if they are emitted
of KI to react with it. from the same tall chimney?
6. Perform a steady-state analysis on the 3-step 10. The sulfur species that is oxidized in water
reaction mechanism below. Assume that both droplets is the bisulfite ion, HSO3, so the rate of
ozone and atomic oxygen are in a steady state, and oxidation is proportional to its concentration multi-
derive an expression for [NO2]兾[NO]. plied by that of the oxidizing agent. Predict how
NO2 9: NO O changes in pH in the droplet will affect the rate of
oxidation if (a) O3 reacts with bisulfite ion, and if (b)
O O2 9: O3 hydrogen peroxide in the protonated form, H3O2,
NO O3 9: NO2 O2 formed in the equilibrium
7. The percentage of sulfur in coal can be deter- H2O2 H Δ H3O2

mined by burning a sample of the solid and passing
the resulting sulfur dioxide gas into a solution of is the species that reacts with bisulfite.
hydrogen peroxide, which oxidizes it to sulfuric
Further Readings
1. O. Klemm, “Local and Regional Ozone: A Stu- 3. A. Sheth and T. Giel, “Understanding the
dent Study Project,” Journal of Chemical Education PM-2.5 Problem,” Pollution Engineering
78 (2001): 1641–1646. (March 2000): 33–35.
2. R. J. Chironna and B. Altshuler, “Chemical 4. (a) A-M. Vasic and M. Weilenmann, “Compari-
Aspects of NOX Scrubbing,” Pollution Engineering son of Real-World Emissions from Two-Wheelers
(April 1999): 33–36; R. K. Agrawal and S. C. and Passenger Cars,” Environmental Science and
Wood, “Cost-Effective NOX Reduction,” Chemical Technology 40 (2006): 149–154. (b) A. Kurniawan
Engineering (February 2001): 78–82. and A. Schmidt-Ott, “Monitoring the Soot
Emissions of Passing Cars,” Environmental Science 6. R. M. Heck and R. J. Farrauto, “Automobile

and Technology 40 (2006): 1911–1915. Exhaust Catalysts,” Applied Catalysis A: General
221 (2001): 443–457.
5. D. Mage et al., “Urban Air Pollution in Megaci-
ties of the World,” Atmospheric Environment 30 7. “Fires from Hell,” New Scientist 31 (August
(1996): 681–686. 2002): 34–37.
C H A P T E R
4
THE ENVIRONMENTAL AND
HEALTH CONSEQUENCES OF
POLLUTED AIR—OUTDOORS
AND INDOORS
topics are used:
 pH and acid–base concepts
 Balancing of redox equations
Background from Chapter 3 used in this chapter:

 Photochemical smog; thermal NO
 Coarse and fine particulates
 Aerosols
 PMx indexes
 ppm, ppb, and ␮g/m3 concentration scales for gases
Introduction
Smog, whether sulfur-based or photochemical, often has unpleasant odors
due to some of its gaseous components. More seriously, the initial pollutants,
intermediates, and final products of the reactions in smog affect human
health and can cause damage to plants, animals, and some materials. In this
chapter, we describe the detrimental effects on animals, plants, and materials
of the gases and particles in polluted air—including the air we encounter
indoors—and methods by which air pollution can be combated. Included in
the discussions are the environmental effects of acid rain, a phenomenon that
results from polluted air.
145
146 Chapter 4 The Environmental and Health Consequences of Polluted Air
Haze
The most obvious manifestation of photochemical smog is a yellowish-
brownish-gray haze that is due to the presence in air of small water droplets
containing products of chemical reactions that occur among pollutants in air.
This haze, familiar to most of us who live in urban areas, now extends period-
ically to once-pristine areas such as the Grand Canyon in Arizona.
Particles whose diameter is about that of the wavelength of visible light,
i.e., 0.4–0.8 ␮m, can scatter light and interfere with its transmission, thereby
reducing visual clarity, long-distance visibility, and the amount of sunlight
reaching the ground. A high concentration in air of particles of diameters
between 0.1 ␮m and 1 ␮m produces a haze. Indeed, one conventional tech-
nique of measuring the extent of particulate pollution in an air mass is to
determine its haziness. The existence of smog in the air can often be deter-
mined by simply looking at buildings or hills in the distance and seeing if
their appearance is partially masked by haze.
The widespread haze in the Arctic atmosphere in winter is due to sul-
fate aerosols that originate from the burning of coal, especially in Russia
and Europe. The enhanced haziness in summertime over much of North
America is due mainly to sulfate aerosols arising from industrialized areas in
the United States and Canada. Fine particles also are largely responsible for
the haze associated with Los Angeles and other locations subject to
episodes of photochemical smog. The smog aerosols contain nitric acid that
has been neutralized to salts. Also present in
these aerosols are carbon-containing products
Nitrate, 4%
that are intermediates in the photochemical
Ammonium, 11%
smog reactions; however, intermediates formed
from fuel molecules having short carbon chains
usually have vapor pressures high enough that
they exist as gases rather than condense onto
particles. The typical composition of the fine
component of an aerosol suspended over conti-
Sulfate, 37% nental areas is illustrated in Figure 4-1.
Organic Since most fine particles in urban air
carbon, 24%
are secondary pollutants, their number can
only be controlled by reducing emissions of
the primary pollutant gases from which they
are created. Thus governments have successively
Other, 19% required more and more stringent emission
controls on vehicles, power plants, etc., as dis-
Elementary cussed in Chapter 3. The switch to low-sulfur
carbon, 5%
gasoline and diesel fuels should make catalytic
FIGURE 4-1 Typical composition of fine continental aerosol. converters on vehicles more efficient in reduc-
[Adapted from J. Heintzenberg, Tellus 41B (1989): 149–160.] ing emissions.
Acid Rain 147
Acid Rain
One of the most serious environmental problems facing many regions of the
world is acid rain. This generic term covers a variety of phenomena, includ-
ing acid fog and acid snow, all of which correspond to atmospheric precipita-
tion of substantial acidity. In this section, the nature of the acids present in
precipitation is discussed.
The phenomenon of acid rain was discovered by Angus Smith in Great
Britain in the mid-1800s, but then it was essentially forgotten until the 1950s.
It refers to precipitation that is significantly more acidic than “natural” (i.e.,
unpolluted) rain, which itself is often mildly acidic due to the presence in it of
dissolved atmospheric carbon dioxide, which forms carbonic acid, H2CO3:
CO2(g) H2O(aq) Δ H2CO3(aq)
The weak acid H2CO3 then partially ionizes to release a hydrogen ion, H,
with a resultant reduction in the pH of the system:
H2CO3(aq) Δ H HCO3
Because of this source of acidity, the pH of unpolluted, “natural” rain is about
5.6 (see Problem 3-10). Only rain that is appreciably more acidic than this—
that is, with a pH of less than 5—is considered to be truly “acid” rain since,
because of natural trace amounts of strong acids, the acidity level of rain in
clean air can be a little greater than that due to carbon dioxide alone. Strong
acids such as hydrochloric acid, HCl, produced by emissions of hydrogen
chloride gas by volcanic eruptions, can produce “natural” acid rain temporar-
ily in regions such as Alaska and New Zealand. On the other hand, the pH
of unpolluted rain may be somewhat greater than 5.6 due to the presence of
weakly basic substances originating with airborne soil particles that have par-
tially dissolved in the droplets.
The two predominant acids in acid rain are sulfuric acid, H2SO4, and
nitric acid, HNO3, both of which are strong acids. Generally speaking, acid
rain is precipitated far downwind from the source of the primary pollutants,
namely sulfur dioxide, SO2, and nitric oxide, NO. The strong acids are cre-
ated during the transport of the air mass that contains the primary pollutants.
O2
SO2 9:
HO
H2SO4
2
O2
NOX 9:
HO
HNO3
2
Consequently, acid rain is a pollution problem that does not respect state or
national boundaries because the atmospheric pollutants often undergo long-
range transport. For example, most acid rain that falls in Norway, Sweden,
and the Netherlands originates as sulfur and nitrogen oxides emitted in other
countries in Europe. Indeed, the modern recognition of acid rain as a problem

stems from observations made in Sweden in the 1950s and 1960s, which were
due to emissions from outside its borders. China now has serious acid rain
problems due to its high emissions of SO2. Acidification is more serious in
southern and southwestern than in northern China, where airborne alkaline
dust originating in deserts neutralizes the acid. Some of the acid rain that
originates in China is carried by the wind to Japan and, on occasion, all the
way to North America. As the late economist-philosopher John Kenneth
Galbraith noted, “Acid rain falls on the just and the unjust and also equally
on the rich and poor.”
The Ecological Effects of Acid Rain

and of Photochemical Smog
Acid rain has a variety of ecologically damaging consequences, and the pres-
ence of acid particles in air may also have direct effects on human health.
However, the effects of acid rain on soil vary dramatically from region to
region. In this section, we investigate the chemical processes underlying the
ecological effects of acid rain.
Nitric oxide is not especially soluble in water, and the acid (sulfurous) that
sulfur dioxide produces upon dissolving in water is a weak one. Consequently,
the primary pollutants NO and SO2 themselves do not make rainwater partic-
ularly acidic. However, some of the mass of these primary pollutants is con-
verted over a period of hours or days into the secondary pollutants sulfuric acid
and nitric acid, both of which are very soluble in water and are strong acids.
Indeed, virtually all the acidity in acid rain is due to the presence of these two
acids. In eastern North America, sulfuric acid greatly predominates because
some electrical power is generated from power plants that use high-sulfur coal.
In western North America, nitric acid attributable to vehicle emissions is pre-
dominant, since the coal mined and burned there is low in sulfur.
Figure 4-2 shows a contour map of the average pH of precipitation in dif-
ferent regions of the world. The lowest pH ever recorded, 2.4, occurred for a
rainfall in April 1974 in Scotland. Indeed, central-west Europe, including the
United Kingdom, has a serious acid rain problem, as can be seen from the
pH 4.0 and 4.5 contours surrounding the area in Figure 4-2. In North
America, the greatest acidity occurs in the eastern United States and in
southern Ontario, since both regions lie in the path of air originally polluted
by emissions from power plants in the Ohio Valley. On the other hand, much
of the acidity that falls in upper New York State stems from emissions in
southern Ontario.
In addition to the acids delivered to ground level during precipitation, a
comparable amount is deposited on the Earth’s surface by means of dry depo-
sition, the process by which nonaqueous chemicals are deposited onto solid
and liquid surfaces at ground level when air containing them passes over the
Acid Rain 149
4.6
4.4–5.6 5.0 4.5
5.0 5.5
4.5 4.0
6.0 6.0
4.0
4.5–5.0 5.0 5.0 6.0
5.9
5.0
4.0–5.0 5.5 6.3
5.5
5.2 4.7
4.7 4.7
5.1
4.1
3.8–5.4
6.3
Estimated distribution of pH
Isolated measurements in remote areas
FIGURE 4-2 Global pattern of acidity of precipitation. [Source: Redrawn from J. H. Seinfeld and
S. N. Pandis, Atmospheric Chemistry and Physics (Chichester: John Wiley, 1998).]
surfaces. Much of the original SO2 gas is not oxidized in the air but rather is
removed by dry deposition from air before reaction can occur: Oxidation and
conversion to sulfuric acid occurs after deposition. Wet deposition processes
encompass the transfer of pollutants to the Earth’s surface by rain, snow, or
fog—i.e., by aqueous solutions.
Neutralization of Acid Rain by Soil

The extent to which acid precipitation affects biological life in a given area
depends strongly on the composition of the soil and bedrock in that area. If
the bedrock is limestone or chalk, the acid can be efficiently neutralized
(“buffered”), since these rocks are composed of calcium carbonate, CaCO3,
which acts as a base and reacts with acid, producing bicarbonate ion,
HCO3, as an intermediate:
CaCO3(s) H(aq) 9: Ca2(aq) HCO3(aq)
HCO3(aq) H(aq) 9: H2CO3(aq) 9: CO2(g) H2O(aq)
The reactions here proceed almost to completion due to the excess of H
that is present. Thus the rock dissolves, producing carbon dioxide and calcium
ion to replace the hydrogen ion. These same reactions are responsible for the
deterioration of limestone and marble statues; fine detail, such as ears, noses,
and other facial features, are gradually lost as a result of reaction with acid
and with sulfur dioxide itself. Also, neutralization by calcium carbonate and
similar compounds that are commonly present as suspended particles in
atmospheric dust is the mechanism by which carbonic acid in normal rainfall
and acid rain over some areas has a pH greater than expected.
In contrast, areas strongly affected by acid rain are those having granite
or quartz bedrock, since the soil there has little capacity to neutralize the acid.
Figure 4-3 shows areas of North America having low soil alkalinity, that is,
low amounts of basic compounds with which acids can react. Large areas
susceptible to acidity are the Precambrian Shield regions of Canada and
Scandinavia. Acid rain resulting from the massive development of the tar
sands to produce synthetic crude oil in northern Alberta, and the SO2 and
NOX emissions that result, are now affecting areas in Manitoba and northern
Saskatchewan that lie upwind from them, since the soils in these two areas
have very little neutralizing capacity (Figure 4-3).
Acidity from precipitation leads to the deterioration of soil. When the
pH of soil is lowered, plant nutrients such as the cations potassium, calcium,
and magnesium are exchanged with H and thereupon leached from it.
Although sulfur dioxide emission
levels fell significantly in recent decades in
both Europe and North America, there
has not been as large a corresponding
change in the pH of the precipitation,
especially in northeastern North America.
The lack of corresponding reduction in
acidity is attributed to a decline over the
same period of fly ash emissions from
smokestacks and of other solid particles,
all of which are alkaline and in the past
neutralized a fraction of the sulfur dioxide
and sulfuric acid in the same way that
calcium carbonate does in soil. Thus the
decline in acidity in precipitation in the
northeastern United States from 1983 to
1994 amounted to 11%, although the sul-
fate ion molar concentrations in precipita-
tion fell not by 5.5% (half that of H), but
rather by 15%. The much smaller nitrate
levels remained essentially unchanged in
FIGURE 4-3 Regions of North America with low soil alkalinity for this period in this region. The change in
neutralizing acid rain. [Source: D. J. Jacob, Introduction to Atmospheric sulfate deposition in the northeastern
Chemistry (Princeton, NJ: Princeton University Press, 1999), p. 233.] United States and south-central Canada
Acid Rain 151
1980–1983 1995–2000
kg/ha/yr kg/ha/yr
35 35
30 30
25 25
20 20
15 15
FIGURE 4-4 Wet sulfate deposition in eastern North America as a four-year mean (kilograms/
hectare per year). [Source: Canadian National Atmospheric Chemistry Database, Meteorological Service
of Canada, Environment Canada.]
from the early 1980s to the late 1990s is shown in Figure 4-4. In Great
Britain, rainfall acidity declined by about 40% in the 1986–1997 period due
to emission controls there.
Because of acid rainwater falling and draining into them, tens of thou-
sands of lakes in the Shield regions of both Canada and Sweden have become
strongly acidified, as have lesser numbers in the United States, Great Britain,
and Finland. Lakes in Ontario are particularly hard hit, since they lie directly
in the path of polluted air and since the soil there contains little limestone.
In a few cases, attempts have been made to neutralize the acidity by adding
limestone or calcium hydroxide, Ca(OH)2, to the lakes; however, this
process must be repeated every few years to sustain an acceptable pH. Adding
phosphate ion to lakes can also control acidity, since it stimulates plant
growth during the natural denitrification process by which nitrate ion,
NO3, is converted to reduced nitrogen with the consumption of large quan-
tities of hydrogen ions, as shown in the reduction half-reaction
2 NO3 12 H 10 e 9: N2 6 H2O
In recent years, a new source of sulfuric acid in lakes has appeared—the oxi-
dation of sulfur in shallow wetlands dried up by global warming and thereby
exposed to the air.
As Problem 4-1 shows, the oxidation of ammonium ion, NH4, to

nitrate ion produces hydrogen ions. Indeed, the large emissions of ammonia
into the air from manure in areas of livestock and poultry farming result in
the atmospheric deposition of ammonium ion, which then is oxidized by soil
microbes. The resulting H contributes to the acidification of soil.
P R O B L E M 4-1
Deduce the balanced redox half-reaction of conversion of ammonium ion,
NH4, to nitrate ion, NO3, and thereby show that H is also produced in
this process.
In Australia, soil acidity has a completely different origin. Acidification

is associated there with the removal of nitrate ion by the harvesting of plant
and animal crops and by soil leaching. Presumably the loss of nitrate prevents
its natural buffering of acidity by the reaction shown above. As in Canadian
lakes, the effects of the acidification have been partially reversed in Australia
by the addition of lime to the soil.
Until recently, acid rain in the United States was considered to be a
problem for its northeastern region. Indeed, one of the hardest-hit regions is
the Catskill Mountains in New York State, whose surface rocks consist of
calcium-poor sandstone and from which most of the nutrients have now been
leached. At the Hubbard Brook Experimental Forest in New Hampshire, half
the calcium and magnesium in soil was leached by 1996 and, as a result, veg-
etative growth almost stopped. However, as a consequence of the reduction
in SO2 emissions, by 2003 over half the lakes in the Adirondack Mountains
of New York State showed some significant recovery from acid rain. On aver-
age, the ability of lake water to neutralize acids increased by an average of
1.6 micromoles of H per liter per year in the 1990s. Unfortunately, full
recovery for these lakes to an acid-neutralizing capacity of 50 micromoles per
liter is predicted to take another 25–100 years to achieve.
Acid rain now is also a concern in the southeastern United States. Here
soils are generally thicker and thus able to neutralize more acid. However,
much of that leaching ability now has been exhausted and acid levels in many
waterways have increased substantially. It has been discovered that the recov-
ery of such soils, and of those in Germany, is slowed once acid precipitation
has declined, because previously stored sulfate ion is then released, causing
more cation leaching and penetration of acidity deeper into the ground.
The regulatory scheme used in the United States of requiring reductions
in sulfur dioxide emissions in certain geographical regions has been extended
by European scientists and regulators into the concept of critical load. This
concept recognizes that different levels of risk from acid rain are faced in dif-
ferent regions. Geographic areas that have buffering capacity can withstand a
much greater load of acid rain before damage occurs than those without the
Acid Rain 153
capacity. Thus, higher sulfur dioxide emissions from a particular region can be
allowed if the area in which the resulting sulfuric acid is usually deposited has
a high critical load. To determine the critical loads, scientists use computer
models that incorporate soil chemistry, rainfall, topography, etc. Use of the
concept has had great success in Sweden, for example.
In using critical loads, pollution control becomes effects-based rather than
source-based. Although the critical-loads concept has been implemented in reg-
ulations in Europe and Canada and is favored by many scientists and politicians
in the United States, it has not been implemented there. Although significant
progress has been made in reducing emissions of SO2, and more reductions are
scheduled both for it and for NOX, scientists predict that these efforts will be
insufficient to allow a full recovery of lakes and forests in the northeastern
United States and south-central Canada.
Acidification reduces the ability of some plants to grow, including those in
fresh-water systems. Because of the decrease in this productivity in lakes and
streams that feed them, the amount of dissolved organic carbon (DOC) in the
surface water has declined. The DOC contains molecules that absorb some of
the ultraviolet from sunlight; thus a decline in DOC levels has allowed more
penetration of UV light into the lower layers of lakes. In addition, global
warming (see Chapters 6 and 7) has resulted in the drying up of some streams
that supplied DOC to lakes. Furthermore, stratospheric ozone depletion has
also allowed more UV to reach the Earth’s surface, including lakes, in the first
place. Thus fresh-water lakes have suffered a “triple whammy” from global
environmental problems.
Release of Aluminum into Soil and

Water Bodies by Acid Rain
Acidified lakes characteristically have elevated concentrations of dissolved
aluminum ion, Al3, and it is now known that many of the biological effects
of acid rain are due to increased levels of aluminum ion dissolved in water
rather than to the hydrogen ion itself.
Aluminum ions are leached from rocks in contact with acidified water by
reaction with the hydrogen ions; under normal, near-neutral pH conditions,
the aluminum is immobilized in the rock by their insolubility.
H
Al compounds(s) 9: Al3
Plots of dissolved aluminum concentration versus water acidity for lakes in

the Adirondack Mountains of New York State and for lakes in Sweden are
illustrated in Figure 4-5. (The chemistry underlying these processes is further
discussed in Chapter 13, as are the reasons why natural waters have pH values
of 7 or 8, rather than the 5.3 of rain.)
Adirondacks, U.S.A. West coast, Sweden
(a) (b)
1.0 1.0
Aluminum concentration
FIGURE 4-5 Aluminum
concentrations versus pH
(mg/L)
of the water in different
fresh-water lakes in (a) the 0.1 0.1
Adirondacks and (b) western
Sweden. Notice the
logarithmic vertical axis.
[Source: M. Havas and
J. F. Jaworski, Aluminum in the
0.01 0.01
4 5 6 7 8 4 5 6 7 8
Canadian Environment (Ottawa:
National Research Council of
pH pH
Canada Report 24759, 1986).]
Scientists believe that both the acidity itself and the high concentrations
of aluminum together are responsible for the devastating decreases in fish
populations that have been observed in many acidified water systems. Different
types of fish and aquatic plants vary in their tolerances for aluminum and
acid, so the biological composition of a lake varies as it gradually becomes
increasingly acidic. Generally speaking, fish reproduction is severely dimin-
ished even at low levels of acidity that can, however, be tolerated by adult
fish. Very young fish, hatched in early spring, also are subject to the shock of
very acidic water that occurs when the acidic winter snow all melts in a short
time and enters the water systems.
Healthy lakes have a pH of about 7 or a little higher; few fish species sur-
vive and reproduce when the pH drops much below 5. As a result, many lakes
and rivers in affected areas are now devoid of their valuable fish; for example,
30% of the salmon rivers in Nova Scotia are too acidic for Atlantic salmon to
survive. The water in many acidified lakes is crystal clear due to the death of
most of the flora and fauna.
However, aluminum levels draining from soils at medium-to-high eleva-
tions in the United States declined significantly over the period 1984–1998
and, if the trend continues, will not be a threat to fish by about 2012.
Effect of Air Pollution on Trees and Crops

In recent years it has become clear that air pollution can also have a severe
effect on trees. The phenomenon of forest decline was first observed on a
large scale in western Germany and occurs mainly at high altitudes. However,
the cause-and-effect relationship behind this forest decline has been very dif-
ficult for scientists to untangle. As discussed above, acidification of the soil
can leach nutrients from it and, as occurs in lakes, solubilize aluminum. This
element may interfere with the uptake of nutrients by trees and other plants.
Apparently both the acidity of the rain falling on affected forests and the tro-
pospheric ozone and other oxidants in the air to which they are exposed pose
significant stresses to the trees. These two stresses alone will not kill them,
but when combined with drought, temperature extremes, disease, or insect
attack, the trees become much more vulnerable.
Forests at high altitudes are most affected by acid precipitation, possibly
because they are exposed to the base of low-level clouds, where the acidity is
most concentrated. Fogs and mists are even more acidic than precipitation,
since there is much less total water to dilute the acid. For example, white
birch trees along the shores of Lake Superior experience dieback in regions
where acid fog occurs, as it frequently does there. Deciduous trees (i.e., those
that lose their leaves annually) affected by acid rain gradually die from their
tops downward; the outermost leaves dry and fall prematurely and are not
replenished the following spring. The trees become weakened as a result of
these changes and become more susceptible to other stressors. In some
regions of Europe and North America, forest soils are limed in order to com-
bat the effects of acidity on trees.
Ground-level ozone itself has an effect on some agricultural crops due to
its ability to attack plants. Apparently the ozone reacts with the gas (ethene)
that the plants emit, generating free radicals that then damage plant tissue.
The rate of photosynthesis is slowed, and hence the total amount of plant
material is reduced, by the action of ozone. As in the case of trees, air pollu-
tion acts as a stressor to plants. The collective damage to North American
crops, e.g., alfalfa in the United States and white beans in Canada, is esti-
mated to be $3 billion a year. Other crops whose yields are adversely affected
by current levels of ozone include wheat, corn, barley, soybeans, cotton, and
tomatoes. The fraction of the world’s cereal crops that are grown in regions of
high ozone, and therefore subject to damage, is predicted to more than triple
by 2025.
The Human Health Effects

of Outdoor Air Pollutants
It is now well established that breathing polluted air can have a dramatic
influence on human health. In this section, the most important effects of out-
door air pollutants are described, and the variation in concentration of the
dominant air pollutants in different countries is discussed.
The effect that pollutants have on human health cannot be deduced
from general laws of biology or physiology; they must be established by exper-
imentation. One can imagine experiments involving animals or human vol-
unteers in which the health effects of exposure to brief periods of artificially
produced high-level pollution are studied. However, the extrapolation of
information gained from short-term studies of high-level pollution to the

long-term exposures at low levels is difficult. In particular, for some pollu-
tants, there may exist a threshold pollutant concentration, or an exposure
below which a particular health effect does not occur. In such cases, predic-
tions obtained by assuming simple direct proportionality between exposure
and effect would be unwarranted. In addition, there could be deleterious
effects of chronic exposure that do not come into play when exposure, even
intense exposure, to pollutants occurs only for brief periods of time.
For these reasons, the best information regarding the effects of pollutants
on health comes from the large-scale “experiment” in which we are all
enrolled as “test animals”—namely, living in a society in which we are rou-
tinely exposed to these pollutants for our whole lives. Because the level of
exposure to any given pollutant varies considerably from place to place, sci-
entists can collect information on health and on pollution levels in different
locations, then correlate them using statistics to establish the effect of one on
the other.
As would be expected, the major effects on human health from air pollu-
tion occur in and through the lungs. For example, asthmatics suffer worse
episodes of their disease when the sulfur dioxide or the ozone or the particu-
late concentration rises in the air that they breathe. In one U.S. study, it was
established that asthma attacks increased by 3% for each increase of 10 ␮g/m3
in the PM10 index (discussed in Chapter 3). A recent study in California
found that asthma can be caused by air pollution, specifically by ozone and
especially among highly active children, who naturally inhale more air into
their lungs.
Another gaseous pollutant of some concern is 1,3-butadiene, which has
the structure CH2“CH¬CH“CH2. This hydrocarbon is known as an air
toxic since there is evidence that it causes cancer—leukemia and non-
Hodgkin’s lymphoma especially—and may also negatively affect human repro-
duction. It is produced as a by-product of the incomplete combustion of
fuels, is produced in forest fires and wildfires, and is a component of cigarette
smoke.
The Human Health Effects of Smogs

In the middle decades of the twentieth century, several Western industrial-
ized cities experienced such serious wintertime episodes of smog from soot
and sulfur pollution that the death rate increased noticeably. For example, in
London, England, in December 1952, about 4000 people died within a few
days—plus 8000 more in the next few months—as a result of the high con-
centrations of these pollutants that had built up in a stagnant, foggy air mass
trapped by a temperature inversion close to the ground. Those at most risk
were young children and elderly persons already suffering from bronchial
problems. A ban on household coal burning, from which most of the pollutants
originated, has now largely eliminated such problems. Scientists are still
unsure whether the main sulfur-containing agent that caused such serious
problems in London was the SO2, the sulfuric acid droplets, or the sulfate
particulates.
Today, due to pollution controls, soot-and-sulfur smogs are no longer a
major problem in Western countries. Deaths from bronchitis have fallen by
over half in the United Kingdom, the result of changes in air quality (and
smoking habits). However, the quality of winter air in some areas of what was
the Eastern bloc of countries, such as southern Poland, the Czech Republic,
and eastern Germany, until recently was very poor on account of the burning
of large amounts of high-sulfur (up to 15% S) “brown coal” for both industrial
and home-heating purposes. For example, although the acceptable limit for
the concentration of SO2 in air is 80 ␮g/m3 in many countries, the level of
this gas in Prague surpassed 3000 ␮g/m3 on occasion. Indeed, four out of five
children admitted to the hospital in some areas of Czechoslovakia in the early
1990s were there for treatment of respiratory problems. However, the average
SO2 level in Prague decreased by about 50% from the early 1980s to the early
1990s, and overall in the Czech Republic SO2 emissions are now only about
10% of 1990 levels. The tremendous improvement of air quality in eastern
Germany since 1990, where mean SO2 levels have dropped from 113 to
6 ␮g/m3, has resulted in a decrease in childhood respiratory infections and an
increase in lung function.
The effects of sulfur dioxide are also evident in cities such as Athens,
where the death rate is found to increase by 12% when the concentrations of
the gas exceed 100 ␮g/m3. Detail on the ancient statues and monuments of
Athens is also being seriously eroded by sulfur dioxide and its secondary pol-
lutants. High levels of sulfur dioxide and of fine particulates, both mainly
from diesel-fueled vehicles, caused about 350 premature deaths in Paris annu-
ally in the late 1980s. And the air in London is not so improved that it does
not affect human health; a recent study concluded that one in every 50 heart
attacks was triggered by outdoor air pollution, from a combination of smoke,
CO, SO2, and NO2.
European cities are not the only ones affected by air pollution. Both
sulfur dioxide and particulate matter levels regularly exceed World Health
Organization (WHO) guidelines in Beijing, Seoul, and Mexico City. In 2002,
13 of the 20 world cities having the highest averages for airborne particulate
matter were located in China; the others were Cairo, Jakarta, and five cities
in India. In many large cities in the developing world, coal is still the predom-
inant fuel and in some cases diesel-powered vehicles substantially worsen
the problem. In Beijing, high SO2 emissions from coal burners that are used
to heat buildings, plus smoke from smelters on the edges of the city, plus
windblown dust and sand from the Gobi Desert combine to produce poor air
quality. Haze over China, produced by air pollution, so reduces sunlight
intensity that it may be cutting food production by as much as 30% across a
third of the country. Indeed, there are a number of cities in China in which
the air quality is among the poorest in the world. According to recent projec-
tions, if no attempts are made to reduce SO2 emissions as industrialization
increases, by 2020 the concentration of the gas in Bombay and the Chinese
cities of Shanghai and Chongqing will be about four times the WHO maxi-
mum safe limit.
It is a historical characteristic that once an undeveloped country starts
industrial development, its outdoor air quality worsens significantly. The sit-
uation continues to deteriorate until a significant degree of affluence is
attained, at which point emission controls are enacted and enforced, and the
air begins to clear. Thus, although the quality of air is now improving with
time in most developed countries, it is worsening in the larger cities of devel-
oping countries. Mexico City and several urban areas in China, especially
Beijing, are generally considered to have the worst urban air pollution in the
world at present. Half the respiratory disease in China is caused by air pollu-
tion. A report by the United Nations Environmental Program estimates that
deaths worldwide from all forms of air pollution amounted to 2.7–3.0 million
in 2001, a figure that may rise to 8 million by 2020.
Although acute smog episodes from soot and sulfur-based chemicals have
been eliminated in the West, many residents in these countries still are chron-
ically exposed to measurable levels of suspended particles containing sulfuric
acid and sulfates due to the long-range transport of these substances from
industrialized regions that still emit SO2 into the air. For example, research has
shown a positive correlation between atmospheric concentrations of ozone and
oxidized sulfur and hospital admissions for respiratory problems in southern
Ontario. There is some evidence that the acidity of the pollution is the main
active agent in causing lung dysfunction, including wheezing and bronchitis
in children. Asthmatic individuals appear to be adversely affected by acidic
sulfate aerosols, even at very low concentrations.
Photochemical smog, which arises from nitrogen oxides, is now more
important than sulfur-based smog in most cities, particularly those of high
population and vehicle density. As discussed in Chapter 3, it consists of gases
such as ozone and an aqueous phase containing water-soluble organic and
inorganic compounds in the form of suspended particles. In contrast to
“London smogs,” which chemically were reducing in nature due to sulfur
dioxide, photochemical smogs are oxidizing.
Ozone itself is a harmful air pollutant. In contrast to sulfur-based chemi-
cals, its effect on the robust and healthy is as serious as on those with pre-
existing respiratory problems. Experiments with human volunteers have shown
that ozone produces transient irritation in the respiratory system, giving rise
to coughing, nose and throat irritation, shortness of breath, and chest
pains upon deep breathing. People with respiratory problems can often tell
from their symptoms—such as the tightening of their chest or the beginning
of a cough—when the air quality is poor. Even healthy, young people often
experience such symptoms while exercising outdoors by cycling or jogging

during smog episodes. Indeed, there is evidence that the daily race times of
cross-country runners increase with increasing ozone concentration in the air
that they inhale. A small percentage of the day-to-day fluctuations in mortal-
ity rate in Los Angeles is explained by variations in the concentrations of air
pollutants. An analysis of 95 urban centers in the United States discovered
that a period of high ozone concentrations increased daily cardiovascular and
respiratory mortality by about 0.5% per 10 ppb increase following a few days
of continuous exposure. It is not yet clear what, if any, long-term lung dys-
function results from exposure to ozone, and indeed this is a controversial
subject among scientists. Exposure to ozone produces a number of indirect
health effects as well—including a decrease in sperm count.
One anticipated effect of ozone is a decreased resistance to disease from
infection because of the destruction of lung tissue. Many scientists believe
that chronic exposure to high levels of urban ozone leads to the premature
aging of lung tissue. At the molecular level, ozone readily attacks substances
containing components with C“C bonds, such as occur in biological tissues
of the lung. As discussed later, the fine particulates produced in the photo-
chemical smog process can have a deleterious health effect on humans.
Most industrialized nations have enacted standards that regulate the
maximum concentrations in air of sulfur dioxide, nitrogen dioxide, NO2, and
carbon monoxide, CO, as well as ozone and fine particulates (see Table 4-1),
and in some cases total reduced sulfur, since all these pollutants cause health
effects at sufficiently high concentrations. For example, several recent North
American studies have statistically linked the rate of hospitalization for
TABLE 4-1 Air Quality Standards, in Parts per Billion, for Pollutants
Time Span European

Pollutant to Average United States Canada Union Australia
O3 8 hr 80 65* 60 80
CO 1 hr 35 31
8 hr 9 13 9 9
SO2 1 day 140 115 48 80
1 year 30 23 20
NO2 1 year 53 53 21 30
PM2.5 (in ␮g/m3) 1 day 35 30* 50 25
*To be implemented by 2010.

congestive heart failure among elderly people to the daily carbon monoxide
concentration in outside air. Mexico City currently has the highest levels of
carbon monoxide among the world’s most polluted cities. Both CO and NO2
are usually more of a problem in indoor air and will be discussed in detail in a
later section.
It has been speculated that pollution due to SO2 and sulfates causes a
decrease in resistance to colon and breast cancer in people living in northern
latitudes. The suggested mechanism of this action is a reduction in the
amount of available UV-B that is necessary to form vitamin D, which is a pro-
tective agent for both types of cancers. Since sulfur dioxide absorbs UV-B and
sulfate particles scatter it, significant concentrations of either substance in air
will reduce the amount of UV-B reaching ground level. Thus too little UV-B
can have detrimental health effects, just as too much of it can—as was out-
lined in Chapter 2.
Finally, we note that there are some positive effects of air pollution on
human health! For example, the rate of skin cancers in areas heavily polluted
by ozone is probably reduced because of the ability of the gas to filter UV-B
from sunlight.
Particulates as Health Risks

Particulate matter in the form of smoke from coal burning has been an air pol-
lution problem for many hundreds of years, especially in the United Kingdom.
John Evelyn wrote in his January 1684 diary that “London by reason of the
excessive coldness of the air, hindering the ascent of the smoke, was so filled
with the fuliginous [sooty] steam of sea-coal, that hardly could one see across
the street, and this filling the lungs with its gross particles exceedingly
obstructed the breast, so as one would scarce breathe.” Indeed, unsuccessful
attempts to control coal burning and punish offenders had begun in the
thirteenth century in Britain. Perhaps Shakespeare was referring to this type
of air pollution in the quotation from Hamlet that opened Chapter 3.
Although serious episodes of such soot-and-sulfur smogs have been
largely eliminated in Western industrialized countries, the air pollution
parameter that correlates most strongly with increases in the rate of disease or
mortality in most such regions is the concentration of respirable (fine) partic-
ulates, PM2.5. It appears that particulate-based air pollution has a greater
effect on human health than that produced directly by pollutant gases.
Substances that dissolve into the body of a particle are said to be
absorbed by it; those that simply stick to the surface of the particle are said to
be adsorbed (see Figure 4-6). An important example of the latter is repre-
sented by the adsorption of large organic molecules onto the surfaces of
carbon (soot) particles, as discussed later in Chapter 12. Many insoluble
airborne particles are surrounded by a film of water, which can itself dissolve
other substances. The adsorption of metal atoms and organic molecules on
the surface of airborne particles may give rise to some of the

Adsorbed
health hazards these particles represent. molecule
Larger particles—coarse ones, according to the defini-
tion in Chapter 3—are of less concern to human health
than are small (fine) ones for several general reasons:
Particle
• Since coarse particles settle out quickly, human expo-
sure to them via inhalation is reduced.
• When inhaled, coarse particles are efficiently filtered
by the nose (including its hairs) and throat and generally
do not travel as far as the lungs. In contrast, inhaled fine Absorbed
molecule
particles usually travel through to the lungs (which is why
they are called respirable), can be adsorbed on cell surfaces
there, and can consequently affect our health. FIGURE 4-6 Contrast
between adsorption and
• The ratio of surface area to mass of large particles is smaller than that absorption of molecules
of small ones; thus, gram for gram, their ability to transport adsorbed gas on/in an airborne particle
molecules to any parts of the respiratory system and to catalyze chemical and (schematic).
biochemical reactions there is correspondingly smaller.
• Devices such as electrostatic precipitators, spray towers, and cyclone col-
lectors that are used to remove particulates from air are efficient only for
coarse particles. Thus, although a device may remove 95% of the total partic-
ulate mass, surface area and respirable particles are reduced by a much lower
fraction; see Problem 4-2. Baghouse filters, which are finely woven fabric
bags through which air is forced, are highly efficient in removing fine parti-
cles in the 1-␮m size range, as well as all the larger ones.
The exhaust from diesel engines has been classified as “likely to be car-
cinogenic to humans” by the U.S. Environmental Protection Agency (EPA).
Studies in California and in Seattle conclude that 70% or more of the risk
to health from air toxics arises from diesel exhaust. Following court deci-
sions, the United States will institute by 2010 a series of new regulations
limiting emissions from on-road diesel vehicles.
P R O B L E M 4-2
An air-filtering device is tested and is found to remove all particles larger
than 1 ␮m in diameter, but almost none of the smaller ones. Calculate the
percentage of the surface area removed by the device for a sample of particu-
lates, 95% of the mass of which is particles of diameter 10 ␮m and 5% of
which is particles of diameter 0.1 ␮m. Assume all particles are spherical and
of equal density. [Hint: Recall that the surface area of a sphere is 4␲r2. Calculate
the surface areas of particles of each size from this formula.]
A number of studies have correlated day-to-day urban morbidity (sick-

ness) rates, as measured by hospital admission rates, for respiratory problems
against the pollution levels during the same short time period. For example,
there have been several reports concerning the immediate effects on the
population of southern Ontario of the pollutants—ozone gas and sulfate
particulates—to which they are most exposed. In one study, the average
number of hospital admissions for respiratory problems correlated best with
the ozone level of the previous day, and to a slightly lesser degree with the
sulfate level from the previous day, for the summers of 1983–1988. Air pol-
lution was found to account for about 6% of summertime hospital respiratory
admissions, a magnitude close to that found in previous investigations in
Ontario and New York State. A recent study found that respiratory admis-
sions correlated significantly with both PM10 and ozone concentrations in
Spokane, Washington—an area where atmospheric sulfur dioxide is essen-
tially nonexistent and therefore can be ruled out as the true culprit in causing
the illnesses.
The strongest links between human health and exposure to airborne par-
ticulate matter are based on recent studies involving cities in the United
States and are the subject of the online Case Study The Effect of Urban Air
Particulates on Human Mortality at the website associated with this chapter.
Smoke
The burning of wood in domestic fireplaces produces large quantities of
particulates, which are emitted from the chimneys into outdoor air unless
catalytic converters are fitted to the smokestack. Indeed, in residential
neighborhoods where wood is the predominant fuel used for heating, wood
stoves contribute up to 80% of the fine particles in the air during the winter
months. Outdoor wood-fired boilers, used to heat water for saunas and swim-
ming pools, have grown so much in popularity that the particulates they emit
have become a significant problem. Some newer wood stoves and boilers
have catalytic converters or secondary combustion chambers in which partic-
ulates and unburned gases are more fully oxidized, thus reducing their emis-
sion to outside air.
Serious episodes of smoky haze pollution over large areas of land have
occurred in recent years in Southeast Asia, especially in Malaysia and
Indonesia. The smoke originates mainly from forest fires that are intention-
ally started in order to clear land that can be subsequently used for agriculture
and to grow trees for their rubber, palm oil, or pulp content. A secondary
source of the smoke is the smoldering underground fires that slowly burn in
underground coal and peat deposits. Indeed, there are estimated to be a quar-
ter million individual coal fires currently burning in Indonesia, as well as
many in China and India, and there are also many peat fires in Malaysia. The
fires are initiated when an outcropping of coal, or of a peat deposit that has
dried after draining, is ignited, typically during one of the fires set to clear the
land. Fires can also be ignited in coal, once exposed to the air, by lightning
strikes and even by spontaneous combustion when the surface pyrite is oxi-
dized and the heat released by this reaction sets the carbon ablaze. These
underground fires can continue to burn for decades after the original forest
fires have stopped.
A so-called Asian brown cloud of particles and gases from forest fires, vehi-
cle exhausts, and domestic cookers—especially in rural areas—that burn
wood, dung, and agricultural waste overhangs most of eastern and southeast-
ern Asia annually from December to May, the main season for home heating.
The brown cloud over the Indian Ocean consists mainly of smoke from the
burning of dried manure in cooking fires. This haze lowers sunlight levels up
to 15%, with a corresponding decline in the yield of crops such as rice and an
alteration to rainfall and monsoon patterns. In contrast to the pollution
aerosol over North America and Europe, to which it is comparable in magni-
tude, the “black carbon” content of the Asian cloud is significant. The
absorption of sunlight by this elemental carbon alters the local hydrological
cycle and hence the weather over the northern Indian Ocean. The lack of
nitric oxide produced in the low-temperature flames of burning biomass cur-
rently limits ozone production over the area, but that will likely be reversed
in the future with increased use of fossil fuels for vehicles.
Large forest fires in northern Canada produce huge quantities of carbon
monoxide and volatile organic compounds (VOCs), which have been found
to travel as far as the U.S. Southeast and which may well increase ozone and
particulate concentrations in the air of this region.
Indoor Air Pollution

The levels of some common air pollutants often are greater indoors than
outdoors, although pollutant concentrations do vary significantly from
one building to another. Since most people spend more time indoors than
outdoors, exposure to indoor air pollutants is an important environmental
problem and may cause more problems to human health than does outdoor
air. Indeed, the inadequate ventilation practices encountered in developing
countries that burn coal, wood, crop residues, and other unprocessed biomass
fuels create smoke and carbon monoxide pollution that produces respiratory
problems and ill health among huge numbers of people in these countries.
Women and young children are particularly affected since they spend more
time indoors. Cooking smoke from biomass fuels increases asthma rates
among elderly men and women. The particulate emissions from traditional
cook stoves used indoors in developing countries can be reduced by 90% by
switching from wood to charcoal. It is estimated that over 400,000 premature
deaths are caused in China annually owing to exposure to dirty household
fuels and to other pollutants in the air.
In the material that follows, we investigate the various indoor air pollu-
tants that are thought to have the most serious effects on human health. To
ensure that the relevant background has been covered, a discussion of several
other indoor air pollutants of interest to human health is deferred until later
chapters: Radon is discussed in Chapter 9, pesticides in Chapter 10, and poly-
cyclic aromatic hydrocarbons (PAHs) in Chapter 12. Chloroform in indoor
air is considered when water purification is discussed, along with indoor air
contamination by chlorinated organic solvents, in Chapter 14.
Formaldehyde
The most controversial indoor organic air pollutant gas is formaldehyde,
H2C“O. It is a widespread trace constituent of the atmosphere since it occurs
as a stable intermediate in the oxidation of methane and of other VOCs.
While its concentration in clean outdoor air is too small to be important—
about 10 ppb in urban areas, except during episodes of photochemical smog—
the level of formaldehyde gas indoors is often orders of magnitude greater, in
certain cases exceeding 1000 ppb (1 ppm). A survey of U.S. homes in the late
1990s found that the indoor formaldehyde concentration usually was in the
5–20 ppb range.
The chief sources of indoor exposure to this gas are emissions from ciga-
rette smoke and from synthetic materials that contain formaldehyde resins
used in urea formaldehyde foam insulation and in the adhesive employed in
manufacturing plywood and particleboard (chipboard). Many useful resins
(which are rigid polymeric materials) are prepared by combining formalde-
hyde with another organic substance. Formaldehyde itself is used in the dye-
ing and gluing of carpets, carpet pads, and fabrics. In the first few months and
years after their manufacture, however, such materials release small amounts
of free formaldehyde gas into the surrounding air. Consequently, new prefab-
ricated structures such as mobile homes that contain chipboard generally
have much higher levels of formaldehyde in their air than do older, conven-
tional homes. Many manufacturers of pressed-wood products have now mod-
ified their production processes in order to reduce the rate at which
formaldehyde is released.
The rate of formaldehyde emission from synthetic materials increases
with temperature and relative humidity and declines as the materials age.
Initially, formaldehyde temporarily trapped as a gas or simply adsorbed onto
the materials is released into the surrounding air. There is also release of
formaldehyde due to the rearrangement and dissociation of amide end-groups
on resin polymers, from R¬NH¬CH2OH to R¬NH2 H2CO. Later, slow
but continuous reactions of water vapor in humid air with the methylene
bridges joining amide groups within the polymer backbone provide a con-
tinuing emission of formaldehyde:
R¬NH¬CH2¬NH¬R H2O 9: 2 R¬NH2 H2CO
Formaldehyde has a pungent odor, with a detection threshold in humans

of about 100 parts per billion, i.e., 0.1 ppm; its odor is often noticeable in
stores that sell carpets and synthetic fabrics. At somewhat higher levels,
many people report irritation to their eyes, especially if they wear contact
lenses, and to their noses, throats, and skin. The formaldehyde in cigarette
smoke can cause eye irritation. Common symptoms of acute (i.e., short-term,
high-level) formaldehyde exposure include coughing, wheezing, bronchitis,
and chest pains. Chronic exposure to low levels of formaldehyde produces
similar effects and respiratory symptoms. Formaldehyde in air may cause chil-
dren to develop asthma and to have more respiratory infections and allergies
and asthma attacks, although evidence for these effects is controversial.
Dampness in homes, allowing the proliferation of dust mites, fungi, and bac-
teria, also plays a large role in increasing lower respiratory tract illnesses,
especially in children.
Formaldehyde is thought to be the most important VOC in producing
what is known as sick building syndrome. This term is used to describe situ-
ations in which the occupants of a building experience acute health effects
and discomfort that seem to be linked to the time they spend in a particular
building, though no specific illness or cause is apparent. Complaints com-
monly include
• headaches;
• irritation of eyes, nose, or throat; dry cough;
• dizziness and nausea; fatigue;
• difficulty in concentrating; and
• dry or itchy skin.
In addition to VOCs emitted from indoor sources, other factors that con-
tribute to the syndrome include inadequate ventilation, pollutants entering
from outside the building, and biological contamination of the air from bac-
teria, molds, pollen, and viruses that have bred in stagnant water that has
accumulated in air vents, etc.
The related compounds acetone, (CH3)2C“O, and 4-butanone (also
called methyl ethyl ketone, MEK) are the ketones most commonly present in
indoor air in U.S. homes, owing to their use as solvents in nail polish and
paint removers, etc.
Formaldehyde is established as a carcinogen (a cancer-causing agent) in
test animals and may also be carcinogenic to humans; it was classified as a
probable human carcinogen by the U.S. EPA in 1987. The expected cancer sites
are in the respiratory system, including the nose; cancers at these sites have
been found for some people who are exposed to the gas in occupational set-
tings. However, studies of human populations exposed to formaldehyde have
led to no clear-cut conclusions concerning an increase in cancer frequency
arising from nonoccupational exposure. From animal studies, an upper limit

to the possible effect in humans can be estimated: It corresponds to an
increase in the cancer rate of one or two cases per 10,000 people after 10 years
of living in a house or trailer with high formaldehyde levels. However, the
lower limit to the effect could well be a zero increase in the cancer rate. In
summary, no scientific consensus has yet been reached on the dangers to
human health of low-level exposure to formaldehyde.
Benzene and Other Gasoline-Related Hydrocarbons

Like formaldehyde, benzene is classified as a hazardous air pollutant, HAP,
sometimes known as air toxics. Benzene, C6H6, is a stable, volatile liquid
hydrocarbon that through the modern age has found a variety of uses. It is a
minor constituent of gasoline and was commonly used as a solvent for many
organic products, including paints and inks. The public is exposed to benzene
vapor indoors from the use of solvents and gasoline, through smoking (mainly
for the smoker but to a lesser extent for those inhaling second-hand smoke),
and from the importing of benzene from outdoor air into the house. The levels
of benzene generally are smaller outdoors and in large buildings than in indi-
vidual homes, especially those with smokers living in them. A significant
fraction of benzene vapor exposure occurs while riding in motor vehicles and
refueling them at gas stations.
Benzene is classified by the U.S. EPA as a known human carcinogen.
Chronic exposure at high occupational levels increases the rate of leukemia
to individuals. Indeed, there were many deaths among workers in the first half
of the twentieth century from exposure to benzene from petroleum-based sol-
vents, such as those used in the rubber and glue industries; in the making of
paints, adhesives, and coatings; and in dry cleaning. It also causes aplastic
anemia, a condition in which an individual is chronically tired and is espe-
cially susceptible to infections because the bone marrow produces insufficient
red blood cells. There continues to be some uncertainty, however, about
whether occupational or domestic exposure to low levels of benzene vapor
does indeed increase the risk for leukemia and multiple myeloma. Recently, it
was estimated that benzene accounted for one-quarter of cancer deaths
caused by air toxics in the United States.
Because of the serious health problems it causes, the use of benzene as a sol-
vent has largely been phased out. In addition, its maximum allowable level in
gasoline has been reduced. Benzene can be replaced in many applications by
toluene, C6H5CH3, which consists of molecules of benzene with one hydrogen
atom replaced by a methyl group. The ¬CH3 group in toluene provides liver
enzymes with a site that is much easier to attack and thereby initiate metab-
olism than any of the very strong bonds in benzene itself. Toluene and the
corresponding dimethylated benzenes called xylenes, the 1,2,4-trimethylated
benzene, and ethylbenzene are all present in modern unleaded gasoline; they
are very commonly detected in indoor air, as are the nonaromatic hydrocarbons
cyclohexane and decane. The concentration of toluene usually greatly exceeds

that of benzene itself. However, there is evidence that methylated benzenes
are demethylated in catalytic converters and that, as a consequence, addi-
tional benzene is emitted into the air under some operating conditions.
Nitrogen Dioxide
Indoor concentrations of NO2 often exceed outdoor values in homes that
contain stoves, space heaters, and water heaters that are fueled by gas. The
flame temperature in these appliances is sufficiently high that some nitrogen
and oxygen in the air combine to form NO, which eventually is oxidized to
nitrogen dioxide. In one study, it was established that NO2 levels in homes
that use gas for cooking or that have a kerosene stove average 24 ppb, com-
pared to 9 ppb for homes that have neither. Peak concentrations near gas
cooking stoves can exceed 300 ppb.
Some nitric oxide is also released from the burning of wood and other
biomass fuels since these natural materials contain nitrogen. However, the
flame temperature used in burning such fuels is much lower than in burning
gas, so little thermal NO is produced from nitrogen in the air.
Nitrogen dioxide is soluble in biological tissue and is an oxidant, so its
effects on health, if any, are expected to occur in the respiratory system.
There have been many studies of the effects on respiratory illness in children
owing to exposure to low levels of NO2 emitted by gas appliances, but the
results of different studies are not mutually consistent and are inadequate for
establishing a cause-and-effect relationship. One study found that a 15-ppb
increase in the mean NO2 concentration in a home leads to about a 40%
increase in lower respiratory system symptoms among children aged 7 to
11 years. Nitrogen dioxide is the only oxide of nitrogen that is detrimental to
health at concentrations likely to be encountered in residences.
Nitrogen dioxide is probably responsible for the finding that indoor con-
centrations of nitrous acid, HNO2, exceed those found outdoors, since the
gas reacts with water to form nitrous and nitric acids:
2 NO2 H2O 9: HNO2 HNO3
Indoor nitrous acid concentrations were found to correlate inversely with
ozone gas concentrations, presumably because the acid is oxidized to nitric
acid by the gas.
Carbon Monoxide
Carbon monoxide, CO, is a colorless, odorless gas whose concentration
indoors can be greatly increased by the incomplete combustion of carbon-
containing fuels such as wood, gasoline, kerosene, or gas. High indoor con-
centrations usually are the result of a malfunctioning combustion appliance,
such as a kerosene heater. Even properly functioning kerosene or gas heaters
in poorly ventilated rooms can result in CO levels in the 50–90-ppm range.
Average indoor and outdoor CO concentrations usually amount to a few

parts per million, though elevated values in the 10–20-ppm range are com-
mon in parking garages due to the carbon monoxide emitted by motor
vehicles. Exhaust fumes containing high levels of CO and other pollutants
can enter homes having attached garages. In developing countries, carbon
monoxide poisoning is a serious hazard when biomass fuels are used to heat
poorly ventilated rooms in which people sleep.
The major danger from carbon monoxide arises from its ability, when
inhaled, to complex strongly with the hemoglobin in blood and thus to
impair its ability to transport oxygen to cells. Hemoglobin’s affinity for CO is
234 times that for oxygen, and once one CO is bound to a given hemoglobin
molecule, the rate of release of its remaining oxygen molecules to cells is
reduced. Recent research has found that mental functioning is reduced dur-
ing short-term exposure to high levels of CO and perhaps also as a result of
long-term exposure to low concentrations, because the brain, like the heart,
is a body organ with a high requirement for oxygen.
One important feature of the reduction in vehicular pollutant emissions
over the last few decades has been the substantial decline in accidental death
from acute carbon monoxide poisoning. In the United States alone, it has
been estimated that more than 11,000 deaths have been avoided as a result.
Smoking tobacco is a significant source of carbon monoxide indoors.
Although nonsmokers usually have less than 1% of their hemoglobin tied up as
the complex with CO, the figure for smokers is many times this value because
of the carbon monoxide that they inhale during smoking. Studies have shown
that increased mortality from heart disease can result even if only several per-
cent of hemoglobin is chronically tied up as the CO complex. Exposure to very
high concentrations of CO results in headache, fatigue, unconsciousness, and
eventually death (if such exposure is sustained for long periods).
Low-priced, easily installed carbon monoxide detectors suitable to warn
residents in homes and offices when high CO levels occur are now widely
available. However, scientists have begun to worry about the poorly known
health effects of chronic exposure to low levels of CO and the fact that such
exposure may be quite common.
Environmental Tobacco Smoke

It is well established that smoking tobacco is the leading cause of lung cancer
and is one of the main contributors to heart disease. Nonsmokers are often
exposed to cigarette smoke, although in lower concentrations than smokers
since it is diluted by air. This environmental tobacco smoke, or ETS (“second-
hand smoke”), has been the subject of many investigations in order to deter-
mine whether or not it is harmful to people who are exposed to it.
ETS consists of both gases and particles. The concentration of some toxic
products of partial combustion is actually higher in sidestream smoke than in
mainstream, since combustion occurs at a lower temperature—and so is less

complete—in the smoldering cigarette compared to one through which air is
being inhaled. Since the sidestream smoke is usually diluted by air before being
inhaled, however, the concentrations of pollutants reaching the lungs of non-
smokers are much lower than those reaching the lungs of smokers themselves.
The chemical constitution of tobacco smoke is complex: It contains
thousands of components, several dozen of which are carcinogens. The gases
in smoke include
• carbon monoxide and carbon dioxide;
• formaldehyde and several other aldehydes, ketones, and carboxylic acids;
• nitrogen oxides, hydrogen cyanide, ammonia, and a number of organic
nitrogen compounds;
• methyl chloride;
• 1,3-butadiene;
• toluene, benzene, and several hundred different PAHs, to be discussed in
Chapters 8 and 12; and
• cadmium and radioactive elements such as polonium (see Chapter 9).
Included in the nitrogen compounds are several nitrosamines, organic nitro-
gen compounds of formula R2N¬N“O, which, together with the PAHs, are
probably the most important respiratory carcinogens in the smoke.
The particulate phase of cigarette smoke is called the tar, and much of it
is respirable in size. The zone in a cigarette that actively burns, as occurs
when a smoker inhales a puff, is quite hot (700–950°C) and produces CO and
H2 as well as the expected CO2 and water vapor. Immediately downstream of
this area is a cooler zone (200–600°C) where smoke constituents such as
nicotine distill out of the tobacco. When this vapor cools farther along the
cigarette path toward the smoker, much of it condenses to aerosol particles
that constitute the particulate phase of the smoke.
Many people experience irritation of their eyes and airways from expo-
sure to ETS. The gaseous components of ETS, especially formaldehyde,
hydrogen cyanide, acetone, toluene, and ammonia, cause most of the odor
and irritation. Exposure to ETS aggravates the symptoms of many people who
suffer from asthma or from angina pectoris, chest pains brought on by exer-
tion. ETS, particularly when it originates from maternal smoking, is known
to induce new cases of asthma in children, especially those of preschool age.
Some recent studies have established correlations between the rate of acute
respiratory illness and the level of indoor PM2.5 (which would include the
total amount of respirable particulates from all sources, including tobacco
smoke). Passive smoking—which involves inhalation of sidestream as well
as already exhaled smoke—is believed by scientists to cause bronchitis,
pneumonia, and other infections such as those of the ear in up to 300,000

infants, as well as several thousand instances of sudden infant death, in the
United States each year. Second-hand smoke may even reduce the cognitive
abilities of children, whether exposed prenatally or when young. Being
exposed to second-hand smoke, whether on the job or by living with a
smoker, approximately doubles a nonsmoker’s chance of developing asthma.
In 1993, the U.S. EPA classified ETS as a known human carcinogen and
estimated that it causes about 3000 lung cancer deaths annually. ETS is also
considered to be responsible for killing as many as 60,000 Americans annu-
ally from heart disease. In a study of American nurses, it was found that non-
smoking women regularly exposed to ETS had a 91% greater rate of heart
attacks than women who had no exposure. Apparently the smoke leads to
hardening of the arteries, a main cause of heart attacks. An analysis of all
recent studies on passive smoking led to the conclusion that the risks of
developing lung cancer and heart disease each are increased by about one-
quarter for nonsmoking spouses of smokers. Longtime workers in bars and
restaurants in which smoking is permitted also have an increased rate of lung
cancer, even if they themselves do not smoke. A British study estimated that
ETS kills 140,000 Europeans annually through cancer and heart disease.
Asbestos
The term asbestos refers to a family of six naturally occurring silicate minerals
that are fibrous (see Chapter 16). Structurally, they are composed of long
double-stranded networks of silicon atoms connected through intervening
oxygen atoms; the net negative charge of this silicate structure is neutralized by
the presence of cations such as magnesium.
The most commonly used form of asbestos, chrysotile, has the formula
Mg3Si2O5(OH)4. It is a white solid whose individual fibers are curly.
Chrysotile, mined mainly in Russia, China, Brazil, Canada (Quebec), and
Kazakhstan, is the principal type of asbestos used in North America. It has
been employed in huge quantities because of its resistance to heat, its
strength, and its relatively low cost. Common applications of asbestos include
its use as insulation and spray-on fireproofing material in public buildings, in
automobile brake-pad lining, as an additive to strengthen cement used for
roofing and pipes, and as a woven fiber in fireproof cloth.
The use of asbestos has been sharply reduced since the 1970s in developed
countries because it is now recognized from studies on the health of asbestos
miners and other asbestos workers to be a human carcinogen. It causes
mesothelioma, a normally rare, incurable cancer of the lining of the chest or
abdomen. In addition, airborne asbestos fibers and cigarette smoke act syner-
gistically: Their combined effect is greater than the sum of their individual
effects (in this case, equal to the product of the two) in causing lung cancer.
There is much controversy concerning whether chrysotile should
be banned outright from further use and whether or not existing asbestos
insulation in buildings should be removed. Many experts feel that existing

asbestos should be left in place unless it becomes damaged enough that
there is a chance that its fibers will become airborne. Indeed, its removal
can dramatically increase the levels of airborne asbestos in a building unless
extraordinary precautions are taken. One scientist stated: “Removing
asbestos is like waking up a pit bull terrier by poking a stick in its ear. We
should let sleeping dogs lie.” Some environmentalists, however, feel that
existing asbestos is a ticking time bomb—that it should be removed as soon
as possible, as one can never predict when building insulation will be
damaged.
Most of the initial concern about asbestos was related to crocidolite, blue
asbestos, and amosite, brown asbestos. Evidence implicating crocidolite in
causing cancer in humans was already well established several decades ago. It
is a material with thin, straight, and relatively short fibers that more readily
penetrate lung passages, making it a more potent carcinogen than the white
form. Crocidolite and amosite are mined in South Africa and Australia; they
were not used much in North America but were used in many areas of
Europe, including the United Kingdom.
More than 15 countries, including the European Union and Australia,
have now banned all forms of asbestos. Some environmentalists and physi-
cians worry that although workers in developed countries wear masks and
overalls and handle white asbestos properly to greatly minimize their expo-
sure to it, these practices are not yet common in developing countries.
Canada, among other countries, has resisted efforts by agencies of the United
Nations to place chrysotile on the list of most hazardous substances.
Review Questions
1. Discuss the relationship between atmospheric 7. Describe the major health effects of outdoor air
particulates and haze. pollutants.
2. What is acid rain? What two acids predominate 8. List four important reasons why coarse particles
in it? usually are of less danger to human health than are
fine particles.
3. Explain why the predominant acid in acid rain
differs in eastern and western North America. 9. What are the main sources of formaldehyde in
indoor air? What are its effects?
4. Using chemical equations, explain how acid rain
is neutralized by limestone that is present in soil. 10. What are the main sources of nitrogen
dioxide and of carbon monoxide in indoor air?
5. Describe the effects of acid precipitation upon
Of benzene?
(a) dissolved levels of aluminum, (b) fish popula-
tions, and (c) trees. 11. What are the three forms of asbestos called?
Why is asbestos of environmental concern?
6. What is the difference in meaning between
absorbed and adsorbed when they refer to particulates?
Additional Problems
1. A sample of acidic precipitation is found to states that the position of equilibrium shifts so as
have a pH of 4.2. Upon analysis it is found to have to minimize the effect of any stress)? [Hint: Write
a total sulfur concentration of 0.000010 M. Calcu- the expression for the acid dissociation constant for the
late the concentration of nitric acid in the sample, weak acid in terms of the concentrations of the reac-
and from the ratio of nitric to total acid decide tants and products, and use the stoichiometry of the
whether the air sample probably originated in east- balanced equation to reduce the number of unknowns
ern or in western North America. to one.]
2. If the pH of rainfall in upstate New York is 5. Calculate the mass of fine particles inhaled by
found to be 4.0, and if the acidity is half due to an adult each year, assuming he/she inhales about
nitric acid and half to the two hydrogen ions 350 L of air per hour and that the average PM2.5
released by sulfuric acid, calculate the masses of index of this air is 10 ␮g/m3. Assuming that each
the primary pollutants nitric oxide and sulfur particle has a diameter of about 1 ␮m and that the
dioxide that are required to acidify one liter of density of the particles is about 0.5 g/mL, calculate
such rain. the total surface area of this annual load of parti-
cles. [Hint: The surface area of a spherical particle is
3. The pH in a lake of size 3.0 km 8.0 km and
equal to 4␲r2, where r is its radius.]
an average depth of 100 m is found to be 4.5.
Calculate the mass of calcium carbonate that 6. The detection threshold of formaldehyde by
must be added to the lake water in order to raise humans is about 100 ppb. Would a typical human
its pH to 6.0. be able to detect formaldehyde at a concentration
of 250 ␮g/m3 if the air temperature was 23°C and
4. The pH of a sample of rain is found to be 4.0.
the pressure 1.00 atm?
Calculate the percentage of HSO4 that is ionized
in this sample, given that the acid dissociation 7. What mass of formaldehyde gas must be
constant for the second stage of ionization of released from building materials, carpets, etc.
H2SO4 is 1.2 102 mol L1. Repeat the calcula- in order to produce a concentration of 0.50 ppm
tion for a pH of 3.0. Is the trend shown by these of the gas in a room having dimensions of
calculations consistent with qualitative predictions 4 m 5 m 2 m?
made according to Le Châtelier’s principle (which
Further Readings
1. C. T. Driscoll et al., “Acidic Deposition in the 2. R. F. Wright et al., “Recovery of Acidified
Northeastern United States: Sources and Inputs, European Surface Waters,” Environmental Science
Ecosystem Effects, and Management Strategies,” and Technology 39 (2005): 64A–72A.
Bioscience 51 (2001): 180–198; J. A. Lynch et al.,
3. F. Laden et al., “Association of Fine Particulate
“Acid Rain Reduced in Eastern United States,”
Matter from Different Sources with Daily Mortality
Environmental Science and Technology 34 (2000):
in Six U.S. Cities,” Environmental Health Perspec-
940–949; M. Heal, “Acid Rain: Is the UK
tives 108 (2000): 941–947.
Coping?” Education in Chemistry (July 2002):
101–104.
4. D. W. Dockery et al., “An Association Between Particulate Air Pollution,” Inhalation Toxicology 7
Air Pollution and Mortality in Six U.S. Cities,” (1995): 1–18.
New England Journal of Medicine 329 (1993):
5. D. R. Gold, “Environmental Tobacco Smoke,
1753–1759; J. Schwartz et al., “The Concentration-
Indoor Allergens, and Childhood Asthma.” Envi-
Response Relation Between PM2.5 and Daily
ronmental Health Perspectives 108, supplement 4
Deaths,” Environmental Health Perspectives 110
(2000): 643–646; “Secondhand Smoke—Is It a
(2002): 1025–1029; C.A. Pope III et al., “Review
Hazard?” Consumer Reports (January 1995): 27–33.
of Epidemiological Evidence of Health Effects of
C H A P T E R
5
THE DETAILED CHEMISTRY
OF THE ATMOSPHERE
topics are used:
 Lewis structures (for nonradicals)
 Activation energy; reaction mechanisms
 Basic organic chemistry (see Appendix to this book)
Background from previous chapters used in this chapter:

 Concept of free radicals (Chapter 1)
 Atmospheric structure (Chapter 1)
 Photochemical reactions (Chapters 1 and 3)
 Stratospheric chemistry (Chapters 1 and 2)
 Photochemical air pollution, smog, NOX (Chapter 3)
Introduction
In Chapters 1 through 4, we have discussed,
in broad terms, chemical processes in the
stratosphere and troposphere, emphasizing
the environmental concerns that have
arisen. In this chapter, the reactions that
occur in clean tropospheric air and the pro-
cesses encountered in the polluted air of
modern cities are analyzed in more detail. In
addition, the processes that deplete ozone in
the stratosphere are systematized. It is only
by understanding the science underlying
such complicated environmental problems
that we can hope to solve them. This Mexico City newspaper salesman wears a mask to help
One of the important characteristics protect himself from air pollution during a photochemical smog
that determines the reactivity of a species is episode. [Guillermo Gutierrez/AP]
175
176 Chapter 5 The Detailed Chemistry of the Atmosphere
BOX 5-1 Lewis Structures of Simple Free Radicals
M ost of the free radicals that are important

in atmospheric chemistry have their
unpaired electron located on a carbon, oxygen,
The procedure is more complicated in
molecules that contain multiple bonds. Thus
in HOCO it is not initially obvious whether it
hydrogen, or halogen atom. In a formula show- is the carbon or the terminal oxygen that
ing the location and position of bonds, the carries the unpaired electron. After a little
specific atomic location can be denoted by manipulation with various bonding schemes,
placing a dot above the relevant atom symbol it becomes clear that the unpaired electron
to represent the unpaired electron, e.g., in the could not be located on an oxygen, since to
notation FB . Characteristically, such an atom fulfill its valence requirement of four, the
forms one fewer bond than usual—its unpaired carbon would have to form three bonds to
electron is not in use as a bonding electron. the other oxygen. Thus the only reasonable
D
Thus a carbon atom on which an unpaired structure is H 9 O 9 C " O.
electron is located forms three rather than If only a simple formula rather than a
four bonds, an oxygen forms one rather than partial or complete Lewis structure is drawn
two bonds, and a halogen or hydrogen forms no for a radical, the superscript dot is placed
bonds if it is the radical site. Usually, the following the formula and does not indicate
unpaired electron exists as a nonbonding elec- which atom carries the unpaired electron.
tron localized on one atom, not as a bonding An example is HCOD, in which the actual
electron shared between atoms. location of the unpaired electron is at car-
For many polyatomic free radicals, the bon, not oxygen.
choice of atom to which the unpaired electron For a few free radicals involving unusual
is to be assigned in deducing the Lewis struc- bonding, such as NOD2 , these rules generate
ture is obvious from the atom–atom connec- a Lewis structure that is not the dominant one;
tions. Thus in the hydroperoxy radical HOO, further discussion of such systems is beyond
the hydrogen atom cannot be the radical site, the scope of this book.
since to be part of the molecule it must form
a bond to the adjacent oxygen; neither can the
central oxygen be the site since it must form
two bonds, one to each neighbor (or one of
them would not be part of the molecule). This PROBLEM 1
leaves the terminal oxygen as the radical site,
Draw simple Lewis structures, showing the
and we can show the bonding network as
locations of the bonds and of the unpaired elec-
H9 O9 O B . If desired, the unbonded electron
tron, for the following free radicals.
pairs can also be shown:
(a) OHD (b) CHD3 (c) CF2ClD
DD D (d) H3COO D D
(e) H3CO (f) ClOOD
H 9 O 9 OC (g) ClO D (h) HCOD (i) NOD
DD DD
whether or not it has unpaired electrons. To emphasize that an atomic or

molecular species is a free radical, in this chapter we shall place a superscript
dot at the end of its molecular formula, signaling the presence of the unpaired
electron. For example, the notation OHD is used for the hydroxyl free radical.
The position of the unpaired electron in the Lewis structure is often impor-
tant in determining the reaction of a free radical. Box 5-1 discusses the
deduction of the Lewis structure for free radicals.
Tropospheric Chemistry
The Principles of Reactivity in the Troposphere
Most gases in the troposphere are gradually oxidized by a sequence of reac-
tions involving free radicals. For a given gas, the sequence can be predicted
from the principles discussed below, which are also systematized in Figure 5-1.
These tropospheric reactions are similar in many ways to those encountered
in the stratosphere, which are discussed later in the chapter.
As mentioned in Chapter 3, the usual initial step in the oxidation of an
atmospheric gas is its reaction with the hydroxyl free radical rather than with
molecular oxygen, O2. With molecules that contain a multiple bond, the
hydroxyl radical usually reacts by adding itself to the molecule at the position
of the multiple bond. Recall the general principle that radical reactions that
are spontaneous are those which produce stable products, i.e., products con-
taining strong bonds. Thus it is understandable that OHD addition does not
occur to an oxygen atom since the O9 O bonds that would result are weak.
Similarly, OHD addition does not occur to CO double bonds since they are
very strong relative to the single O9 O or C 9 O bond that would be
produced. For example, the OHD radical adds to the sulfur atom, forming a
strong bond, but not to an oxygen atom, in sulfur dioxide, SO2:
O
O " S " O OH O"S
OH
(Here and elsewhere in this book we write Lewis structures that assume that
d orbitals in atoms such as sulfur and phosphorus allow these elements to form
double bonds.) Hydroxyl radical does not add to carbon dioxide, O " C " O,
since the molecule contains only very strong C" O bonds. However, OHD
addition does occur to the carbon atom in carbon monoxide, CO, since the
triple bond is thereby converted to the very stable double bond and a new sin-
gle bond is also formed:

C # O OH HO 9 C " O
This process is exothermic because the third C9 O bond in carbon monox-
ide is weak relative to the other two.
(a)
Yes Gas eventually
Is gas water soluble returns to
or fully oxidized? Earth’s surface
No
Does gas Yes

photodecompose
in sunlight?
No
Do gas molecules Yes Free radicals

have multiple bonds •
are produced
that OH • can add to? OH addition occurs (see Fig. 5-1b)
No
Do gas molecules
have an H that OH • Yes
can abstract in an OH • abstraction occurs
exothermic reaction?
No
Gas is inert in troposphere;

will rise to stratosphere
(b)
Does radical have Yes*

NO2• + O-centered radical
a peroxy bond? Oxidizes nitric oxide
No
Is it of type • Yes
Formaldehyde + radical
RH2C—CH2O? C—C splits
(if R is stabilizing)
No
Can H removal
from H—X convert Yes
HOO • + nonradical
X—O • (or X O) to O2 abstracts H
X O (or X O)?
No
FIGURE 5-1 (a) Decision O2 adds to radical site to

tree illustrating the fate of produce peroxy radical
gases emitted into the air.
*Under conditions with significant nitric oxide present and before radical + radical reactions
(b) Decision tree illustrating become important.
the fate of airborne free
radicals.
Generally, OHD does not add to multiple bonds in any fully oxidized
species such as CO2, SO3, and N2O5, since such processes are endothermic
and therefore are very slow to occur at atmospheric temperatures. Similarly,
N2 does not react with OHD because the component of the nitrogen-to-
nitrogen bond that would be destroyed is stronger than the N 9 O bond that
would be formed. It doesn’t react with O2 because a high activation energy is
required for this reaction to occur.
For molecules that do not have a reactive multiple bond but do contain
hydrogen, OHD reacts with them by the abstraction of a hydrogen atom to
form a water molecule and a new reactive free radical. For CH4, NH3, H2S,
and CH3Cl, for instance, the reactions are
CH4 OHD 9: CHD3 H2O

NH3 OHD 9: NHD2 H2O
H2S OHD 9: SHD H2O
CH3Cl OHD 9: CH2ClD H2O
Because the H9 OH bond formed in these reactions is very strong, the

processes are all exothermic; thus only small activation energy barriers exist
to impede these reactions (see Box 1-2).
P R O B L E M 5-1
Why aren’t gases such as CF2Cl2 (a CFC) readily oxidized in the troposphere?
Would the same be true for CH2Cl2?
P R O B L E M 5-2
The abstraction of the hydrogen atom in HF by OHDis endothermic. Comment
briefly on the expected rate of this reaction: Would it be (at least potentially)
fast, or necessarily very slow in the troposphere?
P R O B L E M 5-3
The hydroxyl radical does not react with gaseous nitrous oxide, N2O, even
though the molecule contains multiple bonds. What can you deduce about
the probable energetics (endothermic or exothermic character) of this reac-
tion from the observed lack of reactivity?
A few gases emitted into air can absorb some of either the UV-A or the
visible component of sunlight, and this input of energy is sufficient to break
one of the bonds in the molecule, thereby producing two free radicals. For
example, most molecules of atmospheric formaldehyde gas, H2CO, react by

photochemical decomposition after absorption of UV-A from sunlight:
UV-A (338 nm)
H2CO 999999999: HD HCOD
In all the cases discussed, the initial reaction of a gas emitted into air pro-
duces free radicals, almost all of which are extremely reactive. The predomi-
nant fate in tropospheric air for most simple radicals is reaction with diatomic
oxygen, often by an addition process: One of the oxygen atoms attaches, or
“adds on,” to the other reactant, usually at the site of the unpaired electron. For
instance, O2 reacts by addition with the methyl radical, CHD3 :
CHD3 O2 9: CH3OOD
Notice that CH3OOD itself is a free radical; the terminal oxygen forms
only one bond and carries the unpaired electron:
DD D D
H3C 9 O 9 OC or just H3C9 O 9 O
DD DD
Species such as HOOD and CH3OOD are called peroxy radicals since they
contain a peroxide-like O9 O bond; recall that HOOD is the hydroperoxy
radical.
As radicals go, peroxy radicals are less reactive than most. They do not
readily abstract hydrogen since the resulting peroxides would not be very sta-
ble energetically. Since the transfer of H to the peroxy radical would be
endothermic and thus would possess a large activation energy, abstraction
reactions for peroxy radicals are usually so slow that they are of negligible
importance (in contrast to those for OHD). Peroxy radicals in the tropo-
sphere do not react with atomic oxygen because of the extremely low
concentrations of the free atom in this region of the atmosphere. The most
common fate of peroxy radicals in tropospheric air, except for the cleanest
type of air, such as that over oceans, is reaction with nitric oxide, NOD, by
the transfer of the “loose” oxygen atom (see the later section on stratospheric
chemistry), thereby forming nitrogen dioxide, NOD2 , and a radical that has
one fewer oxygen atoms:
HOOD NOD 9: OHD NOD2

CH3OOD NOD 9: CH3OD NOD2
It is by this type of reaction that most atmospheric NOD is oxidized to NOD2 , at least
in polluted air. Recall that this reaction also is typical of the types
encountered in stratospheric chemistry (see Chapters 1 and 2) and that NOD
oxidation by ozone in sunlit conditions yields a null reaction.
For free radicals that contain nonperoxy oxygen atoms, the reaction with
molecular oxygen frequently involves the abstraction of an H atom by O2.
This process occurs provided that, as a result, another new bond within the
system is formed: A single bond involving oxygen is converted to a double one,
or a double bond involving oxygen is converted to a triple one. As examples,
consider the three reactions below in which a C 9O single (or double) bond
is converted to a double (or triple) one as a consequence of the loss of a
hydrogen atom:
CH3 9 OB O2 9: H2C"O HOOD
HO 9 CB "O O2 9: O" C"O HOOD
D
H9 C 9 O O2 9: C # O HOOD
Such processes do not occur unless a new bond is created in the product free
radical, since the strength of the newly created H 9 OO bond alone is not
sufficient to compensate for the breaking of the original bond to hydrogen.
If there is no suitable hydrogen atom for O2 to abstract, then when it
collides with a radical, it instead adds to it at the site of the unpaired elec-
tron, as was previously discussed for simple radicals. For example, radicals of
the type R9 CB " O, where R is a chain of carbon atoms, add O2 to form a
peroxy radical:
O
R9 C " O O2 R9C
O9O
The only exception to the generalization that oxygen-containing radicals
react with O2 occurs when the radical can decompose spontaneously in a
thermoneutral or exothermic fashion. An example of this rare phenomenon is
discussed later in the section on photochemical smog.
These generalizations are summarized in the form of the decision trees
diagrammed in Figure 5-1. By using these diagrams you can deduce the
sequence of reactions by which most atmospheric gases in the troposphere are
oxidized.
The Tropospheric Oxidation of Methane

Gaseous methane, CH4, is released into the atmosphere in large quantities as
a result of anaerobic (i.e., O2-free) biological decay processes and of the use of
coal, oil, and, especially, natural gas. It is the predominant hydrocarbon in the
atmosphere. Details concerning its production, and the effects on climate of
atmospheric methane, are discussed in Chapter 6. Here, however, we shall be
concerned with its conversion to carbon dioxide. A similar series of reactions
is followed by other alkanes and other VOCs lacking multiple bonds.
The sequence of reactions by which methane is slowly oxidized in the

atmosphere can be deduced by applying the principles outlined above and
summarized in Figure 5-1, as discussed below.
Since CH4 is not very soluble in water, does not absorb sunlight, and
contains no multiple bonds, the sequence is initiated by a hydroxyl radical
abstracting a hydrogen atom from a methane molecule, giving the methyl
radical, CHD3 :
CH 4 OHD 9: CHD3 H2O (1)
Since the CHD3 radical contains no oxygen, we deduce that it adds O2, pro-
ducing a peroxy radical:
CHD3 O2 9: CH3OOD (2)
Further, since CH3OOD is a peroxy radical, we deduce that except in very

clean air, it reacts with NOD molecules in air to oxidize them by transfer of an
oxygen atom:
CH3OOD NOD 9: CH3OD NOD2 (3)
The radical CH3OD contains a C9 O bond that can become C " O upon loss
of one hydrogen, so we conclude from our principles that in the next step O2
abstracts an H atom, producing the nonradical product formaldehyde, H2CO:
CH3OD O2 9: H2CO HOOD (4)
Thus methane is converted to formaldehyde as the first stable inter-

mediate in its oxidation. Since formaldehyde is reactive as a gas in the
atmosphere, the mechanism is not complete at this point. After several
hours or days in the sunlight, most formaldehyde molecules decompose
photochemically by the absorption of UV-A from sunlight, resulting in
the cleavage of a C 9 H bond and the consequent formation of two
radicals:
UV-A (338 nm)
H2CO 999999999: HD HCOD (5)
A minority of formaldehyde molecules react with OHD by H atom

abstraction, yielding the same HCOD radical; see Problem 5-7 for the impli-
cations of this alternative route.
The hydrogen atom from formaldehyde photolysis is itself a simple
radical, and therefore it reacts by addition to O2 to yield HOOD:
HD O2 9: HOOD (6)
Meanwhile, the H9 CB " O radical reacts by yielding an HD atom CH4

to O2, to produce carbon monoxide and HOOD, since by this route
OH
a double bond is converted to a triple one: H2O
HCOD O2 9: CO HOOD (7)

CH3
Thus carbon monoxide also is an intermediate in the oxidation of O2

methane. Indeed, most of the CO in a clean atmosphere is derived
from this source. Since CO is not a radical and does not absorb visi-
ble or UV-A light, we deduce that it reacts ultimately by hydroxyl CH3OO
radical addition to its triple bond:
NO
NO2
C # O OH H9O9C"O (8)
This radical can convert its O9 C bond to O " C by loss of H, so CH3O

we deduce that O2 readily abstracts the hydrogen: O2
HOO
H 9 O9 CB " O O2 9: O" C " O HOOD (9)
H2CO
Carbon in its fully oxidized form of carbon dioxide is ultimately
produced from methane by this sequence of steps, which are sum- UV-A
H !: HOO
O2
marized in Figure 5-2. If we add up the nine steps involved and can-
cel common terms, the overall reaction is seen to be
HCO
CH4 5 O2 NOD 2 OHD 99:
UV-A
O2
CO2 H2O NOD2 4 HOOD HOO
If to this result is added the conversion of the four HOOD radicals CO

back to OHD by reaction with four NOD molecules, the revised
overall reaction is OH
UV-A
CH4 5 O2 5 NOB 99: CO2 H2O 5 NO2B 2 OHB
HOCO
We conclude that NOD is oxidized to NOD2 synergistically, i.e., in a O2

mutually cooperative process, when methane is oxidized to carbon HOO
dioxide. Note also that the number of OHD free radicals is increased
as a result of the process, due to the photochemical decomposition CO2
of formaldehyde. Thus hydroxyl radical is not only a catalyst in the
overall reaction but also a product of it. FIGURE 5-2 Steps in the
The initial step of the mechanism — the abstraction by OHD of a hydrogen
atmospheric oxidation of
methane to carbon dioxide.
atom from methane — is a slow process, requiring about a decade to occur on
average. Once this has happened, however, the subsequent steps leading to
formaldehyde occur very rapidly. The slowness of the initial step in methane
Combustion of C-containing oxidation, and the increasing amounts of the gas released from
substances the surface of the Earth, have led to an increase in the atmo-
spheric concentration of CH4 in recent times, as discussed
CH4 !: H2CO !: CO !: CO2 further in Chapter 6.
Under conditions of low nitrogen oxide concentration,
H2S !: SO2 !: H2SO4 such as occur over oceans, the mechanism of methane oxida-
tion differs in some of the steps. In particular, instead of oxidiz-
S in coal or oil ing NOD, the peroxy radicals often react with each other,
combining to produce a (nonradical) peroxide:
NH3 !: NO !: NO 2 !: HNO3 2 HOD2 9: H2O2 O2
N2 in air via (Other

Under these conditions, then, the oxidation of methane in
combustion nitrates) clean air decreases, rather than increases, the concentration of
free radicals.
In general, during the atmospheric oxidation of any of the
(O from NO 2) !: O3 !: O2
hydrides (simple hydrogen-containing molecules such as CH4,
H2S, and NH3), one or more stable species are encountered
(Free radicals) !: H2O2 !: H2O O2 along the reaction sequence before the totally oxidized prod-
uct is formed. These intermediates are also formed independ-
FIGURE 5-3 Stable
species (i.e., nontransients)
ently by various pollution processes. Figure 5-3 summarizes the sequences for
and their additional hydrides and partially oxidized materials from the viewpoint of the stable
sources during sequential species; close reflection will persuade you that the net result is the OHD-
atmospheric oxidation induced oxidation of the reduced and partially oxidized gases emitted into the
processes. air from both natural and pollution sources. In a few cases, for instance, for
methane and methyl chloride, the initiation reaction is sufficiently slow that
a few percent of these gases survive long enough to penetrate to the strato-
sphere by the upward diffusion of tropospheric air. Most hydrocarbons react
much more quickly than methane (since their C ¬ H bonds are weaker, or
fast reactions with OHD other than by hydrogen abstraction are possible)
and are classified as nonmethane hydrocarbons (NMHC) to emphasize this
distinction.
P R O B L E M 5-4
Using the reaction principles developed above (the decision trees in Figure 5-1
will help here), predict the sequence of reaction steps by which atmospheric
H2 gas will be oxidized in the troposphere. What is the overall reaction?
P R O B L E M 5-5
Deduce two short series of steps by which molecules of methanol, CH3OH,
are converted to formaldehyde, H2CO, in air. The mechanisms should differ
according to which hydrogen atom you decide will react first, that of CH3 or
that of OH.
P R O B L E M 5-6
Write equations showing the reactions by which atmospheric carbon monox-
ide is oxidized to carbon dioxide. Then, by adding the process by which
HOOD is returned to OHD, deduce the overall reaction.
P R O B L E M 5-7
Deduce the series of steps, and the overall reaction as well, for the oxidation of
a formaldehyde molecule to CO2, assuming that for the particular H2CO mole-
cule involved, the initial reaction is abstraction of H by OHD rather than
photochemical decomposition. Overall, is there any increase in the number of
free radicals as a result of the oxidation if it proceeds in this manner?
Photochemical Smog: The Oxidation

of Reactive Hydrocarbons
Notwithstanding the great complexity of the process, the most important fea-
tures of the photochemical smog phenomenon can be understood by consid-
ering only its few main categories of reactions; these differ in speed, but not
much in type, from those occurring in clean air.
We shall restrict our attention to the most reactive VOCs, namely
hydrocarbons that contain a C " C bond. (Readers unfamiliar with the basics
of organic chemistry are advised to consult the Appendix, where the nature
of such molecules is explored.) The simplest example is ethene (ethylene),
C2H4; its structure can be written in condensed form as H2C" CH2; its full
structural formula is
H H
C"C
H H
In similar hydrocarbons, one or more of the four hydrogens are replaced by
other atoms or groups, often an alkyl group containing a short chain of carbon
atoms such as CH3 9 or CH3CH2 9 , which will be designated simply as R,
since it is generally not the chain but rather the C "C part of the molecule
that is the reactive site in atmospheric reactions.
Consider a general hydrocarbon RHC " CHR. In air it reacts with
hydroxyl radical by addition to the C " C bond:
R R R R
C"C OH C 9 C 9 OH
H H H H
This addition reaction is a faster process, due to its lower activation energy,
than the alternative of abstraction of hydrogen, so we can neglect the
abstraction process in molecules containing a C" C link. Because the reac-
tion of addition of OHD to a multiple bond is much faster than H abstraction
from methane and other alkane hydrocarbons, RHC " CHR molecules in
general are much faster to react than are alkanes.
As anticipated from the reaction principles, the carbon-based radical
produced from the reaction of hydroxyl radical with the hydrocarbon adds O2
to yield a peroxy radical, which in turn oxidizes NOD to NOD2 :
O
R R O R O R
R R
O2 NO
C 9 C 9 OH C 9 C 9 OH NO2 C 9 C 9 OH
H H H H H H
Once much of the NOD has been oxidized to NOD2 , photochemical

decomposition by sunlight of the latter gives NOD plus O, which then quickly
combines with molecular oxygen to give ozone, as discussed in Chapter 3. It is
a characteristic of air pollution driven by photochemical processes that ozone
from NOD2 photodecomposition builds up to much higher levels than are found
in clean air. Nitrogen dioxide is the only significant tropospheric source of the
atomic oxygen from which ozone can form.
As mentioned previously, the ozone concentration does not build up
substantially as a result of this sequence until most of the NOD has been con-
verted to NOD2 , since NOD and O3 mutually self-destruct if both are present in
significant concentrations. It is only after most NOD has been oxidized to NOD2
as a result of reactions with peroxy free radicals that the characteristic buildup of
urban ozone occurs, as can be seen in Figure 3-4; the transition that occurred at
about 9 A.M. on a particular smoggy day in the 1960s in Los Angeles (when smog
levels were higher than in more recent years) is illustrated.
One might anticipate from our reactivity principles (Figure 5-1) that
the two-carbon radical mentioned above (RCHO B CH(R)OH) would lose H by
abstraction by O2, but instead it decomposes spontaneously by cleavage of the
C9 C bond to give a nonradical molecule containing a C" C bond and
another radical, RHCB OH:
O R R OH
R
C 9 C 9 OH C"O R9C
H H H H
It happens that the reaction requires no energy input, i.e., H is close to zero,
because in this case the formation of a C " O bond from C9 O compensates
energetically for loss of the C 9C bond. Since the decomposition of this rad-
ical is not endothermic, its activation energy is small and thus the process
occurs spontaneously in air.
The carbon-based radical RHCB OH produced in the preceding reaction
subsequently reacts with an O2 molecule. Since loss of the hydroxyl hydrogen
from this radical allows the C 9 O bond to become C "O, the oxygen mole-
cule abstracts the H atom and produces an aldehyde.
OH R
R9C O2 HOO C"O
H H
If we add all the above reactions, the net reaction thus far is
RHC " CHR OHD 2 O2 NOD 9: 2 RHC " O HOOD NOD2
Thus the original RHC "CHR pollutant molecule is converted into two
aldehyde molecules, each possessing half the number of carbon atoms.
Indeed, as shown in Figure 3-4, by about noon on the very smoggy day in Los
Angeles, most of the reactive hydrocarbons emitted into the air by morning
rush-hour traffic had been converted to aldehydes. By midafternoon, most of
the aldehydes had disappeared, since they had largely been photochemically
decomposed into HCOD and RD (alkyl) free radicals.
RHCO 999: RD HCOD

sunlight
The sunlight-induced decomposition of aldehydes and of ozone leads to a

huge increase in the number of free radicals in the air of a city undergoing
photochemical smog, although in absolute terms the concentration of radi-
cals is still very small.
The steps in the conversion of the original RHC " CHR molecule into
aldehydes, and then of the latter to carbon dioxide (see Problem 5-8), are sum-
marized in Figure 5-4. As indicated by the results of Problem 5-8, the net effect
of the synergistic oxidation of nitric oxide and RHC " CHR is the production
of carbon dioxide, nitrogen dioxide, and more hydroxyl radicals. Thus the
reaction is autocatalytic — its net speed will increase with time since one of its
products, here OHD, catalyzes the reaction for other reactant molecules.
P R O B L E M 5-8
Rewrite the net reaction shown above for RHC " CHR, assuming that R is
H. Deduce the series of steps by which the formaldehyde molecules will
RHC " CHR
(1) OH

RHC 9 CH(OH)R
(2) O2

RHC(9 O 9 O) 9 CH(OH)R
(3) NO
NO2
RHC(9 O ) 9 CH(OH)R
Spontaneous cleavage
(4) of C 9 C bond
(5)

RHC " O RHCOH
O2
HOO
RHC " O
(6) UV

R HCO
(7a) O2 (7b) O2
CO
ROO HOO
(8a) NO (8b) NO
FIGURE 5-4 Mechanism
of the RHC "CHR
oxidation process in
photochemical smog. NO2 RO OH NO2
subsequently undergo photochemical decomposition and, by a further series

of steps, be oxidized to carbon dioxide. Add these steps to the net reaction.
Also add the reactions by which HOOD oxidizes NOD. What is the final net
reaction obtained by adding all these processes together?
P R O B L E M 5-9
Repeat Problem 5-8, but this time assume that the alkyl group R in the
aldehyde RHCO produced by photochemical smog is a simple methyl group,
CH3, and that, when the aldehyde undergoes photochemical decomposition
by sunlight, the radicals CHD3 and HCOD are produced. Using the air reactiv-
ity principles, deduce the sequence of reactions by which these radicals are
oxidized to carbon dioxide, and determine the overall reaction of conversion
of RHCO to CO2. Assume formaldehyde photolyzes.
Photochemical Smog: The Fate of the Free Radicals

In later stages of photochemical smog formation, reactions that occur
between two radicals are no longer insignificant, since their concentrations
have become so high. Because their rates are proportional to the product of
two radical concentrations, these processes are important when the radical
concentrations are high; i.e., they occur quickly under such conditions.
Generally, the reaction of two free radicals yields a stable, nonradical
product:
radical radical 9: nonradical molecule
One important example of a radical – radical reaction is the combination

of hydroxyl and nitrogen dioxide radicals to yield nitric acid, HNO3, a process
that, as we saw in Chapter 1, also occurs in the stratosphere:
OHD NO2B 9: HNO3
This reaction is the main tropospheric sink for hydroxyl radicals. The average
lifetime for an HNO3 molecule is several days. By then it either has dissolved
in water and been rained out or has been photochemically decomposed back
into its components.
Similarly, combination of OHD with NOD gives nitrous acid, HONO,
also written HNO2. In sunlight the nitrous acid is almost immediately
photochemically decomposed back to OHD and NOD, but at night it is sta-
ble and therefore its concentration climbs. The observed gigantic increase
by dawn in the concentration of OHD radicals in the air of smog-ridden
cities, which serves to start the oxidation of hydrocarbons, is due largely to
the decomposition of the HONO that had been created the previous
evening:
OHD NOD 9: HONO 999: OHD NOD

sunlight
It is a characteristic of the later stages in the day of a smog episode that

oxidizing agents such as nitric acid are formed in substantial quantities.
The reaction of two OHD radicals, or of two hydroperoxy radicals, HOOD,
produces another atmospheric oxidizing agent, hydrogen peroxide, H2O2,
which, as we have already seen, is also produced in this way in clean atmo-
spheres devoid of nitrogen oxides:
2 OHD 9: H2O2
2 HOOD 9: H2O2 O2
The latter reaction occurs also in clean air when the concentration of
NOX is especially low and was encountered in stratospheric chemistry in
Chapter 1.
The fate of the R 9CB "O radicals, produced by H atom abstraction by
OHD from aldehydes in the ways discussed above, is to combine with O2 and
so produce the free radical
O
R9C
O9O
When NOD is plentiful, this complex species, as expected, behaves as a

peroxy radical and oxidizes nitric oxide. In the afternoon, when the concen-
tration of NOD is very low, the radical reacts instead in a radical – radical
process by adding to NOD2 to yield a nitrate. For the common case for which
R is CH3, the nitrate product formed is peroxyacetylnitrate, or PAN, which
is a potent eye irritant in humans and is also toxic to plants.
O O
CH39 C NO2 CH39 C
O9O O 9 O 9 NO2
PAN
Overall then, the afternoon stage of a photochemical smog episode is charac-

terized by a buildup of oxidizing agents such as hydrogen peroxide, nitric acid,
and PAN, as well as ozone.
Another important species that is present in the later stages of smog

episodes is the nitrate radical, NOD3 , produced when high concentrations of
NOD2 and ozone occur simultaneously:
NOD2 O3 9: NOD3 O2
Although NOD3 is photochemically dissociated to NOD2 and O rapidly during

the daytime, it is stable at night and plays a role similar to OHD in attacking
hydrocarbons in the hours following sundown:
NOD3 RH 9: HNO3 RD
Thus at night, when the concentration of the short-lived hydroxyl radicals

goes almost to zero since no new ones are being produced due to the absence
of O*, NOD3 rather than OHD initiates the oxidation of reduced gases in the
troposphere. The similarity between OHD and NOD3 is not surprising since
both react as 9 O B radicals and form very stable O 9 H bonds when they
abstract hydrogens.
In summary, an episode of photochemical smog in a city such as Los
Angeles begins at dawn, when sunlight initiates the production of hydroxyl
radicals from the nitrous acid and from the ozone left over from the previous
day. The initial input of nitric oxide and reactive hydrocarbons from morning
rush-hour vehicle traffic reacts first to produce aldehydes (see Figure 3-4),
the photolysis of which increases the concentration of free radicals and
thereby speeds up the overall reaction. The increase in free radicals in the
morning serves to oxidize the nitric oxide to nitrogen dioxide; photolysis of
the latter causes the characteristic rise in ozone concentrations about mid-
day. Oxidants such as PAN and hydrogen peroxide are also produced,
especially in the afternoons due to the high free-radical concentration pres-
ent at that time. The late afternoon rush-hour traffic produces more nitric
oxide and hydrocarbons, which presumably react quickly under the condi-
tions of high free-radical concentration. The smog reactions largely cease at
dusk due to the lack of sunlight, but some oxidation of hydrocarbons contin-
ues due to the presence of the nitrate radical. The nitrous acid that forms
after dark is stable until dawn, when its decomposition helps initiate the
process for another day.
P R O B L E M 5-10
Annotate (in pencil) the top of Figure 3-4 to show the dominant reaction
occurring in the polluted air in the following time segments: (a) 5 A.M. – 8 A.M.;
(b) 8 A.M. – 12 noon.
P R O B L E M 5-11
Some formaldehyde molecules photochemically decompose to the molecular
products H2 and CO rather than to free radicals. Deduce the mechanism and
overall reaction for the oxidation to CO2 for formaldehyde molecules that
initially produce the molecular products.
P R O B L E M 5-12
Deduce the series of steps by which ethylene gas, H2C "CH2, is oxidized to
CO2 when it is released into an atmosphere undergoing a photochemical
smog process. Assume in this case that aldehydes react completely by photo-
chemical decomposition rather than by OHD attack.
P R O B L E M 5-13
Radical – radical reactions can also occur in clean air, particularly when the
nitrogen oxide concentration is very low. Predict the product that will be
formed when the CH3OOD radical intermediate of methane oxidation
combines with the HOOD free radical. Note that long oxygen chains are
unstable with respect to O2 expulsion.
Oxidation of Atmospheric SO2: The Homogeneous

Gas-Phase Mechanism
When the sky is clear or when clouds occupy only a few percent of the
tropospheric volume, the predominant mechanism for the conversion of SO2 to
H2SO4 is a homogeneous gas-phase reaction that occurs by several sequential
steps. As usual for atmospheric trace gases, the hydroxyl radical initiates the
process. Since SO2 molecules contain multiple bonds but no hydrogen, it is
expected (see Figure 5-1) that the OHD will add to the molecule at the sulfur
atom:
O
O " S " O OH O"S
OH
Since a stable molecule, namely sulfur trioxide, SO3, can be produced from
this radical by the removal of the hydrogen atom, the reaction principles
predict that the next reaction in the sequence is that between the radical and
an O2 molecule to abstract H:
O O
O"S O2 HOO O " S
OH O
The sulfur trioxide molecule rapidly combines with a gaseous water molecule
to form sulfuric acid. Finally, the H2SO4 molecules react with water, whether
in the form of water vapor or as a mist, to form an aerosol of droplets, each of
which is an aqueous solution of sulfuric acid. The sequence of steps from
gaseous SO2 to aqueous H2SO4 is
SO2 OHD 9: HSOD3

HSOD3 O2 9: SO3 HOOD
SO3 H2O 9: H2SO4(g)
H2SO4(g) many H2O 9: H2SO4(aq)
The sum of these reaction steps is
SO2 OHD O2 many H2O 9: HOOD H2SO4(aq)
When we include the return of HOOD to OHD via reaction with NOD, the
overall reaction is seen to be OHD-catalyzed co-oxidation of SO2 and NOD:
D
SO2 NOD O2 many H2O 999999: NOD2 H2SO4(aq)
OH catalysis
For representative concentrations of the OHD radical in relatively clean

air, a few percent of the atmospheric SO2 is oxidized per hour by this mecha-
nism. The rate is much faster for air masses undergoing photochemical smog
reactions since the concentration of OHD there is much higher. However,
generally only a small amount of sulfur dioxide is oxidized in cloudless air; the
rest is removed by dry deposition before the reaction has time to occur.
Dissolved sulfur dioxide, SO2, is oxidized to sulfate ion, SO42, by trace
amounts of the well-known oxidizing agents hydrogen peroxide, H2O2, and
ozone, O3, that are present in the airborne droplets, as already discussed in
Chapter 3. Indeed, such reactions currently are thought to constitute the main
oxidation pathways for atmospheric SO2, except under clear sky conditions
when the gas-phase homogeneous mechanism predominates. The ozone and
hydrogen peroxide result mainly from sunlight-induced reactions in photo-
chemical smog. Consequently, oxidation of SO2 occurs most rapidly in air that
has also been polluted by reactive hydrocarbons and nitrogen oxides. Since
the smog reactions occur predominantly in summer, rapid oxidation of SO2 to
sulfate also is characteristic of the summer season.
Systematics of Stratospheric Chemistry

There are many similarities between the chemical reactions discussed in Chap-
ters 1 and 2 for the stratosphere and those outlined above for the troposphere.
For example, a characteristic process in both regions of the atmosphere is
hydrogen atom abstraction. The stratosphere and troposphere differ, however,
in which reactions are dominant. In the stratosphere OHD, O*, ClD, and BrD
are all important in abstracting a hydrogen atom from stable molecules such as
methane, whereas only the hydroxyl and nitrate radicals are important in this
respect in the troposphere. In the following material we systematize the Chap-
ters 1 and 2 chemistry that is important in the stratosphere, especially in
regard to processes of ozone depletion.
Processes Involving Loosely Bound Oxygen Atoms

Many of the species in the stratosphere have a loosely bound oxygen atom,
denoted Y, which is readily detached from the rest of the molecule in several
characteristic ways. In Table 5-1 we list the molecules Y 9 O that contain a
loose oxygen. In every case, dissociation of this oxygen atom requires much less
energy than is required to break any of the remaining bonds, so the resulting
Y units remain intact. Notice that the Y species, except for O2, are the free
radicals that in Chapters 1 and 2 we called X when we discussed ozone destruc-
tion catalysts. In terms of electronic structure, all “loose” oxygens are joined by
a single bond to another electronegative atom that possesses one or more
TABLE 5-1 Molecules Containing Loose Oxygen Atoms
Molecule Structure of Y 9O Bond

Y9 O Y9 O Energy in kJ/mol Comment
O3 O2 9 O 107 The most loose

oxygen
BrOD Br 9O 235
HOOD HO 9O 266
ClOD Cl 9O 272
NOD2 ON 9O 305 The least loose
oxygen
Systematics of Stratospheric Chemistry 195
nonbonding electron pairs. The interaction between the nonbonded electron

pairs on this atom and those on the oxygen weakens the single bond.
The characteristic reactions involving loose oxygen are collected below.
• Reaction with Atomic Oxygen Here the oxygen atom detaches the loose
oxygen atom by combining with it:
Y9 O O 9: Y O2
These reactions are all exothermic since the O " O bond in O2 is much
stronger than the Y9 O bond.
• Photochemical Decomposition The Y9 O species absorbs UV-B, and in
some cases even longer wavelength light, from sunlight and subsequently
releases the loose oxygen atom:
Y 9 O sunlight 9: Y O
• Reaction with NOª Nitric oxide abstracts the loose oxygen atom:
Y 9O NOD 9: Y NOD 2
This reaction is exothermic since the ON9 O bond strength (see Table 5-1)
is the greatest of those involving a loose oxygen. (Recall the general prin-
ciple that exothermic free-radical reactions are relatively fast.)
• Abstraction of Oxygen from Ozone Abstraction of the loose oxygen atom
from ozone (only) to form the Y9 O species is characteristic of OHD, ClD, BrD,
and NOD. Thus all these radicals act as catalytic ozone destroyers, X:
O2 9 O X 9: O2 XO
The reaction involving ozone is exothermic since ozone contains the weakest
of the bonds involving a loose oxygen. The other YO species do not undergo
this reaction to an important extent either because it is endothermic and
therefore negligibly slow or because the atmospheric X species react more
quickly with other chemicals.
• Combination of Two YO Molecules If the concentration of YO species
becomes high, they may react by the collision of two of them (identical or differ-
ent species). If at least one is O3 or HOOD, an unstable chain of three or more
oxygen atoms is created when they collide and join; in these circumstances, the
loose oxygens combine to form one or more molecules of O2, which are expelled:
2 O2 9 O 9: 3 O2
2 HO 9 OD 9: HOOH O2
HO 9OD O9 O2 9: OHD 2 O2
HO 9ODDO 9Cl 9: HOCl O2
When neither is O3 or HOOD, the two Y 9 O molecules combine to form

a larger molecule, which subsequently often decomposes photochemically:
2 NOD2 9: N2O4
2 ClOD 9: ClOOCl99: 9: 2 ClD O2
sunlight
sunlight
ClOD NOD2 ERRF ClONO2
ClOD BrOD 9: ClD BrD O2
The Y9 O9 O 9Y molecules have little thermal stability, and even at mod-

erate temperatures they may dissociate back to their Y 9 O components
before light absorption and photolysis have time to occur.
P R O B L E M 5-14
Which of the following species do(es) not contain a loose oxygen?
(a) HOOD (b) OHD (c) NOD (d) O2 (e) ClOD
P R O B L E M 5-15
From which Y 9O species
(a) does NOD abstract an oxygen atom?
(b) does atomic oxygen abstract an oxygen atom?
(c) does sunlight in the stratosphere detach an oxygen atom?
(d) do the Y9 O9 O9Y species (with identical Y groups) form in the
stratosphere?
(e) is O2 produced when two identical Y 9 O species react?
P R O B L E M 5-16
Using the principles above, predict what would be the likely fate of BrOD
molecules in a region of the stratosphere that in concentrations was particu-
larly (a) high in atomic oxygen, (b) high in ClOD, (c) high in BrOD itself, and
(d) high in sunlight intensity.
P R O B L E M 5-17
Using the principles above, deduce what reaction(s) could be sources of
atmospheric (a) ClONO2 (b) ClOOCl (c) ClD atoms
P R O B L E M 5-18
Draw the Lewis structure for the free radical FOD. On the basis of this struc-
ture, could you predict whether it contains a loose oxygen?
P R O B L E M 5-19
What is the expected product when ClOD reacts with NOD? What are the
possible fates of the product(s) of this reaction? Devise a mechanism
incorporating (a) this reaction, (b) the reaction of ClD with ozone, and
(c) the photochemical decomposition of NOD2 to NOD and atomic oxygen. Is
the net result of this cycle, which operates in the lower stratosphere, the
destruction of ozone?
Review Questions
1. Explain why OHD reacts more quickly than 7. What is the fate of OHD radicals that react
HOOD to abstract hydrogen from other with NOD? With NOD2 ? With other OHD?
molecules.
8. What is the fate of NOD2 molecules that
2. How does OHD react with molecules that photodissociate? That react with ozone? That react
contain hydrogen but not multiple bonds? with RCOOD radicals?
3. What are the two different initial steps by 9. Why does the production of high concentrations
which atmospheric formaldehyde, H2CO, is of NOD2 lead to an increase in ozone levels in air?
decomposed in air? Why does this not occur if much NOD is present?
4. What is the reaction by which most nitric 10. What is the formula of nitrate radicals? Explain
oxide molecules in the troposphere are oxidized how they are similar in reactivity to hydroxyl
to nitrogen dioxide? radicals.
5. What are the two common reactions by which 11. Explain how atmospheric sulfur dioxide is
diatomic oxygen reacts with free radicals? oxidized by gas-phase reactions in the atmosphere.
6. Explain why photochemical smog is an 12. Explain what is meant by the term loosely
autocatalytic process. bound oxygen. What are its four characteristic
reactions in stratospheric chemistry?
Additional Problems
1. Write the two-step mechanism by which CO is overall reaction by which ethane, H3C9CH3,
oxidized to CO2. Also include the sequence of is oxidized in the atmosphere. Assume that the
reactions by which the hydroperoxy radical so aldehydes produced in the mechanism undergo
produced oxidizes NOD to NOD2, the nitrogen photochemical decomposition to RD and HCOD.
dioxide is photolyzed to NOD and atomic oxygen,
3. When the concentration of nitrogen oxides in
and oxygen atoms produce ozone. By adding the
a region of the air is very low, peroxy radicals
steps, show that the atmospheric oxidation of
combine with other species rather than oxidize
carbon monoxide can increase the ozone
nitric oxide. Deduce the mechanism, including
concentration by a catalytic process.
the overall equation, for the process by which
2. Using the reactivity principles developed in carbon monoxide is oxidized to carbon dioxide
this chapter, deduce the series of steps and the under these conditions, assuming that the
hydroperoxy radicals react with ozone. From your 5. Draw complete Lewis structures for NO2,
result, would you predict that ozone levels would HONO, and HNO3. (Resonance structures and
be abnormally high or low in air masses having formal charges are not required.)
low nitrogen oxide concentration? [Hint: See the
6. In Problem 1-2, the longest wavelength of light
generalities in the section on the systematics of strato-
that could dissociate an O atom from O3 was calcu-
sphere chemistry concerning reactions that produce long
lated and determined to occur in the IR region of the
oxygen chains.]
spectrum. Using the information in Table 5-1, calcu-
4. Predict the most likely reaction (if any) that late the longest wavelength of light that could pho-
would occur between a hydroxyl radical and each tolytically cleave the loose hydrogen atom in the case
of the following atmospheric gases: of each of the remaining molecules listed in that
(a) CH3CH2CH3 (b) H2C"CHCH3 table. What region of the electromagnetic spectrum
(c) HCl (d) H2O does each correspond to?
Further Readings
1. R. Atkinson, “Atmospheric Chemistry of Airborne Toxics, Polycyclic Aromatic Hydro-
VOCs and NOX,” Atmospheric Environment 34 carbons, and Particles,” Science 276 (1997):
(2000): 2063 – 3101. 1045 – 1051.
2. B. J. Finlayson-Pitts and J. N. Pitts, 4. J. H. Seinfeld and S. N. Pandis, Atmospheric
Atmospheric Chemistry (New York: Wiley, 1986). Chemistry and Physics (New York: Wiley, 1998).
[A comprehensive guide to the detailed chemistry [Another comprehensive guide to the detailed
of the atmosphere.] chemistry of the atmosphere.]
3. B. J. Finlayson-Pitts and J. N. Pitts, Jr.,
“Tropospheric Air Pollution: Ozone,
Log on to www.whfreeman.com/envchem4e/ and click on Chapter 5.
Instrumental Determination of NOX via Chemiluminescence 199
Environmental Instrumental Determination of NOX

Instrumental
Analysis I
via Chemiluminescence
In the preceding chapters, we have seen that nitro- reaction vessel by use of a vacuum pump that
gen oxides play a leading role in atmospheric constantly evacuates the chamber. Typical cell
chemistry, both in the stratosphere and at ground pressures are approximately 1 to 100 torr. The
level. In this box, we see how the concentration of amount of light produced in the reaction is
NO and NO2 gases in environmental air samples proportional to the amount of whichever reac-
can be determined using a sophisticated, modern tant is not in excess in the reaction chamber.
method of analysis. If ozone is provided in excess (from a steady
ozone generator in this case), then the light
hen chemicals react to produce light,
W the process is termed chemilumines-
cence. If conditions for a particular reaction
output reflects changes in NO concentration.
The light created by the reaction is detected by
a photomultiplier tube (PMT) whose output is
are well known and can be controlled in an
fed to a computer system. The computer soft-
analytical instrument, chemiluminescence can
ware correlates the amount of light produced
be used as a sensitive and selective means of
with the quantity of reactant by referring to the
determining the concentration of components
relation between light intensity and NO con-
in the reaction. A few well-known chemical
centration, which is obtained from previous
reactions that produce chemiluminescence
calibration experiments. In instruments of this
are the basis for methods in tropospheric and
kind, the PMT signal is often integrated over
stratospheric environmental analysis. One of
short time periods (e.g., 10 seconds) using
the most common of these methods is the
what is referred to as a photon counting sys-
detection of nitric oxide (NO) and nitrogen
tem, which improves sensitivity.
dioxide (NO2).
The schematic diagram of this instrument,
The chemiluminescence reaction that
shown in the figure below, includes the reaction
produces light in this method is the gas-phase
chamber, ozone generator, PMT, computer, and
reaction of NO with ozone (O3):
NO O3 9: NO2* O2
In the NO detector, this reaction takes place Atmospheric air in
in a small steel reaction vessel under controlled
conditions. The excited-state nitrogen dioxide Light emission
created in this reaction, designated by NO2*,
very quickly returns to ground state by giving Reaction Vacuum
off light in the red and infrared range of the
Computer PMT
* chamber pump
light spectrum (600 to 2800 nanometers):
NO2* 9: NO2 light (l 600 to 2800 nm) O3
The amount of light produced by this reaction O3 generator

is dependent on pressure and temperature. A
constant low pressure is maintained in the
200 Environmental Instrumental Analysis I
Environmental Instrumental Determination of NOX

Instrumental
Analysis I
via Chemiluminescence (continued)
vacuum pump. Gas from the atmosphere is gas-phase components also commonly present,
sucked directly into the reaction chamber and such as NH3, can be minimized by decreasing
immediately mixed with an excess of O3 (i.e., the temperature in the catalyst chamber
more O3 than NO). Typical sampling volumes described above (Environmental Protection
are 1000 standard cubic centimeters per minute National Service, 2000).
(sccm). Some instruments have gold-plated Instruments of this kind have been used on
surfaces inside to prevent surface reactions and airplane-based stratospheric and tropospheric
increase the light-collection abilities of the sampling projects by the National Atmospheric
light chamber. The light produced is detected and Space Administration and the National
by the PMT mounted immediately adjacent to Center for Atmospheric Research. Similar
the reaction chamber and separated by a trans- instrumentation has been used for tropospheric
parent window or a filter that can block out studies of urban pollution, using laboratory-
light from interfering reactions. based “smog chambers,” and in indoor air
This same instrument can be used to pollution studies.
determine NO2 by incorporating a chemical The figure below shows the variation in
reduction step for the incoming air, in which concentration of NO as an airborne scientific
NO2 is reduced to NO by a hot metal catalyst expedition equipped with this kind of NO
before entering the reaction chamber. NO is detector flew through cumulonimbus clouds—
then determined as before, but now the signal tall, vertically developed, and actively raining
includes input from the presence of the air’s (Ridley et al., 1987).
NO and NO2. If alternating signals are gener- The researchers were flying level at 9.3-km
ated in a short time period—one with the altitude while sampling the tropospheric air
atmospheric air stream that has been reduced
and the other without reduction—by means of 1000
a switching valve, then the concentration of
Airplane passing
both nitrogen oxides can be determined: through clouds
800
NO concentration signal generated by
NO concentration (pptv)
unreduced air flow

600
NO2 concentration signal generated by
reduced air flow signal from unreduced
air flow 400
The limits of detection and selectivity (ability

to determine NO or NO2 in the presence of 200
interferants) over O3, SO2, and CO—all com-
mon atmospheric gases—are very good. Less
0
than 1 ppbv NO can be routinely determined 13 13.1 13.2 13.3 13.4 13.5 13.6 13.7 13.8
using this method (Department for Environ- Local time
ment UK, 2004). Interferences from reduced
Instrumental Determination of NOX via Chemiluminescence 201
over the Pacific Ocean west of Hawaii. The period at a lab at the South Pole have shown a
regions of the flight path involving clouds are relatively constant NO concentration at the
noted. The concentration of NO in parts per snow pack surface. The overall concentrations
trillion by volume is plotted on the y-axis and of NO at that South Polar site were also signif-
local time is plotted on the x-axis. These data icantly higher than at other polar sites (some-
demonstrate the production of NO in electri- times by orders of magnitude) where similar
cally active clouds. examinations had been carried out, so it
This method of NO and NO2 measure- appears that the interesting meteorological
ment has also been used in experiments carried conditions present at 90° S—including con-
out at Antarctica at the South Pole (Davis et al., stant sunlight during austral summer—directly
2004). Earlier presumptions were that no nitric affect the production of NO. If you look care-
oxide was produced in that pristine setting fully at the graph, you can see a dip in NO
since internal combustion engines, which are concentration that took place near midnight
the major source of NO in urban environ- (0:00 h). This occurred when the shadow from
ments, were absent. However, in the austral a nearby building temporarily fell on the sam-
summer of 24-hour daylight, nitric oxide is pling site, decreasing the production of NO
continuously produced by sunlight photolysis from the snow’s nitrate ions. Plotted on the
of nitrate anion in the snow pack. And so, same figure is urban air NO concentration for a
unlike diurnal variations of NO such as those sampling site in Houston, Texas on August 17,
seen in urban environments (see figure below), 2006 (TCEQ, 2006). The common urban diur-
time-course studies over an entire 24-hour nal variation of NO is clear.
References: D. Davis, G. Chen, M. Buhr, J. Crawford,
70 2500
D. Lenschow, B. Lefer, R. Shetter, F. Eisele,
L. Mauldin, and A. Hogan, “South Pole NOX Chem-
istry: An Assessment of Factors Controlling Variabil-
60 ity and Absolute Levels,” Atmospheric Environment
2000 38 (2004): 5375–5388.
Snow pack NO (pptv)
50 Department for Environment UK, “Nitrogen Dioxide

Urban NO (ppbv)
1500
in the United Kingdom, 2004,” http://www.defra.gov
40 .uk/environment/airquality/aqeg/nitrogen-dioxide/
index.htm
30 Environmental Protection National Service UK,
1000
“Monitoring Methods for Ambient Air, 2000,”
20 http://publications.environment-agency.gov.uk/pdf/
GEHO1105BJYB-e-e.pdf
500
10 B. A. Ridley, M. A. Carroll, and G. L. Gregory, “Mea-
surements of Nitric Oxide in the Boundary Layer and
0 0 Free Troposphere over the Pacific Ocean,” Journal of
0 4 8 12 16 20 24 Geophysical Research 92(D2) (1987): 2025–2047.
Time (hours) TCEQ (Texas Commission on Environmental Quality),
http://www.tceq.state.tx.us.
PART II
ENERGY AND
CLIMATE CHANGE
Contents of Part II
Chapter 6 The Greenhouse Effect
Chapter 7 Fossil-Fuel Energy, CO2 Emissions, and
Global Warming
Chapter 8 Renewable Energy, Alternative Fuels, and the
Hydrogen Economy
Chapter 9 Radioactivity, Radon, and Nuclear Energy
Environmental Instrumental Analysis II

 Instrumental Determination of Atmospheric Methane
Scientific American Feature Article

 A Plan to Keep Carbon in Check
C H A P T E R
6
THE GREENHOUSE EFFECT
topics are used:
 Combustion
 Molecular shape, bond angles and distances
 Polymers

 Sunlight wavelength regions (UV, visible, IR) (Chapter 1)
 Absorption spectra (Chapter 1)
 ppm/ppb concentration scale
for gases (Chapter 1)
 CFCs and their replacements
(Chapter 2)
 Tropospheric ozone; nitrous
oxide (Chapter 3)
 Aerosols; sulfur dioxide
(Chapter 3)
Introduction
Everyone has heard the prediction that
the greenhouse effect will significantly
affect climates around the world in the
future. The terms greenhouse warming
and global warming in ordinary usage
simply mean that average global air
temperatures are expected to increase
by several degrees as a result of the
buildup of carbon dioxide and other
greenhouse gases in the atmosphere. Global warming may have led to the dramatic breakup of the Larsen Ice
Indeed, most atmospheric scientists Shelf off Antarctica in 2002. [GSFC/LaRC/JPL/MISR Team/NASA.]
205
206 Chapter 6 The Greenhouse Effect
believe that such global warming has already been under way for some time
and is largely responsible for the air temperature increase of about two-thirds
of a Celsius degree that has occurred since 1860.
The phenomenon of rapid global warming—with its demands for large-
scale adjustments—is generally considered to be our most crucial worldwide
environmental problem, although both positive and negative effects would
be associated with any significant increase in the average global temperature.
No one currently is sure of the extent or timing of future temperature
increases, nor is it likely that reliable predictions for individual regions will
ever be available much in advance of the events in question. If current mod-
els of the atmosphere are correct, however, significant warming will occur in
coming decades. It is important that we understand the factors that are
driving this increase so that we can, if we wish, take steps to avoid potential
catastrophes caused by rapid climate change in the future.
In this chapter, the mechanism by which global warming could arise is
explained, and the nature and sources of the chemicals that are responsible
for the effect are analyzed. The extent of the atmospheric warming to date
and other indications that change is under way are also discussed. The predic-
tions concerning global warming in the future, and an analysis of steps that
could be taken to minimize it, are presented in Chapters 7 and 8.
The Mechanism of the Greenhouse Effect

The Earth’s Energy Source
The Earth’s surface and atmosphere are kept warm almost exclusively by
energy from the Sun, which radiates energy as light of many types. In its radi-
ating characteristics, the Sun behaves much like a blackbody, i.e., an object
that is 100% efficient in emitting and in absorbing light. The wavelength,
␭peak, in micrometers, at which the maximum emission of energy occurs by a
radiating blackbody decreases inversely with increasing Kelvin temperature, T,
according to the relationship
␭peak 2897/T
Since for the surface of the Sun, from which the star emits light, the temper-
ature T ' 5800 K, then from the equation it follows that ␭peak is about
0.50 ␮m, a wavelength that lies in the visible region of the spectrum (and
corresponds to green light). Indeed, the maximum observed solar output
(see the dashed portion of the curve in Figure 6-1) occurs in the range of
visible light, i.e., that of wavelengths between 0.40 and 0.75 ␮m. Beyond the
“red limit,” the maximum wavelength for visible light, the Earth receives
infrared light (IR) in the 0.75–4-␮m region from the Sun. Of the energy
received at the top of the Earth’s atmosphere from the Sun, slightly over half
the total is IR and most of the remainder is visible light. At the opposite end
Energy
Incoming FIGURE 6-1 Wavelength

Outgoing
solar light distributions (using different
light from Earth
(UV, visible, IR) scales) for light emitted by
(thermal IR)
the Sun (dashed curve) and
by Earth’s surface and
troposphere (solid curve).
0.1 0.2 0.3 0.5 1.0 1.5 2 3 5 10 15 20 30 50 [Source: Redrawn from
J. Gribbin, “Inside Science:
UV Visible light Infrared light
The Greenhouse Effect,” New
Wavelength ( μ m) Scientist, supplement
(22 October 1988).]
of the visible wavelength spectrum from IR, beyond the “violet” limit, lies
ultraviolet light (UV), which has wavelengths less than 0.4 ␮m and is a
minor component of sunlight, as discussed in Chapter 1.
Of the total incoming sunlight of all wavelengths that impinges upon the
Earth, about 50% is absorbed at its surface by water bodies, soil, vegetation,
buildings, and so on. A further 20% of the incoming light is absorbed by
water droplets in air (mainly in the form of clouds) and by molecular gases—
the UV component by stratospheric ozone, O3, and diatomic oxygen, O2,
and the IR by carbon dioxide, CO2, and especially water vapor.
The remaining 30% of incoming sunlight is reflected back into space by
clouds, suspended particles, ice, snow, sand, and other reflecting bodies, with-
out being absorbed. The fraction of sunlight reflected back into space by an
object is called its albedo, which therefore is about 0.30 for the Earth overall.
Clouds are good reflectors, with albedos ranging from 0.4 to 0.8. Snow and ice
are also highly reflecting surfaces for visible light (high albedos), whereas bare
soil and bodies of water are poor reflectors (low albedos). Thus the melting of
sea ice in polar regions to produce open water greatly increases the fraction of
sunlight absorbed there and decreases the Earth’s overall albedo. Planting
trees in snow-covered forests reduces the albedo of the surface and may actu-
ally contribute to global warming.
Historical Temperature Trends

The trends in average surface temperature for the past 2000 years, as recon-
structed for most of that period from indirect evidence such as tree ring
growth, is shown in Figure 6-2a. (The Medieval Warm Period early in the
(a)
Average change in temperature (˚C)

0.4
0.2
–0.2
–0.4
–0.6
FIGURE 6-2 (a) Recon- 200 400 600 800 1000 1200 1400 1600 1800 2000
struction of changes in Year
average global surface (b)
temperatures over the 14.8
last two millennia.
[Source: M. E. Mann and
14.4
Temperature (˚C)
P. D. Jones, “Global Surface

Temperatures over the
Past Two Millennia,” 14.0
Geophysical Research
Letters 30 (2003): 1820.]
(b) Global average 13.6
land–ocean temperature
at the Earth’s surface from 13.2
1880 to 2005.
1880 1905 1930 1955 1980 2005
[Source: L. Brown et al., Vital
Signs 2006–7 (New York: Year
Norton, 2007).]
millennium was apparently restricted to the North Atlantic region, so it is

not very evident on the global plot.) Notice the consistently downward trend
in temperature until the beginnings of the Industrial Revolution.
The warming of the climate during the twentieth century stands in stark
contrast to the gradual cooling trend in the previous 900 years of the millen-
nium, producing a “hockey stick” shape to the temperature plot in Figure 6-2a.
The trends in global average surface temperature over the last century and a
half are illustrated in detail in Figure 6-2b. Air temperature did not increase
continuously throughout the twentieth century. A significant warming trend
occurred in the 1910–1940 period, due to a lack of volcanic activity and a
slight increase in the intensity of sunlight. This period was followed by some
cooling over the next three decades, due to aerosols resulting from increased
volcanic activity. These decades were succeeded in turn by a warming period
that has been sustained from about 1970 to the present and that has so far
amounted to a temperature increase of about 0.6°C; this is attributed almost

entirely to anthropogenic influences, as discussed in detail in this chapter.
Eleven of the 12 years of the 1995–2006 period are among the 12 warmest
since 1850, when instrument records began. The warmest years on record
were 1998 and 2005.
Earth’s Energy Emissions and the Greenhouse Effect

Like any warm body, the Earth emits energy; indeed, the amount of energy
that the planet absorbs and the amount that it releases must be equal over the
long term if its temperature is to remain level. (Currently, the planet is
absorbing slightly more than it is emitting, thereby warming the air and the
oceans.) The emitted energy (see the solid portion of the curve in Figure 6-1)
is neither visible nor UV light, because the Earth is not hot enough to emit
light in these regions. Since the temperature of the Earth’s surface is approx-
imately 300 K, then according to the equation above for ␭peak, if the Earth
acted like a blackbody, its wavelength of maximum emission would be about
10 ␮m. Indeed, the Earth’s emission does peak in that general region, actually
at about 13 ␮m, and consists of infrared light having wavelengths starting at
about 5 ␮m and extending, albeit weakly, beyond 50 ␮m (Figure 6-1, solid
curve). The 5–100-␮m range is called the thermal infrared region since such
energy is a form of heat, the same kind of energy a heated iron pot would
radiate.
Infrared light is emitted both at the Earth’s surface and by its atmosphere,
though in different amounts at different altitudes since the emission rate is
very temperature sensitive: In general, the warmer a body, the more energy it
emits per second. The rate of release of energy as light by a blackbody increases
in proportion to the fourth power of its Kelvin temperature:
rate of energy release kT 4
where k is a proportionality constant. Thus doubling its absolute tempera-

ture increases sixteen-fold (24) the rate at which a body releases energy.
More realistically, for contemporary surface conditions of planet Earth, a
one-degree rise in temperature would increase the rate of energy release
by 1.3%.
P R O B L E M 6-1
Calculate the ratio of the rates of energy release by two otherwise identical
blackbodies, one of which is at 0°C and the other at 17°C. At what temper-
ature is the rate of energy release twice that at 0°C?
Greenhouse
Outgoing IR gas Absorption
Re-emission Heat
Air near
surface is
warmed
FIGURE 6-3 The green-
house effect: Outgoing IR
absorbed by greenhouse
gases is either re-emitted
(left side of diagram) or Ear th’s surface
converted to heat (right
side).
Some gases in air absorb thermal infrared light—though only at charac-

teristic wavelengths—and therefore the IR emitted from the Earth’s surface
and atmosphere does not all escape directly to space. Very shortly after its
absorption by atmospheric gases such as CO2, the IR photon may be re-
emitted. Alternatively, the absorbed energy may quickly be redistributed as
heat among molecules that collide with the absorber molecule, and it may
eventually be re-emitted as IR by them. Whether re-emitted immediately by
the initial absorber molecule or later by others in the area, the direction
of the photon is completely random (Figure 6-3). Consequently, some of this
thermal IR is redirected back toward the Earth’s surface and is reabsorbed
there or in the air above it.
Because the air absorbs IR photons and redistributes the energy as heat
to surrounding molecules, the air temperature in the region of the absorb-
ing molecule increases. However, this air mass does not heat up without
limit as its molecules trap more and more of the outgoing infrared light
because there is an opposing phenomenon that prevents such a catastro-
phe. As explained above, the rate of energy emission increases with tem-
perature, so the molecules that have shared the excess energy themselves
emit more and more energy as infrared light as they warm up (Figure 6-3).
The water droplets and vapor in clouds are also very effective in absorbing
infrared light emitted from beneath them. The temperature at the tops of
clouds is quite cool relative to the air beneath them, so clouds do not radi-
ate as much energy as they absorb. Overall, air temperatures increase only
enough to re-establish the planetary equality between incoming and outgoing
energy.
The phenomenon of interception of outgoing IR by atmospheric con-

stituents and its dissipation as heat to increase the temperature of the atmo-
sphere (as illustrated in Figure 6-3) is called the greenhouse effect. It is
responsible for the average temperature at the Earth’s surface and the air close
to it being about 15°C rather than about 18°C, the temperature it would
be if there were no IR-absorbing gases in the atmosphere. The surface is
warmed as much by this indirect mechanism as it is by the solar energy it
absorbs directly! The very fact that our planet is not entirely covered by a
thick sheet of ice is due to the natural operation of the greenhouse effect,
which has been in operation for billions of years.
The atmosphere operates in the same way as a blanket, retaining within
the immediate region some of the heat released by a body and thereby
increasing the local temperature. The phenomenon that worries environ-
mental scientists is that increasing the concentration of the trace gases in air
that absorbs thermal IR light (piling on more blankets, so to speak) would
result in the conversion to heat of an even greater fraction of the outgoing
thermal IR energy than occurs at present, which would thereby increase
the average surface temperature well beyond 15°C. This phenomenon is
sometimes referred to as the enhanced greenhouse effect (or artificial global
warming) to distinguish its effects from the one that has been operating natu-
rally for millennia.
The principal constituents of the atmosphere—N2, O2, and Ar—are
incapable of absorbing IR light; the reasons for this will be discussed in the
following section. The atmospheric gases that in the past have produced most
of the greenhouse warming are water vapor (responsible for about two-thirds
of the effect) and carbon dioxide (responsible for about one-quarter). Indeed,
the absence of water vapor and of clouds in the dry air of desert areas leads to
low nighttime temperatures there since so little of the outgoing IR is redi-
rected back to the surface, even though the daytime temperatures are quite
high on account of direct absorption of solar energy by the surface. More
familiar to people living in temperate climates is the crisp chill in winter air on
cloudless days and nights. Cloudy nights are usually warmer than clear ones
because clouds reradiate IR that they have absorbed from surface emissions.
The greenhouse effect may be better understood by considering the fol-
lowing approximate model. Using physics, the temperature of an Earth that
had no greenhouse gases in its air but was balanced with respect to incoming
and outgoing energy would be 18°C, or 255 K. Since, according to the
equation above, the rate of energy emission from such a planet would be
k (255)4, it follows that the rate of energy input from the Sun, whether or not
the Earth’s atmosphere contained greenhouse gases, would also be k(255)4.
Overall, the real Earth acts as if about 60% of the energy it emits as infrared
light is eventually transmitted into space, the remainder being the fraction
that is not only absorbed by greenhouse gases but that is also reradiated
downward and further heats the surface and atmosphere. Thus the rate at
which the Earth loses energy to space as IR is not simply kT 4, but rather
0.6 kT 4. Since we know that
rate of loss of energy from Earth rate of energy input from Sun
it follows for the real Earth that
0.6 kT 4 k (255)4
Taking the fourth root of both sides, we obtain an expression for the
temperature:
T (255)兾0.60.25
so
T 290 K
From this model, the Earth’s calculated surface temperature is 290 K, i.e.,
17°C, an increase of 35 degrees by the operation of the natural greenhouse
effect.
In reality, however, very little of the IR emitted at or near the Earth’s
surface escapes into space. Rather it is absorbed by the air close to the ground,
then re-emitted. A simple model of the atmosphere that incorporates this
effect is discussed in Box 6-1. The IR from the air close to the ground that is
emitted upward is mainly absorbed by the next layer of air, which is heated by
it, though to a lesser extent than is the layer underneath, and is partially
re-emitted. With increasing altitude, the fraction of the IR received from the
air lying below a given level is less and less likely to be absorbed, since the
atmosphere becomes thinner and thinner. Thus more and more of the IR is
likely to pass upward into space. Indeed, very little of the IR emitted into the
upper troposphere is absorbed since the air is thin at such altitudes. Because
less and less IR is absorbed with increasing altitude, less and less is degraded
into heat; there is therefore a natural tendency for the air to cool the higher
the altitude. In reality, other factors such as convection currents in air also
play an important role in determining the decline in temperature with alti-
tude. The temperature at the top of the troposphere, from which the emitted
IR reaches outer space, is only 18°C, so overall the real Earth does radiate
energy into space at the same temperature as was computed for the planet if it
had no greenhouse gases. Thus the Earth emits the same amount of energy—
equal to the amount absorbed from sunlight—into space with or without the
operation of the greenhouse effect.
Earth’s Energy Balance

The current energy inputs and outputs from the Earth—in watts (i.e., joules
per second) per square meter of its surface and averaged over day and night,
over all latitudes and longitudes, and over all seasons—are summarized
BOX 6-1 A Simple Model of the Greenhouse Effect
he calculation in the main text of the sunlight by the surface, since only half the air’s
T Earth’s surface temperature assumed a
specific value for the fraction of IR emitted
energy escapes upward and is released into
space. Define rateb as the total energy release
from the surface that was transmitted through rate from the air mass and ratea as the absorp-
the atmosphere to outer space. However, this tion rate from sunlight. Since we know that
fraction—and the temperature—can be calcu- the rate of energy emission rises with the
lated from the physics of the situation. Con- fourth power of the temperature, it follows
sider a model Earth containing an atmosphere that for any two Kelvin temperatures Ta and
that consists of a single, uniform layer of air Tb involving the same type of blackbody, the
that is completely nontransparent to outgoing ratio of rates of energy emission is given by
IR emitted from the surface, i.e., an atmo- (rateb/ratea) (Tb/Ta)4
sphere that absorbs all the IR and that con-
verts it temporarily to heat. The layer of air In our case, the rate ratio must be 2/1, and we
itself is assumed to act as a blackbody that know that Ta is 255 K. Thus
emits IR equally upward into space and down- (Tb/255)4 2.0
ward back to the surface (Figure 1).
If a balance is to be achieved on Earth Taking square roots of both sides twice, we
between incoming and outgoing energy, the obtain
air mass in the model must emit twice as much (Tb/255) 2.00.25 1.189
energy (2X) per second as is absorbed (X) from
so
Tb 303 K
Space This simple model predicts the Earth’s
surface (and air) temperature to be 303 K, or
30°C, compared to the actual value of 15°C.
X The model is unrealistic and leads to an over-
Air estimation of the greenhouse effect, because it
assumes that all the IR escaping from the
surface is absorbed and that the atmosphere is
completely uniform and acts exactly as a
2X X blackbody. Earth’s actual surface temperature
of 15°C is more consistent with a slightly more
complicated model, in which about one-third
of the IR emitted from the surface passes
Surface
through the atmosphere unabsorbed, and
about two-thirds is absorbed by the air and
subsequently re-emitted. The most accurate
FIGURE 1 Energy released by the Earth’s surface and model consists of a sequence of several layers
absorbed and released by the atmosphere according to of air, with temperatures decreasing with alti-
the model. tude, each layer acting as a blackbody.
in Figure 6-4. A total of 342 watts/m2 (W/m2)

Sun
are present in sunlight outside the Earth’s
atmosphere. Of this, 235 W/m2 are absorbed by
the atmosphere and the surface; this much
342
energy must be re-emitted into space if the
235 planet is to maintain a steady temperature.
Emitted Because of the presence of greenhouse gases,
Visible and IR
by Earth however, emission of only 235 W/m2 from the
surface would not be sufficient to ensure this
107 balance. Because absorption of IR by green-
235 house gases heats the surface and lower atmo-
Reflection
sphere, the amount of IR released by them is
(atmosphere Absorbed IR increased. Given the current concentration of
and surface) greenhouse gases in air, the balance is achieved
155
and 235 W/m2 escape from the top of the
Absorbed 67
by air 168 390 atmosphere into space if 390 W/m2 are emitted
from the surface, i.e., when 155 W/m2 of IR do
not escape into space.
Absorbed Emitted
by surface by surface
Ironically, an increase in CO2 concen-
Earth
tration is predicted to cause a cooling of the
stratosphere. This phenomenon occurs for two
reasons.
FIGURE 6-4 Globally
and seasonally averaged • First, more outgoing thermal IR is absorbed at low altitudes (the tropo-
energy fluxes to and from sphere), so less is left over to be absorbed by and warm the gases in the
the Earth, in watts per
square meter of surface.
stratosphere.
[Source: Data from Chapter 1 • Second, at stratospheric temperatures, CO2 emits more thermal IR
of J. T. Houghton et al.,
Climate Change 1995—The
upward to space and downward to the troposphere than it absorbs as
Science of Climate Change photons—most of the absorption at these altitudes is due to water vapor and
(Intergovernmental Panel on ozone—so increasing its concentration cools the stratosphere.
Climate Change) (Cambridge:
Cambridge University Press, The observed cooling of the stratosphere has been taken to be a signal that
1996).] the greenhouse effect is indeed undergoing enhancement.
Molecular Vibrations: Energy Absorption

by Greenhouse Gases
Light is most likely to be absorbed by a molecule when its frequency almost
exactly matches the frequency of an internal motion within the molecule.
For frequencies in the infrared region, the relevant internal motions are the
vibrations of the molecule’s atoms relative to each other.
The simplest vibrational motion in a molecule is the oscillatory motion
of two bonded atoms X and Y relative to each other. In this motion, called a
Molecular Vibrations: Energy Absorption by Greenhouse Gases 215
(a) Bond-stretching vibration
X9Y
R
X99Y X9Y
R
X9Y X9Y
R
(b) Angle-bending vibration
Y Y Y Y Y
X Z X Z X Z X Z
X Z
FIGURE 6-5 The two kinds of vibrations within molecules. Bond stretching (a) is illustrated
for a diatomic molecule XY. The variable R represents the average value of the X–Y distance.
In (b), the angle-bending vibration is shown for a triatomic molecule XYZ. The average XYZ
angle is indicated by ␾.
bond-stretching vibration, the X-to-Y distance increases beyond its average

value R, then returns to R, then contracts to a lesser value, and finally returns
to R, as illustrated in Figure 6-5a. Such oscillatory motion occurs in all bonds
of all molecules under all temperature conditions, even at absolute zero. A
huge number (about 1013) of such vibrational cycles occur each second. The
exact frequency of the oscillatory motion depends primarily on the type of
bond—i.e., whether it is single or double or triple—and on the identity of the
two atoms involved. For many bond types, e.g., the C ¬ H bond in methane
and the O ¬ H bond in water, the stretching frequency does not fall within
the thermal infrared region. The stretching frequency of carbon–fluorine
bonds does, however, occur within the thermal infrared range; thus any mol-
ecules in the atmosphere with C ¬ F bonds will absorb outgoing thermal IR
light and enhance the greenhouse effect.
The other relevant type of vibration is an oscillation in the distance
between two atoms X and Z bonded to a common atom Y but not bonded to
each other. Such motion, called a bending vibration, alters the XYZ bond
angle from its average value ␾. All molecules containing three or more
atoms possess bending vibrations. The oscillatory cycle of bond angle
increase, followed by a decrease, and then another increase, etc., is illus-
trated in Figure 6-5b. The frequencies of many types of bending vibrations in
most organic molecules occur within the thermal infrared region.
If infrared light is to be absorbed by a vibrating molecule, there must be a
difference in the relative positions of the molecule’s center of positive charge
(its nuclei) and its center of negative charge (its electron “cloud”) at some
point during the motion. More compactly stated, in order to absorb IR light,
the molecule must have a dipole moment during some stage of the vibration.
Technically, there must be a change in the magnitude of the dipole moment
during the vibration, but this is more or less guaranteed to be the case if there
is a nonzero dipole moment at any point in the vibration. The positive and
negative centers of charge coincide in free atoms and (by definition) in
homonuclear diatomic molecules like O2 and N2, and the molecules have
dipole moments of zero at all times in their stretching vibration. Thus argon
gas, Ar, diatomic nitrogen gas, N2, and diatomic oxygen, O2, do not absorb
IR light.
For carbon dioxide, during the vibratory motion in which both C9O
bonds lengthen and shorten simultaneously, i.e., synchronously, there is at
no time any difference in position between the centers of positive and neg-
ative charges, since both lie precisely at the central nucleus. Consequently,
during this vibration, called the symmetric stretch, the molecule cannot
absorb IR light. However, in the antisymmetric stretch vibration in CO2,
the contraction of one C9O bond occurs when the other is lengthening, or
vice versa, so that during the motion the centers of charge no longer neces-
sarily coincide. Therefore, IR light at this vibration’s frequency can be
absorbed since, at some points in the vibration, the molecule does have a
dipole moment.
; : : :
O“C“O O“C“O
symmetric antisymmetric
stretch stretch
Similarly, the bending vibration in a CO2 molecule, in which the three atoms
depart from a colinear geometry, is a vibration that can absorb IR light since
the centers of positive and negative charge do not coincide when the mole-
cule is nonlinear.
Molecules with three or more atoms generally have some vibrations that
absorb IR, since even if their average shape is highly symmetric with a zero
dipole moment, they undergo some vibrations that reduce this symmetry
and produce a nonzero dipole moment. For example, CH4 molecules have an
average structure that is exactly tetrahedral, and hence a zero average dipole
moment, because the polarities of the C9H bonds exactly cancel each
other in this geometry. The zero dipole is maintained during the vibration in
which all four bonds simultaneously stretch or contract. However, during
the vibrational motions in which some of the bonds stretch while others
contract, and those in which some H9C9H bond angles become greater
than tetrahedral while others become less, the molecule has a nonzero
dipole moment. Molecules of CH4 undergoing such unsymmetrical vibra-
tions can absorb infrared light.
P R O B L E M 6-2
Deduce whether the following molecules will absorb infrared light due to
internal vibrational motions:
(a) H2 (b) CO (c) Cl2 (d) O3 (e) CCl4 (f) NO
P R O B L E M 6-3
None of the four diatomic molecules listed in Problem 6-2 actually absorb
much, if any, of the Earth’s outbound light in the thermal infrared region.
What does this imply about the frequencies of the bond-stretching vibra-
tional motion of those molecules that can, in principle, absorb IR light?
The Major Greenhouse Gases

Carbon Dioxide: Absorption of Infrared Light
As stated previously, the absorption of light by a molecule occurs most
efficiently when the frequencies of the light and of one of the molecule’s
vibrations match almost exactly. However, light of somewhat lower or higher
frequency than that of the vibration is absorbed by a collection of molecules.
This ability of molecules to absorb infrared light over a short range of fre-
quencies rather than at just a single frequency occurs because it is not only
the energy associated with vibration that changes when an infrared photon is
absorbed; there is also a change in the energy associated with the rotation
(tumbling) of the molecule about its internal axes. This rotational energy of
a molecule can be either slightly increased or slightly decreased when IR light
is absorbed to increase its vibrational energy. Consequently, photon absorp-
tion occurs at a slightly higher or lower frequency than that corresponding to
the frequency of the vibration. Generally, the absorption tendency of a gas
falls off rapidly for light frequency that lies farther and farther in either
direction from the vibrational frequency.
The absorption spectrum for carbon dioxide in a portion of the infrared
range is shown in Figure 6-6. For CO2, the maximum absorption of light in the
thermal infrared range occurs at a wavelength of 15.0 ␮m, which corresponds to
a frequency of 2 1013 cycles per second (hertz). The absorption occurs at this
particular frequency because it matches that of one of the vibrations in a CO2
molecule, namely the OCO angle-bending vibration. Carbon dioxide also
strongly absorbs IR light having a wavelength of 4.26 ␮m, which corresponds to
the 7 1013 cycles per second (hertz) frequency of the antisymmetric OCO
stretching vibration.
P R O B L E M 6-4
Calculate the energy absorbed per mole and per molecule of carbon dioxide
when it absorbs infrared light (a) at 15.0 ␮m and (b) at 4.26 ␮m. Express the
per mole energies as fractions of that required to dissociate CO2 into CO and
atomic oxygen, given that the enthalpies of formation of the three gaseous
species are 393.5, 110.5, and 249.2 kJ/mol, respectively. [Hint: Recall
the relationship between wavelength and energy in Chapter 1. Avogadro’s constant
6.02 1023.]
100
Fraction of light transmitted through the gas

80
60
FIGURE 6-6 The infrared

absorption spectrum for
40
carbon dioxide. The scale
for wavelength is linear
when expressed in
wavenumbers, which 20
have units of cm1;
Ranges of maximum absorption
wavenumber 10,000/
wavelength in nm. 0
[Source: Redrawn from
A.T. Schwartz et al., Chemistry
in Context: Applying Chemistry
3 4 5 6 7 8 9 10 12 1416
to Society, American Chemical
Wavelength ( μ m) of transmitted light
Society (Dubuque, IA:
Wm. C. Brown, 1994).]
The carbon dioxide molecules that are now present in air collectively
absorb about half of the outgoing thermal infrared light with wavelengths in
the 14–16-␮m region, together with a sizable portion of that in the 12–14-
and 16–18-␮m regions. It is because of CO2’s absorption that the solid curve
in Figure 6-7, representing the amount of IR light that actually escapes from
our atmosphere, falls so steeply around 15 ␮m; the vertical separation
between the curves is proportional to the amount of IR of a given wavelength
that is being absorbed rather than escaping. Further increases in the CO2
concentration in the atmosphere will prevent more of the remaining IR from
escaping, especially in the “shoulder” regions around 15 ␮m, and will further
warm the air. (Although carbon dioxide also absorbs IR light at 4.3 ␮m due
to the antisymmetric stretching vibration, there is little energy emitted from
the Earth at this wavelength—see Figure 6-1—so this potential absorption is
not very important.)
Carbon Dioxide: Past Concentration and Emission Trends

Measurements of air trapped in ice-core samples from Antarctica indicate
that the atmospheric concentration of carbon dioxide in preindustrial times
(i.e., before about 1750) was about 280 ppm. The concentration had
increased by one-third, to 382 ppm, by 2006. A plot of the increase in the
annual atmospheric CO2 concentration over time is shown in Figure 6-8.
Light leaving
the upper
Light emitted atmosphere
from surface H2O
FIGURE 6-7 Experimen-
tally measured intensity
(black curve) of thermal
IR light leaving the Earth’s
Light intensity
surface and lower atmo-

sphere (above the Sahara
desert) compared with
the theoretical intensity
(green curve) that would
be expected without
O3
absorption by atmospheric
greenhouse gases. The
H2O 15 m m
regions in which the
CO2 various gases have their
CH4 N2O greatest absorption are
0
indicated.
7.1 10.0 16.7
[Source: E. S. Nesbit, Leaving
Wavelength ( μ m) Eden (Cambridge: Cambridge
University Press, 1991).]
385
360 375
365
CO2 concentration (ppm)
355
345
320 FIGURE 6-8 The historic
335 variation in the atmo-
spheric concentration of
1978 1982 1986 1990 1994 1998 2002 2006
carbon dioxide. The insert
shows the trend, with
seasonal fluctuations, in
280 recent times.
[Source: Main graph: Adapted
from J. L. Sarmiento and
N. Gruber, “Sinks for
1000 1200 1400 1600 1800 2000 Anthropogenic Carbon,”
Year Physics Today 55 (August
2002): 30; Insert: NOAA.]
The insert to the figure shows details of the increase in recent times. In the
period from 1975 to 2000, the concentration grew at an average annual rate
of about 0.4%, or 1.6 ppm—almost double that of the 1960s. The rate of
increase in the first half-decade of the twenty-first century rose to about
2.0 ppm annually.
The seasonal fluctuations in the CO2 concentrations are due to the spurt
in the growth of vegetation in the spring and summer, which removes CO2
from air, and the vegetation decay cycle in fall and winter, which increases it.
In particular, huge quantities of CO2 are extracted from the air each spring
and summer by the process of plant photosynthesis:
sunlight
CO2 H2O ¡ O2 polymeric CH2O
The term polymeric CH2O used for the product in this equation is an umbrella
word for plant fiber, typically the cellulose that gives wood its mass and bulk.
The CO2 “captured” by the photosynthetic process is no longer free to
function as a greenhouse gas—or as any gas—while it is packed away in this
polymeric form. The carbon that is trapped in this way is called fixed carbon.
However, the biological decay of this plant material, the reverse of the reac-
tion, which occurs mainly in the fall and winter, frees the withdrawn carbon
dioxide. Notice that the global carbon dioxide fluctuations follow the seasons
of the Northern Hemisphere, since there is so much more land mass—and
hence much more vegetation—there compared to the Southern Hemisphere.
Much of the considerable increase in anthropogenic contributions to the
increase in carbon dioxide concentration in air is due to the combustion of
fossil fuels—chiefly coal, oil, and natural gas—that were formed eons ago
when plant and animal matter was covered by geological deposits before it
could be broken down by air oxidation.
On average, each person in the industrial countries is responsible for the
release of about 5 metric tons (a metric ton is 1000 kg, i.e., 2200 lb, whereas a
conventional ton is 2000 lb) of CO2 from carbon-containing fuels each year!
There is considerable variation in the per capita releases among different
industrialized countries; this is discussed in Chapter 7. Some of the per capita
carbon dioxide output is direct, e.g., that released as gases when vehicles are
driven and homes are warmed by burning a fossil fuel. The remainder is indi-
rect, arising when energy is used to produce and transport goods; heat and cool
factories, classrooms, and offices; produce and refine oil—in fact, to accom-
plish virtually any constructive economic purpose in an industrialized society.
This topic is also discussed in greater depth in Chapter 7.
A significant amount of carbon dioxide is added to the atmosphere when
forests are cleared and the wood burned to provide land for agricultural use. This
sort of activity occurred on a massive scale in temperate climate zones in past
centuries (consider the immense deforestation that accompanied the settlement
of the United States and southern Canada) but has now shifted largely to the
tropics. The greatest single amount of current deforestation occurs in Brazil and
involves both rain forest and moist deciduous forest, but the annual rate of defor-
estation on a percentage basis is actually greater in Southeast Asia and Central
America than in South America. Overall, deforestation accounts for about one-
quarter of the annual anthropogenic release of CO2, the other three-quarters
originating mainly in the combustion of fossil fuels. Notwithstanding forestry
harvesting operations, the total amount of carbon contained in the forests of the
Northern Hemisphere (including their soils) is increasing, and in recent decades
the annual increment approximately equaled the decreases in stored carbon
cited above in Asia and South and Central America.
P R O B L E M 6-5
Carbon dioxide is also released into the atmosphere when calcium carbonate
rock (limestone) is heated to produce the quicklime, i.e., calcium oxide, used
in the manufacture of cement:
CaCO3(s) ¡ CaO(s) CO2(g)
Calculate the mass, in metric tons, of CO2 released per metric ton of lime-
stone used in this process. What is the mass of carbon that the air gains for
each gram of carbon dioxide that enters the atmosphere? Note that at least as
much carbon dioxide is released from combustion of the fossil fuel needed to
heat the limestone as is released from the limestone itself.
The growth of the total annual emissions, in terms of the mass of carbon,
of carbon dioxide from fossil-fuel combustion and cement production since
the start of the Industrial Revolution is shown by the uppermost (black)
curve in Figure 6-9. The contributions to this total are shown by the other
curves. Historically, the emission rate in the second half of the twentieth cen-
tury grew rapidly, the rate of increase being about five times greater than that
in the first half. The annual growth rate in emissions from 2000 to 2005 rose
to 3%, compared to 1% in the 1990s, due mainly to a rebound in coal produc-
tion (gray curve) and continuing growth in oil (green curve) and natural gas
(dashed curve) usage.
Carbon Dioxide: Atmospheric Lifetime

and Fate of Its Emissions
The lifetime of a carbon dioxide molecule emitted into the atmosphere is a
complicated measurement since, in contrast to most gases, it is not decomposed
chemically or photochemically. On average, within a few years of its release into
the air, a CO2 molecule will likely dissolve in surface seawater or be absorbed
by a growing plant. However, many such carbon dioxide molecules are released
back into the air a few years later on average, so this disposal is only a temporary
8000
7000
Total
Millions of metric tonns of carbon

6000
FIGURE 6-9 Annual
global CO2 emissions since
5000
the Industrial Revolution.
The black line gives total
emissions from fossil-fuel 4000
combustion and cement
manufacture. The contribu-
tions from solids (mainly 3000 Oil
coal) are shown by the gray
line, from liquids (mainly
2000
petroleum) by the green
line, and from gases Coal
(mainly natural gas) by 1000
the dashed black line. Gas
[Source: U.S. Department
of Energy Carbon Dioxide 0
1863 1877 1891 1905 1919 1933 1947 1961 1975 1989 2003
Information Analysis Center,
cdiac.ornl.gov/trends/
Year
emis/glo.htm]
sink for the gas. The only permanent sink for it is deposition in the deep waters
of the ocean and/or precipitation there as insoluble calcium carbonate. How-
ever, the top few hundred meters of seawater mix slowly with deeper waters;
thus carbon dioxide that is newly dissolved in surface water requires hundreds
of years to penetrate to the ocean depths. Consequently, although the oceans
will ultimately dissolve much of the increased CO2 now in the air, the time
scale associated with this permanent sink is very long, hundreds of years.
Because the processes involving the interchange of carbon dioxide
among the air, the biomass, and shallow ocean waters and between shallow
and deep seawater are complicated, it is not possible to cite a meaningful
average lifetime for the gas in air alone. Rather we should think of new CO2
fossil-fuel emissions as being rather quickly allocated among air, the shallow
ocean waters, and biomass, with interchange among these three compart-
ments occurring continuously. Then slowly, over a period of many decades
and even centuries, almost all this new carbon dioxide will eventually enter
its final sink, the deep ocean. In effect, the atmosphere rids itself of almost
half of any new carbon dioxide within a decade or two but requires a much
longer period of time to dispose of the rest. It is commonly quoted as taking
50 to 200 years for the carbon dioxide level to adjust to its new equilibrium
concentration if a source of it increases. In summary, the effective lifetime of
Atmosphere (total stored ~800 Gt)
Net loss of 0.9 Net loss of 2.2
7.2 1.5 2.4

22.2 20.0
Fossil-fuel Forests FIGURE 6-10 Annual

combustion fluxes of CO2 to and from
+ the atmosphere, in units of
Cement megatonnes of carbon. The
production Oceans total amounts stored in
(total stored ~38,000 Gt) various locations are shown
Land in bold. Note that the
(total fossil fuel stored ~6000 Gt) values for the air/ocean
interchange include natural
as well as anthropogenic
carbon. [Data source:
Sediments
UNESCO SCOPE Policy Briefs
2006 #2. The Global Carbon
Cycle.]
additional CO2 in the atmosphere should be considered to be long, on the

order of many decades or centuries, rather than the few years required for its
initial dissolution in seawater or absorption by biomass.
The annual inputs and outputs of anthropogenic carbon dioxide to and
from our atmosphere, as of the early 2000s, are summarized in Figure 6-10.
(Releases and absorption by natural processes are overall in balance and are
not included in the diagram.) Fossil-fuel combustion and cement production
released 7.2 gigatonnes (Gt, i.e., billions of tonnes, equivalent to petagrams,
1015 g) of the carbon component (only) of CO2 into the air, of which 4.4 Gt
(about 60%) did not find a sink. The upper layers of the ocean absorbed about
22 Gt of carbon but released only about 20 Gt, giving a net absorption by this
principal sink of almost 2 Gt. The carbon released by slash-and-burn tropical
deforestation and other land-use changes amounted to about 1 Gt less than
that absorbed by forest growth and soil storage. Because overall more than
half the anthropogenic CO2 emissions are quickly removed, over the short
and medium term the gas continues to accumulate in the atmosphere.
The variations over the last century and a half in the various annual
sources and sinks for CO2 are summarized in Figure 6-11. Notice the year-to-
year variations in the amount of the gas absorbed by the oceans and especially
in that absorbed by land sinks (biomass). Although the fraction of the new
emissions that remains in the atmosphere undergoes substantial variations
from year to year, its average increment is increasing with time.
8 Land use
6 Other emissions
Sources
4
FIGURE 6-11 Annual CO2 flux (Pg C/y)
fluxes of anthropogenic 2
CO2 to and from various Fossil-fuel
sources and sinks from emissions
0
1850 to 2005. Note that Ocean
the unit of picograms
2
(1012 g) is equivalent to
Atmosphere
the megatonne unit used
4
in Figure 6-10, since
Sinks
1 megatonne 106 tonnes,

1 tonne 1000 kg, and 6
1 kg 1000 g.) Land
[Source: M. Raupach (Global 8
Carbon Project), Carbon in
the Earth System: Dynamics
1850 1900 1950 2000
and Vulnerabilities (Beijing,
November, 2006).]
The increase in growth rate of certain types of trees due to the increased
concentration of carbon dioxide in the air is called CO2 fertilization. Some
scientists suspect that the rate of photosynthesis is speeding up as the level of
CO2 and the air temperature increase and that the formation of greater
amounts of fixed carbon represents an important sink for the gas. Indeed, an
increase in the biomass of northern temperate forests is the most likely sink
to account for the annual atmospheric CO2 loss for which scientists had pre-
viously been unable to assign a cause. This increased activity in photosynthe-
sis has been confirmed by satellite data for the region between 45°N and
70°N. Boreal (evergreen) forests of the Northern Hemisphere currently store
almost 1 Gt of carbon into standing biomass alone. Much of the increase in
the biomass of temperate forests at high latitudes occurs in the soil, especially
as peat. The anthropogenic releases of CO2 amount only to about 4% of the
enormous amounts produced by nature, so a very small variation in the rate
at which carbon is absorbed into biomass could have a large effect on the
residual amount of CO2 that accumulates in the atmosphere. Unfortunately,
scientists still do not completely understand the global carbon cycle. As Fig-
ure 6-8 indicates, however, there is no doubt that the atmospheric CO2 con-
centration is increasing.
P R O B L E M 6-6
(a) Given that the atmospheric burden of carbon (as CO2) increases by about
4.7 Gt annually, calculate the increase in the ppm concentration of carbon
dioxide that this brings about. (b) Given that its total concentration was
382 ppm in 2006, calculate the total mass of CO2 that was present in the air.
After converting to mass of carbon, does your answer agree with the value
listed in Figure 6-10? Note that the mass of the atmosphere 5.1 1021 g
and that air’s average molar mass 29.0 g/mol. [Hint: Express the amounts of
CO2 and air as moles, and recall the definition of ppm units in moles.]
Green Chemistry: Supercritical Carbon Dioxide in the

Production of Computer Chips
In this example of green chemistry, we see how waste CO2—which would
normally be vented to the atmosphere—can be put to good use as a solvent.
We will also see how using CO2 as a solvent pays additional environmental
dividends in terms of both energy and resource conservation and reduction of
wastes.
As technology relentlessly pervades our planet, the demand for inte-
grated circuits (ICs) and computer chips increases dramatically each year.
Computer chips are used in almost any electronic device one can imagine,
including telephones, televisions, radios, automobiles, trucks, computers, air-
planes, rockets, smart bombs, calculators, and cameras. It is estimated that
the combination of the average personal computer, keyboard, monitor, and
printer has a mass of about 25 kg and contains about 9 g of silicon and metal
in the ICs that are the heart of each computer.
The manufacture of computers, other electronic devices, and chips
involves high-tech, high-paying, highly skilled, and highly sought-after jobs.
Facilities involved in these activities are considered by most people to be
“clean” industries, especially when compared to the automobile and chemical
industries. It is a little-known fact, except to those who work in the field or
study the chip-manufacturing process, that chip making actually creates more
waste than any other process involved in the manufacture of computers and
is very energy intensive! By some measures, chip manufacturing is orders of
magnitude more wasteful and polluting than the production of automobiles.
It is estimated that the fabrication of the chips in your computer generated
about 196 kg of waste (4500 times the mass of the average chip) and used
about 10,600 L of water. The ratio of the mass of the materials (chemicals and
fossil fuels) needed to produce a chip to the mass of the chip is estimated at
630:1, while the analogous ratio for the production of an automobile is
approximately 2:1. Consequently, there are ongoing efforts to find less
resource-intensive and less wasteful methods of chip production.
Photolithography
Coat with
Clean wafer Deposit SiO2 Soft bake
photoresist
Photoresist Photoresist
SiO2 SiO2 SiO2
Si Si Si Si
Photolithography continued
Expose (hv) Remove

Develop resist Hard bake Etch SiO2
photoresist photoresist
Photo- Photo- Photo- Photo- Photo- Photo- Photo- Photo-

resist resist resist resist resist resist resist resist
SiO2 SiO2 SiO2 SiO2 SiO2 SiO2 SiO2
Si Si Si Si Si
FIGURE 6-12 The fabrication of integrated circuits. [Source: L. Rothman, G. Jacobson, and
C. Taylor, “Supercritical CO2 Resist Remover–SCORR,” a proposal submitted to the Presidential Green
Chemistry Challenge Awards Program, 2002.]
The process of producing a 2-g computer chip entails many steps and
requires 72 g of chemicals, 32 L of water (mostly for rinsing), and 700 g of
process gases. For production and use over a four-year lifetime, a 2-g chip
requires 1.6 kg of fossil fuels. A typical chip-manufacturing facility uses mil-
lions of liters of highly purified water per month. A few of these steps are out-
lined in Figure 6-12. The process begins with the mechanical or chemical
cleaning of the surface of highly purified silicon, followed by deposition of sil-
icon dioxide; then a process known as photolithography defines the shape
and pattern of individual components on an IC.
Photolithography begins with the deposition of a photoresist polymer,
followed by baking and exposure of selected areas of the polymer to light. The
light causes the polymer to cross-link, i.e., form bonds that link the polymer
chains to one another at many positions along each chain (see Figure 6-13).
The chip is then developed (a process that removes the photoresist polymer
from the unexposed areas) and hard baked, the SiO2 is etched, and the
light
Polymer chains Cross-linked polymer chains

FIGURE 6-13 The cross-
linking of polymer chains.
remaining photoresist polymer is removed, creating a pattern on the surface

of the chip. The removal of the photoresist is accomplished with large
amounts of aqueous solutions of strong acid (sulfuric or hydrochloric) or base,
or by use of organic solvents (halogenated or polycyclic aromatics). The chip
is then rinsed several times with copious amounts of highly purified water and
dried with alcohol. The removal of the photoresist is very resource- and
energy-intensive and creates large amounts of waste. The layering, develop-
ing, and etching process is repeated several times for each chip.
Scientists at Los Alamos National Laboratories in New Mexico and SC
Liquids in Nashua, New Hampshire, were awarded a Presidential Green
Chemistry Challenge Award in 2002 for their development of a new process
for removing photoresist in chip manufacturing, known as SCORR (super-
critical carbon dioxide resist remover). The process employs supercritical car-
bon dioxide (see Box 6-2) as the solvent for removal of the photoresist (the
last step of Figure 6-12). The use of SCORR offers several environmental
benefits over traditional methods, including the following:
• The rinse step is no longer necessary, thus eliminating the need for mil-
lions of liters of highly purified water, the energy required to produce this
water, and the associated wastewater. This also reduces the amount of fossil
fuel required to produce the highly purified water and the accompanying for-
mation of carbon dioxide.
• The need for (and waste from) hazardous and toxic chemicals such as
strong acids or bases or organic solvents in the photoresist removal step is
eliminated or reduced. This also enhances worker safety.
• The need for alcohols used for drying after the aqueous rinse step is
eliminated.
• The carbon dioxide is recovered after each use and reused.
• The only waste left after evaporation (and recovery) of the carbon diox-
ide is the spent photoresist, which is unregulated.
BOX 6-2 Supercritical Carbon Dioxide
he supercritical fluid state of matter is pro- 31.3°C, as illustrated in the phase diagram in
T duced when gases or liquids are subjected
to very high pressures and, in some cases, to
Figure 1. Depending upon exactly how much
pressure is applied, the physical properties of
elevated temperatures. At pressures and tem- the supercritical fluid vary between those of a
peratures at or beyond the critical point, sepa- gas (relatively lower pressures) and those of a
rate gaseous and liquid phases of a substance no liquid (higher pressures); the variation of prop-
longer exist. Under these conditions, only the erties with P or T is particularly acute near the
supercritical state, with properties that lie critical point. Thus the density of supercritical
between those of a gas and those of a liquid, carbon dioxide varies over a considerable
exists. For carbon dioxide, the critical pressure range, depending upon how much pressure
is 72.9 atm and the critical temperature is only (beyond 73 atm) is applied to it.
10,000
1000 Solid
Supercritical
fluid
100 Liquid
Pressure (atm)
10
Critical point
1 31°C at 72.8 atm
0.1
0.01
Gas
0.001
–120 –80 –40 0 40 80
Temperature (°C)
FIGURE 1 Phase diagram for carbon dioxide.
The carbon dioxide used in this process can be obtained as a waste by-
product of other processes (as indicated in Chapter 1 during the discussion
of using carbon dioxide as a blowing agent). Processes such as producing
ammonia and drilling for natural gas yield large amounts of this gas, which
would normally be released to the atmosphere and add to its concentration of
carbon dioxide. If we can capture this “unwanted” by-product and find con-
structive (and environmentally sound) uses for carbon dioxide, then we have
not only prevented its release into the atmosphere; we may also have reduced
our reliance on valuable resources and prevented the formation of other pol-
lutants. SCORR, the use of carbon dioxide as a blowing agent (green chem-
istry section, Chapter 2), and the use of carbon dioxide as a solvent for
various cleaning purposes (green chemistry section, Chapter 3) are all exam-
ples of this. In general, chemists are seeking ways to find beneficial uses for by-
products of other processes and reactions that would normally be considered
waste and would add to the environmental burden of the planet. The use of
carbon dioxide as a blowing agent and solvent for cleaning and photoresist
removal offers three significant examples of this paradigm.
Employing the SCORR process yields several additional advantages. As
the architecture of computer chips continually becomes smaller, water
(because of its high surface tension) will no longer be able to penetrate these
small spaces. Supercritical fluids have low viscosity, low surface tension, and
high diffusivity. Because of these properties, they are ideal for cleaning rough,
irregular surfaces with small openings. Supercritical carbon dioxide offers the
answer to the cleaning problems associated with the smaller features of the
new generations of chips. Other advantages of the SCORR process include
the facts that (1) cleaning times are cut in half, (2) eliminating the rinse step
allows for greater throughput (more chips in less time), and (3) carbon diox-
ide is less costly than conventional solvents.
Water Vapor: Its Infrared Absorption and

Role in Feedback
Water molecules, always abundant in air, absorb thermal IR light through
their H ¬ O ¬ H bending vibration; the peak in the spectrum for this
absorption occurs at about 6.3 ␮m. As a consequence, almost all the rela-
tively small amount of outgoing IR in the 5.5- to 7.5-␮m region is intercepted
by water vapor (see Figure 6-7). (The symmetric and antisymmetric stretch-
ing vibrations for water occur near 2.7 ␮m, outside the thermal IR region.
The symmetric stretch in a symmetric but nonlinear molecule like H2O does
absorb IR.) Absorption of light leading to increases in the rotational energy
of water molecules, without any change in vibrational energy, removes ther-
mal infrared light of 18-␮m and longer wavelengths. In fact, water is the most
important greenhouse gas in the Earth’s atmosphere, in the sense that it
produces more greenhouse warming than does any other gas, although on a
per molecule basis it is a less efficient IR absorber than is CO2.
Although human activities, such as the burning of fossil fuels, produce
water as a product, the concentration of water vapor in air is determined pri-
marily by temperature and by other aspects of the weather. Virtually all the
H2O in the troposphere arises from the evaporation of liquid and solid water
on the Earth’s surface and in clouds. The rate at which water evaporates and
the maximum amount of water vapor that an air mass can hold both increase
sharply with increasing temperature. Indeed, the equilibrium vapor pressure
of liquid water increases exponentially with temperature. The rise in air tem-
perature that is caused by increases in the concentration of the other green-
house gases, and by other global warming factors, heats the surface water and
ice, thereby causing more evaporation to occur. Indeed, the average atmo-
spheric content of water vapor has increased since at least the 1980s.
The consequent increase in the water vapor concentration from global
warming due to increased CO2, etc. produces an additional amount of global
warming due to H2O(g) that is comparable in magnitude to the original
amount due to the other greenhouse gases, because water vapor is a green-
house gas! This behavior of water is an example of the general phenomenon
called positive feedback: The operation of a phenomenon produces a result that
itself further amplifies the result. Feedback is a reaction to change; with positive
feedback, the reaction accelerates the pace of future change. On the other
hand, a system whose output reduces the subsequent level of output displays
negative feedback. An example of negative feedback from daily life is the
attempt by a business to raise its profits by increasing its prices. However, the
rise in price often results in a reduction in demand for the item of concern,
and the rise in profits is less than anticipated. (No value judgment as to the
desirability of the effect is implied by the terms positive and negative; only the
increase or decrease in the pace of change is meant.)
Since it comes about as an indirect effect of increasing the levels of
other gases, and since it is not within our control, the warming increment
due to water is usually apportioned without further comment into the direct
warming effects of the other gases. Consequently, water is not usually listed
explicitly among gases whose increasing concentrations are enhancing the
greenhouse effect.
Water in the form of liquid droplets in clouds also absorbs thermal IR.
However, clouds also reflect some incoming sunlight, both UV and visible,
back into space. It is not yet clear whether the additional cloud cover pro-
duced by increasing the atmospheric water content will have a net positive or
a net negative contribution to global warming. Clouds over tropical regions
are known to have a zero net effect on temperature, but those in northern lat-
itudes produce a net cooling effect since their ability to reflect sunlight out-
weighs their ability to absorb IR. Thus, if increased air temperatures produce
more of the latter type of cloud, the enhancement of global warming by the
greenhouse effect would be damped. However, no one is sure that additional
northern cloud cover would occur at the same altitudes and act in the same
manner as do the current clouds. Overall, the net effect of clouds on global
warming is still subject to some uncertainty.
The Atmospheric Window

As a result of absorption of IR light of other wavelengths, mainly by carbon
dioxide, methane, and water, it is essentially only infrared light from 8 to
13 ␮m that escapes the atmosphere efficiently (see Figure 6-7). Since light of
these wavelengths passes largely unimpeded, this portion of the spectrum is

called the atmospheric window.
The injection into the atmosphere, even in trace amounts, of gases that
can absorb thermal IR light will lead to additional global warming, i.e., to
enhancing the greenhouse effect. Particularly serious are pollutant gases that
absorb thermal IR in the atmospheric window region, since the absorption by
H2O and CO2 in other regions is already so great that there remains little
such light for trace gases to absorb. In particular, the fraction of light absorbed
by a gas as it passes through the atmosphere is logarithmically related to its
concentration, C (Beer–Lambert law). Thus the additional global warming
produced by carbon dioxide is logarithmically related to the increases in its
concentration. However, because logarithmic functions are almost linear
near C 0, the warming produced by trace gases is linearly proportional to
their concentration increases (see Additional Problem 5).
In considering which potential pollutants might contribute to global
warming, recall that we can dismiss free atoms and homonuclear diatomic
molecules, as they cannot absorb IR light. Heteronuclear diatomic molecules
such as CO and NO are also not of direct concern since their only vibration—
bond stretching—has a frequency that lies outside the thermal IR region.
In general, however, most long-lived gases consisting of molecules with three
or more atoms are of concern since they possess many vibrations that absorb
IR, one or more of which usually fall in the thermal infrared region. The
important trace greenhouse gases, i.e., those whose concentration is small in
absolute terms but whose ability even at these levels to warm the air is substan-
tial, are detailed below, following a discussion of their average lifetimes in the
atmosphere.
Atmospheric Residence Time

The extent to which a substance accumulates in some compartment of the
environment, such as the atmosphere, depends upon the rate, R, at which it
is received from the source and the mechanism by which it is eliminated,
i.e., its sink. Commonly, the rate of elimination via the sink is directly
proportional to the concentration, C, of the substance in the organism or
environmental compartment. In chemistry, this is known as a first-order
relationship, since the power to which the independent variable is raised is
unity. If the rate constant for the elimination process is defined as k, the rate
of elimination is kC:
rate of intake R
rate of elimination kC
In some cases, such as the atmospheric sink for methane, a reaction involving
a second substance is involved, and k incorporates the steady-state concen-
tration of this other substance.
If none of the substance is initially present, that is,

if C0 0, then initially the rate of elimination must
be zero. The concentration then builds up solely due
1.0 to its input or ingestion, as illustrated near the origin
Concentration C (units of CSS)
CSS = R/k in Figure 6-14. However, as C rises, the rate of elimi-

0.8 (steady-state nation rises and increases since it is proportional
conditions) to C; eventually it matches the rate of intake if R is
a constant. Once this equality is achieved, C does
0.6 not vary thereafter; it is in a steady state, which as we
saw in Chapter 1 is defined as the state for which
0.4 dC/dt 0. Since under these steady-state conditions
rate of elimination or loss rate of intake
0.2
kC R
0 It follows that the steady-state value for the concentra-
0 1 2 3 4 5 6 7 8 tion, CSS, is
Time t (units of k –1)
CSS R/ k
FIGURE 6-14 Increase Often the speed of elimination or loss of a sub-
in concentration with time stance is discussed in terms of the half-life period, t0.5, the length of time
to eventually reach the
steady-state value, CSS.
required for half of it to decay under the condition that all new input has now
ceased. Under the latter condition, we know
dC/ dt kC
Bringing to the left side of the equation all the terms involving C and putting
to the right side the time dependence, we have
dC/ C kdt
If we integrate both sides of the equation, we can find how C changes with
time:
1 dC/ C k 1 dt
Performing the integration, we obtain
ln C kt constant
Thus we see that the logarithm of the concentration will decline linearly
with time for the substance. At time t 0, we have ln C a constant, so we
see that the (integration) constant equals the logarithm of the original con-
centration, C0, the concentration at t 0. Thus
ln C ln C0 kt
From the property of logarithms that log x log y log(x/y), we obtain the
simpler equation
ln(C/ C0) kt
or, in exponential form,
(C/C0) ekt
It is convenient to discuss the rate of decline of a substance in terms of
its half-life. Substituting C 0.5C0 into the logarithmic equation above
yields
ln(0.5C0 /C0) kt1/2
But ln(0.5) 0.693, so we obtain
t1/2 0.693/k
We can use this final result to advantage to substitute for k in our equa-
tion for the steady-state concentration a chemical achieves when it is being
both created and destroyed:
CSS R/k
We obtain
CSS R t0.5 /0.693 or CSS 1.44R t0.5
Clearly, the longer the half-life of a substance in its elimination process, the higher
the steady-state accumulation level it will achieve. The variations with time of
concentrations and rates for systems of this type illustrated in Figure 6-14 are
for the specific case where R and k (and hence C) are expressed in units of
CSS, and time t is expressed in units of k.
Every atmospheric gas that is present at or near a steady state has its own
characteristic residence time, tavg, which equals the average amount of time
one of its molecules exists in air before it is removed by one means or another.
Also known as the average lifetime, the tavg of a substance is equal mathemat-
ically to the time required for its overall concentration to fall to 1/e times its
initial value, where e is the base of natural logarithms. Since at that time
C C0/e, then
C0 /e
ln a b = - ktavg
C0
But ln(1/e) 1, so
tavg 1/k
Substituting this expression for k into CSS gives us CSS R/tavg. Sometimes
this expression is more useful in the form
tavg CSS / R
since it tells us the lifetime of a substance if we know its steady-state concen-

tration and rate of input into the environment.
In order to assess the impact of any substance on the enhanced green-
house effect, it is necessary to know how long the substance is expected to
remain in the atmosphere, since the longer its atmospheric lifetime, the
greater will be its total effect. Thus, e.g., if the steady-state atmospheric
concentration of a gas is 6.0 ppm and if its global rate of input, as deter-
mined by dividing the yearly amount of input by the volume of the atmo-
sphere, is 2.0 ppm/year, then according to the preceding equation, its
average residence time is 6.0 ppm/2.0 ppm/year, or 3.0 years.
The residence times of greenhouse gases such as nitrous oxide and the
CFCs are many decades, so the influence of recent emissions of them will
extend over long periods of time. In contrast, methane has a residence time
of only about a decade.
The analysis above is applicable only to substances having a single first-
order sink process. Thus it does not apply to carbon dioxide, for example,
since this gas has many different sinks (dissolution in the oceans, absorption
by plant matter, etc.) and sources.
P R O B L E M 6-7
If the average steady-state residence time of a trace atmospheric gas is
50 years and its input rate is 2.0 106 kg/year, what is the total amount of it
in the atmosphere?
P R O B L E M 6-8
The steady-state concentration of an atmospheric gas of molar mass 42 g/mol
is 7.0 ␮g/g of air and its residence time is 14 years. What is the annual total
release of the gas into the atmosphere as a whole? See Problem 6-6 for addi-
tional data.
Other Greenhouse Gases

Methane: Absorption and Sinks
After carbon dioxide and water, methane, CH4, is the next most important
greenhouse gas. A methane molecule contains four C9H bonds. Although
C9H bond-stretching vibrations occur well outside the thermal IR region,
HCH bond-angle-bending vibrations absorb at 7.7 ␮m, near the edge of the ther-
mal IR window; consequently, atmospheric methane absorbs IR in this region.
In contrast to the century-long lifetime of carbon dioxide emissions, mol-
ecules of methane in air have an average lifetime of only about a decade. As
discussed in Chapters 3 and 5, the dominant sink for atmospheric methane,
accounting for almost 90% of its loss from air, is its reaction with molecules
of hydroxyl, OH, the very reactive gas present in air in tiny concentration:
CH4 OH ¡ CH3 H2O
This reaction is the first step of a sequence that transforms methane ultimately
to CO and then to CO2 (see Chapter 5 for details).
CH4 ¡ ¡ CH2O ¡ ¡ CO ¡ ¡ CO2
The yearly loss of methane by this reaction currently amounts to about 507 Tg
(where 1 Tg, or teragram, is 1012 g—1 million metric tons), and the net sink
from all processes amounts to about 577 Tg per year.
The other two sinks for methane gas are its reaction with soil and its loss
to the stratosphere, to which a few percent of emissions eventually rise.
Methane reacts there with OH, or atomic chlorine or bromine, or excited
atomic oxygen; reaction with the latter produces hydroxyl radicals and even-
tually water molecules:
O* CH4 ¡ OH CH3
OH CH4 ¡ H2O CH3
Stratospheric water vapor acts as a significant greenhouse gas. About one-
quarter of the total global warming caused by increased methane emissions is
not brought about directly, but rather is due to this effect in the stratosphere
whereby the region’s water content is increased. Due to decreased levels of
ozone and increased levels of carbon dioxide, the stratosphere has undergone
cooling in recent decades; the increase in water vapor has reduced the
amount of this cooling, thus contributing to the warming of the atmosphere
overall.
Per molecule, increasing the amount of methane in air causes a much
larger warming effect than does adding more carbon dioxide, since each CH4
molecule is much more likely to absorb a thermal IR photon that passes
through it than does a CO2 molecule. The effect of the methane is restricted
to the first decade or two after its release, however, because it is highly likely
to be oxidized during this period. When considered over the century after its
emission, a kilogram of methane is still about 23 times more effective in rais-
ing air temperature than the same mass of carbon dioxide; the ratio is about
three times that value over the first 20 years. However, because CO2 is so
long-lived in air and its concentration has increased 80 times more, methane
has been less important in heating the atmosphere. To date, methane is
25
Emissions (millions of tonnes per year)

600
550
20 Total methane emissions
Growth rate (ppb/year)

500
15 450
400
FIGURE 6-15 Changes 10
over the twentieth century Methane growth rate 350
in the annual emission
(black line) and annual
300
5
growth in atmospheric 250
concentration (green line)
0 200
of methane. [Source: “Global
1900 1920 1940 1960 1980 2000
Methane Rise Slows,” Atmo-
sphere (CSIRO Newsletter) Year
(April 1999).]
estimated to have produced about one-third as much global warming as has

carbon dioxide.
Methane: Emission Sources

About 70% of current methane emissions are anthropogenic in origin. The
manner in which total methane emissions rose over the last century is illus-
trated by the black line in Figure 6-15. As in the case of carbon dioxide,
post–World War II rates increased annually much more quickly than had
been the case before. In the last 20 years, however, the emission rate for
methane has leveled off (Figure 6-15).
Most of the methane produced from plant decay results from the process
of anaerobic decomposition, which is decomposition of formerly living mat-
ter in the absence of air, i.e., under oxygen-starved conditions. This process
converts cellulose (approximate empirical formula CH2O) into methane and
carbon dioxide:
2 CH2O ¡ ¡ CH4 CO2
Anaerobic decomposition occurs on a huge scale where plant decay occurs
under waterlogged conditions, e.g., in natural wetlands such as swamps and
bogs and in rice paddies. Indeed, the original names for methane were swamp
gas and marsh gas. Wetlands are the largest natural source of methane emis-
sions, though emissions from this source have decreased sharply over the past
centuries as wetlands have been drained. The huge increase in rice produc-
tion over the same period has presumably led to correspondingly large
increases in methane emissions from this source.
The expansion of wetlands that occurs by the deliberate flooding of land
to produce more hydroelectric power adds to the total natural emissions of
the gas. Deep, small reservoirs produce and emit much less methane than do
shallow ones that contain large volumes of flooded biomass, such as those in
the Brazilian Amazon, especially if the trees are not first removed. Indeed, the
combined global warming effect of the methane and carbon dioxide produced
by a large, shallow reservoir created to generate hydroelectric power can, for
many years, exceed that of the carbon dioxide that would have been emitted
if a coal-fired power plant were used to generate the same amount of electri-
cal power! Hydroelectric power is not a zero-emission form of energy produc-
tion if land is flooded to create it.
The anaerobic decomposition of the organic matter in garbage in land-
fills is another important source of methane in air. Food waste in the landfill
produces the greatest amount of methane. In some communities, methane
from landfills is collected and burned to generate heat, rather than being
allowed to escape into the air. Although the combustion of methane pro-
duces an equal number of molecules of carbon dioxide, because the per mole-
cule effect of CO2 molecules is so much smaller than that of CH4 molecules,
the net greenhouse effect of the emission is thereby greatly reduced in rela-
tion to the amount of CO2 absorbed from the air when the plant matter was
growing.
The burning of biomass, such as forests and grasslands in tropical and
semitropical areas, releases methane to the extent of about 1% of the carbon
consumed, along with larger amounts of carbon monoxide (both compounds
are products of incomplete—poorly ventilated—combustion).
Ruminant animals—including cattle, sheep, and certain wild animals—
produce huge amounts of methane as a by-product in their stomachs when
they digest the cellulose in their food. The animals subsequently emit the
methane into the air by belching or flatulence. The decrease in the popula-
tion of some methane-emitting wild animals (e.g., buffalo) in recent cen-
turies has been far exceeded by the huge increase in the population of cattle
and sheep. The net result has been a large increase in emissions of methane
from animal sources.
It was reported by researchers in 2006 that plants, especially those grow-
ing in tropical areas, emit methane into the air as part of their aerobic metab-
olism, not just through the action of bacteria in anaerobic environments. The
rate of emission of methane increases sharply with air temperature, approxi-
mately doubling for a 10° rise. If aerobic methane release from plants does
occur, some of the observed decrease in global methane emission rates in the
1990s may have occurred because extensive tropical deforestation during that
period would have greatly reduced the number of methane-emitting plants.
Ironically, tropical forests cleared for livestock production may have pro-
duced as much methane as the ruminants that are now raised on that land!
However, research reported by other scientists in 2007 failed to confirm that
methane is produced aerobically and emitted by living plants.
Methane is released into air when natural gas pipelines leak, when coal is
mined and the CH4 trapped within it is released into the air, and when the
BOX 6-3 Determining the Emissions of “Old Carbon”

Sources of Methane
he relative abundances of carbon isotopes that has been trapped in the ground for so
T in atmospheric carbon dioxide can be used
to help deduce its origin by the following logic.
long that its 14C content has diminished to
almost zero as a result of radioactive decay
The carbon in all living matter contains a through the ages. Most methane containing
small, constant fraction of a radioactive iso- old carbon is released into the air as a
tope, carbon-14 (14C), taken in via the carbon by-product of the mining, processing, and
cycle when photosynthesis captures atmo- distribution of fossil fuels. Methane trapped
spheric CO2 and when animals in turn feed off in coal is released into the atmosphere when
plant matter. This fact underlies the radiocar- this material is mined, as is methane in oil
bon dating methods used by archaeologists and when it is pumped from the ground. The
anthropologists: When an organism dies, its 14C transmission of natural gas, which is almost
decays at a known first-order rate that makes entirely methane, involves losses into the air
the date of its death calculable. (The assump- due to leakage from pipelines and is the
tions justifying these methods are that biotic largest of the atmospheric sources of old car-
carbon and atmospheric carbon in CO2 are bon. Measurements of the methane levels in
balanced — in equilibrium with one another — the air of various cities have indicated that
and that the level of atmospheric 14C is con- much of the loss from pipelines in the past
stant. The principles underlying radioactive occurred in eastern Europe. Finally, there is
decay are discussed in Chapter 9.) probably a small contribution to the old carbon
However, in the case of atmospheric source from methane trapped in permafrost in
methane, the average fraction of 14C is less far northern latitudes; the methane was formed
than the value found in living tissue. This by the decay of plant matter that lived there
indicates that a significant fraction of the many thousands of years ago when the polar
CH4 escaping into air must be “old carbon” climate was much warmer than it is today.
gases dissolved in crude oil are released—or incompletely flared—into the air
when the oil is collected or refined. Emissions from these sources have likely
leveled off in the last decade. The technique by which scientists determine
the component of atmospheric methane arising from fossil-fuel sources is dis-
cussed in Box 6-3.
In summary, there are six different significant sources of atmospheric
methane, of which natural wetlands make the greatest contribution (~25%).
The current relative importance of the five important anthropogenic sources
of atmospheric methane is thought to be:
energy production/distribution ~ ruminant animal livestock
rice production ~ biomass burning ~ landfills
Currently, the net sink for methane is thought to outweigh its sources by
about 47 Tg/year, producing a slight net decrease in atmospheric methane
concentration.
Methane: Concentration Trend and

Possible Future Increases
Historically (i.e., before 1750), the methane concentration in air was approx-
imately constant at about 0.75 ppm, i.e., 750 ppb. It has more than doubled
since preindustrial times, to about 1.77 ppm; almost all of this increase
occurred in the twentieth century because the emissions grew quickly, espe-
cially in the 1950–1980 period (see Figure 6-15). By the early 1990s, how-
ever, the rate of concentration increase had declined rapidly, and since that
time it has fallen to zero in some years (see Figure 6-16b), so the methane
concentration in air has been almost constant recently (Figure 6-16a). The
rise in the atmospheric CH4 level that has occurred since preindustrial times
is presumed to be the consequence of such human activities as increased food
production and fossil-fuel use, as discussed above.
(a)
1750
Concentration (ppb)
1700
1650
Change in concentration (ppb per year)
(b)
+15
+10
+5
–5 FIGURE 6-16 Atmo-

spheric methane (a) concen-
–10 tration and (b) annual
’84 ’85 ’86 ’87 ’88 ’89 ’90 ’91 ’92 ’93 ’94 ’95 ’96 ’97 ’98 ’99 ’00 ’01 ’02 ’03 ’04 ’05
fluctuation in concentration
Year in recent decades.
[Source: NOAA.]
It is not known with certainty why the growth rate in methane concen-
tration decreased recently. Since the rate of change in concentration is pro-
portional to the difference between the rate of change in the emission rate
and the rate of change in the destruction rate, change in either one or both
rates could be responsible; neither can be measured directly very accurately.
Natural gas pipelines carry ~90% methane, about 1.5% of which is lost to the
atmosphere. Part of the decline in the emission rate of methane into the air
was likely due to much-decreased emissions from pipelines in the former
Soviet Union, which a few decades ago leaked much more gas than at pres-
ent. However, increasing use of fossil fuels in northern Asia has probably now
replaced some of these emissions. The draining, and drying out from global
warming, of wetlands has resulted in decreased methane emissions from this
natural source in recent decades. Some scientists have speculated that the
declines in the early 1990s were related to the air temperature decreases asso-
ciated with the explosion of Mount Pinatubo. The rate of oxidation of CH4
by OH would also have increased if the concentration of hydroxyl radical
increased overall.
P R O B L E M 6-9
The concentration of atmospheric methane is about 1.77 ppm, and the rate
constant for the reaction between CH4 and OH is 3.6 1015 cm3 mole-
cule1 s1. Calculate the rate, in Tg per year, of methane destruction by reac-
tion with hydroxyl radical, the concentration of which is 8.7 105 molecules
cm3. See Problem 6-6 for additional data.
Some scientists have speculated that the rate of release of methane into air
could greatly increase in the future as a consequence of temperature rises from the
enhanced greenhouse effect. For instance, higher temperatures would accelerate
the anaerobic biomass decay of plant-based matter, as occurs in a common land-
fill. In turn, the additional release of methane would itself cause a further rise in
temperature. This is another example of positive feedback.
Methane release from biomass decay among the extensive bogs and tun-
dra in Canada, Russia, and Scandinavia could also increase with increasing
air temperature and would also constitute positive feedback. However, the
rate of biomass decay and of plant growth, and thus of CH4 production, also
depends on soil moisture and therefore on rainfall, which probably would be
affected by climate change in an as yet uncertain direction, so the net feed-
back from these sources could be positive or negative.
There is much methane currently immobilized in the permafrost of far
northern regions; it was produced from the decay of plant materials during
warm spells in the region but became trapped due to glaciation as temperatures
became lower and lower at the start of the last ice age. Melting of the
permafrost due to global warming could release large amounts of this methane.
Melting would also allow the decomposition of organic matter currently pres-
ent in the permafrost, with the consequent release of more methane.
In addition, there are monumental amounts of methane trapped at the
bottom of the oceans, on continental shelves, in the form of methane hydrate.
This substance has the approximate formula CH4 # 6 H2O and is an example
of a clathrate compound, i.e., a rather remarkable structure that forms when
small molecules occupy vacant spaces (holes) in a cage-like polyhedral struc-
ture formed by other molecules. In the present case, methane is caged in a
3-D ice lattice structure formed by the water molecules. The melting point of
the structure is 18°C, somewhat higher than that of pure ice. Clathrates
form under conditions of high pressure and low temperature, such as are
found in cold waters and under ocean sediments. The methane was produced
over thousands of years by bacteria that facilitated the anaerobic decomposi-
tion of organic matter in the sediments.
If seawater warmed by the enhanced greenhouse effect penetrates to the
bottom of the oceans, the clathrate compounds could decompose and release
their own methane, as well as reservoirs of pure methane currently trapped
below them, to the air above. Methane trapped far below the permafrost in
northern areas and in offshore areas in the Arctic also exists in the form of
clathrates; it would be released eventually if the Arctic warmed sufficiently.
Measurements made thus far do not indicate any significant emissions from
these sources. It has been suggested by some scientists that CH4 released from
clathrates may be oxidized to CO2 before it reaches the air, thereby greatly
reducing the global warming potential.
Although the uncertainties concerning methane feedback are large, the
stakes are higher than with any other gas. A few scientists believe that sev-
eral positive climate feedback mechanisms, including those involving
methane, could possibly combine to trigger an unstoppable warming of the
globe. This worst-case scenario is called the runaway greenhouse effect. Such
climate change would threaten all life on Earth, as the temperature would
rise markedly, ocean currents would probably shift, and rainfall patterns
would be very different from those we know. The possibility that the North
Atlantic ocean current, which brings warm water from the south and thereby
warms Europe, could cease to operate because of rapid global warming—
induced by rapid increases in methane or carbon dioxide—is one of the most
dramatic predictions about the possible consequences of the enhanced
greenhouse effect.
P R O B L E M 6-10
Calculate the mass of methane gas trapped within each kilogram of methane
hydrate.
Nitrous Oxide
Another significant greenhouse trace gas is nitrous oxide, N2O, also known
as “laughing gas”; its molecular structure is NNO rather than the more sym-
metrical NON. Its bending vibration absorbs IR light in a band at 8.6 ␮m,
i.e., within the window region, and in addition one of its bond-stretching
vibrations is centered at 7.8 ␮m, on the shoulder of the window and at the
same wavelength as one of the absorptions for methane. Per molecule, N2O
is 296 times as effective as CO2 in causing an immediate increase in global
warming. Like that of methane, the atmospheric concentration of nitrous
oxide was constant until about 300 years ago, at which time it began to
increase, although the level has increased from 275 ppb (preindustrial) by
only 16% to 320 ppb. The yearly growth rate in the 1980s was about 0.25%
but fell significantly in the early 1990s for reasons that are uncertain. The
increased amounts of nitrous oxide that have accumulated in the air since
preindustrial times have produced about one-third of the amount of the
additional warming that methane has induced.
Less than 40% of nitrous oxide emissions currently arise from anthro-
pogenic sources. In 1990 it was discovered that the traditional procedure,
using nitric acid, HNO3, of synthesizing adipic acid (a raw material in the
preparation of nylon) resulted in the formation and release of large amounts
of nitrous oxide. Since that time, nylon producers have instituted a plan to
phase out N2O emissions.
The greater part of the natural supply of nitrous oxide gas comes from
release from the oceans, and most of the remainder is contributed by processes
occurring in the soils of tropical regions. The gas is a by-product of the biolog-
ical denitrification process in aerobic (oxygen-rich) environments and in the
biological nitrification process in anaerobic (oxygen-poor) environments; the
chemistry of both processes is illustrated in Figure 6-17. In denitrification,
fully oxidized nitrogen in the form of the nitrate ion, NO3, is reduced mostly
to molecular nitrogen, N2. In nitrification, reduced nitrogen in the form of
ammonia or the ammonium ion is oxidized mostly to nitrite, NO2, and
nitrate ions. Chemically, the existence of the nitrous oxide by-product in both
processes is simple to rationalize: Nitrification (oxidation) under oxygen-
limited conditions yields some N2O, which has less oxygen than the intended
nitrite ion; denitrification (reduction) under oxygen-rich conditions yields
some N2O, which has more oxygen than the intended nitrogen molecule.
Nitrification is more important than denitrification as a global source of N2O.
Normally, about 0.001 mole of nitrous oxide is emitted per mole of nitrogen
oxidized, but this value increases substantially when the ammonia or
ammonium concentration is high and relatively little oxygen is present. Over-
all, the increased use of fertilizers for agricultural purposes probably accounts
for the majority of anthropogenic emissions of nitrous oxide. The decomposi-
tion of livestock-produced manure under aerobic conditions, including its use
By-product
Nitrous oxide
FIGURE 6-17 Nitrous

oxide production as a
by-product during the
biological cycling of
nitrogen.
as a fertilizer, contributes significantly to nitrous oxide emissions; manure

produces very little N2O if decomposed anaerobically.
Apparently, nitrous oxide released from new grasslands is particularly sig-
nificant in the years following the burning of a forest. Some portion of the
nitrate and ammonium fertilizers used agriculturally, particularly in tropical
areas, is similarly converted (an unintended effect, to be sure) to nitrous
oxide and released into the air. Tropical forests in wet areas are probably a
huge natural source of the gas.
At one time it was believed that fossil-fuel combustion released nitrous
oxide as a by-product of the chemical combination of the N2 and O2 in air, but
this belief was based on faulty experiments. Only when the fuel itself contains
nitrogen, as do coal and biomass (but not gasoline or natural gas), does N2O
form; apparently, N2 from air does not enter into this process at all. However,
some of the NO produced from atmospheric N2 during fuel combustion in auto-
mobiles is unavoidably converted to N2O rather than to N2 in the three-way
catalytic converters currently in use and is subsequently released into air. Some
of the newer catalysts developed for use in automobiles do not suffer from this
flaw of producing and releasing nitrous oxide during their operation.
As mentioned in Chapter 1, there are no sinks for nitrous oxide in the
troposphere. Instead, all of it rises eventually to the stratosphere, where each
molecule absorbs UV light and decomposes, usually to N2 and atomic oxygen,
or reacts with atomic oxygen.
CFCs and Their Replacements

Gaseous compounds consisting of molecules with carbon atoms bonded
exclusively to fluorine and/or chlorine atoms have perhaps the greatest
potential among trace gases to induce global warming, since they are both
very persistent and absorb strongly in the 8- to 13-␮m atmospheric window
region. Absorption due to the C ¬ F bond stretch is centered at 9 ␮m. The
C ¬ Cl bond stretch and various bond-angle-bending vibrations involving
carbon atoms bonded to halogens also occur at frequencies that lie within the
window region.
As discussed in Chapter 2, chlorofluorocarbons (CFCs) have already
been released into the atmosphere in large quantities and have long resi-
dence times. Due to this persistence and to their high efficiency in absorbing
thermal IR in the window region, each CFC molecule has the potential to
cause the same amount of global warming as do tens of thousands of CO2
molecules. The net effect of CFCs on global temperature is small, however.
The heating that the CFCs produce by the redirection of thermal infrared
is partially canceled by a separate effect, the cooling that they induce in
the stratosphere due to their destruction of ozone. (Recall from Chapter 1
that the stratosphere is heated when oxygen atoms, recently detached
photochemically from ozone molecules, collide with O2 molecules to pro-
duce an exothermic reaction.) However, the decrease in stratospheric
ozone allows more UV light to reach the lower atmosphere and the surface
and to be absorbed there. The cooling and heating effects produced by
CFCs occur at very different altitudes, so that their net effect on the
Earth’s weather may be substantial.
Ironically, the use of CFCs in insulating freezers, refrigerators, and air
conditioners has reduced the energy requirements of this equipment and so
has reduced CO2 emissions resulting from electricity production.
The influence of CFCs on climate in the future will be reduced as a result
of the requirements of the Montreal Protocol, which banned further produc-
tion in developed countries after 1995, as discussed in Chapter 2. Most of the
HCFC and HFC replacements for CFCs (with the notable exception of HFC-
143a) have shorter atmospheric lifetimes and absorb less efficiently in the
center of the atmospheric window region; thus on a molecule-for-molecule
basis, they pose less of a greenhouse threat. However, if their levels of produc-
tion and release become high in future decades because of expanding world
population and increasing affluence, they will make significant contributions
to global warming if they are released into the air. For this reason, many peo-
ple feel that these substances must be used only in closed systems from which
leakage to the atmosphere does not occur and that they must be recovered
from equipment before its eventual disposal. Indeed, prevention of the
chronic release of long-lived gases of all types to the atmosphere is a principle
now agreed to by many scientific, business, and governmental groups. Mea-
surements reported in 2002 indicate that the loss of the refrigerant HFC-134a
(see Chapter 2) from the air-conditioning units of modern cars has a global
warming impact that is about 4–5% of that from the carbon dioxide emitted
from the cars.
P R O B L E M 6-11
Fully fluorinated compounds such as tetrafluoromethane and hexafluoroethane
are released as by-product wastes into the air in the production of aluminum.
They were also briefly considered as CFC replacements. Will such molecules
have a sink in the troposphere? Will they act as greenhouse gases? Would your
answers be the same for monofluoromethane and monofluoroethane?
Sulfur Hexafluoride
Sulfur hexafluoride, SF6, is a little-known greenhouse gas. It has some
importance, however, because it is such a good absorber of thermal IR—
23,900 times greater than CO2 in global warming potential—and because,
like other fully fluorinated compounds, it is so long-lived in the atmosphere
(3200 years). It is used by electric utilities and in the semiconductor industry
as an insulating gas. Formerly, it was vented to the air during routine mainte-
nance of equipment but now is mainly recycled instead.
Tropospheric Ozone
Like methane and nitrous oxide, tropospheric ozone, O3, is a “natural” green-
house gas, but one which has a short tropospheric residence time. Although the
ozone molecule is homonuclear, in its bent structure the central oxygen is not
equivalent to the terminal oxygen atoms; consequently, the O9O bonds are
somewhat polar. For that reason, the dipole moment of O3 molecules changes
during the symmetrical stretch vibration, which occurs in the atmospheric
window region between 9 and 10 ␮m, and the molecules can absorb this IR
light. The dip near 9 ␮m in the window region of the outgoing thermal IR
distribution (Figure 6-7) is due to absorption by this vibration in atmospheric
ozone molecules. Ozone’s bending vibration occurs at 14.2 ␮m, near that for
CO2, and thus does not contribute much to the enhancement of the green-
house effect, since atmospheric carbon dioxide already removes much of the
outgoing light at this frequency. The antisymmetric stretching vibration of
O3 occurs at 5.7 ␮m, where there is very little outgoing IR.
As explained in Chapter 3, ozone is formed in the troposphere as a result
of pollution from power plants and motor vehicles, from forest fires and grass
fires, as well as from natural processes. As a result of these anthropogenic
activities, the levels of ozone in the troposphere probably have increased
since preindustrial times. The best guess is that approximately 10% of the
increased global warming potential of the atmosphere results from increases
in tropospheric ozone, although this value is very uncertain. The amount of
thermal IR absorbed by stratospheric ozone has probably dropped slightly due

to the recent decline in ozone levels.
The Climate-Modifying Effects of Aerosols

In Chapter 2, we saw that the initial neglect by scientists of the effects of
atmospheric aerosol particles, specifically ice crystals in the stratosphere, led to
a large underestimation of the amount of ozone that would be destroyed by
chlorine. Similarly, neglect of aerosols led to misleading predictions about the
extent of global warming to be expected. It is now realized that aerosols off-
set and thereby mask a significant fraction of the atmospheric temperature
increase that would have otherwise occurred due to the anthropogenic green-
house gas emissions. The types of particulate matter of most importance in this
context are particles expelled by powerful volcanic eruptions into the upper
atmosphere and those produced by industrial processes and expelled into the
lower troposphere. In order to understand how aerosols can affect global warm-
ing, it is necessary to understand how they interact with light.
The Interaction of Light with Particles

All solids and liquids—including atmospheric particles—have some ability
to reflect light. Atmospheric particles can reflect incoming sunlight, with the
consequence that some of it is directed back into space and so is unavailable
later for absorption at the surface (see Figure 6-18). The particles can also
reflect outgoing infrared light, with the consequence that some of it is
redirected back toward the Earth’s surface rather than escaping from the
atmosphere. The redirection of light by a particle is sometimes called scatter-
ing; reflection backward is backscattering.
(b)
Incoming (a)
sunlight
FIGURE 6-18 Interaction

Reflection
of sunlight with suspended Ordinary droplets
atmospheric particles.
(a) Modes of interaction.
(b) Illustration of the indi- Absorption
rect effect of producing
increased reflection by
small water droplets as Airborne
compared to larger ones particle
having the same total Sulfate-centered droplets
volume.
Certain types of suspended particulates in air reflect some of the sunlight

that shines on them back into space and so have a significant albedo value;
this reflection of sunlight by the aerosol cools the air mass and the surface
below it, since none of the reflected light is subsequently absorbed and then
converted to heat.
Some types of aerosol particles can absorb certain wavelengths of light
(Figure 6-18a). Once absorbed, the energy that was associated with the light
is rapidly converted into heat, which then is shared with the surrounding air
molecules as a result of their collisions with the heated particle. Thus
absorption of light by a particle leads to warming of the air immediately sur-
rounding it. The absorption of sunlight, with consequent warming, is signifi-
cant only for dark-colored particles such as those composed primarily of soot,
often called carbon black, and of ash particles from volcanoes. The contribu-
tion of carbon black to global warming has only recently been fully appreci-
ated. The emission into the atmosphere of carbon black is greatest in
developing countries, where incomplete combustion of coal and biomass is
widespread. Its effect globally is to increase air temperatures by its absorption
of sunlight, with the subsequent export of this tropospheric air to other areas.
However, its local effect may be cooling, since it blocks sunlight from reach-
ing the surface. Carbon black’s effects on local climate may be substantial,
increasing drought in some areas and flooding in others.
Recall from Chapter 3 that the sulfur dioxide gas predominantly released as
a pollutant from the burning of fossil fuels—especially coal—and from the
smelting of nonferrous metals creates a sulfate aerosol. Pure sulfate aerosols do
not absorb sunlight since none of their constituents—water, nitric and sulfuric
acids, and the ammonium salts thereof—absorb light in the visible or the UV-A
regions. The sulfate aerosols are not particularly effective in trapping outgoing
thermal IR emissions. Only if tropospheric sulfate aerosols incorporate some
soot will absorption of sunlight by these particles be significant.
Overall, however, anthropogenic sulfate-rich aerosols produced in
abundance—especially in the Northern Hemisphere—reflect sunlight back
into space much more effectively than they absorb it, so they significantly
increase Earth’s average albedo. As a result, less sunlight is available to be
absorbed and converted to heat in the lower troposphere and at the surface.
Thus the net effect of the sulfate aerosols is to cool the air near ground level and
thereby to offset some of the global warming induced by greenhouse gases.
In addition to the direct effect of sulfate aerosols in reflecting sunlight,
there are indirect effects that arise because the sulfate particles act as nuclei
for the formation of small water droplets.
• Such small droplets are more effective in backscattering light than are an
equal mass of larger ones (see Figure 6-18b).
• Small droplets are also less likely to coalesce into raindrops, so their
clouds are longer-lived than otherwise expected and can thus reflect sunlight
for longer periods.
Both these indirect effects result in more sunlight being reflected back into
space, thereby cooling the Earth’s surface. In addition, the “Asian brown
cloud” (Chapter 4) formed by aerosol particles reduces the strength of the
essential monsoon rains over India and Asia.
Some scientists have proposed that sulfate particles be injected artificially
into the stratosphere, where they would reflect sunlight and thereby offset
some of the effects of global warming. The lifetime of the particles in the
stratosphere is several years, depending on altitude, so the sulfate would
have to be replenished regularly. Although the injection of sulfate particles is
considered to be a short-term solution, until controls for carbon dioxide emis-
sions have been put in place, a few scientists have proposed injecting solid
reflecting objects of macroscopic size high above the atmosphere, where they
would reflect sunlight and counter global warming on a long-term basis.
Such geoengineering of the Earth’s climate is considered controversial by
many scientists and policymakers because of the uncertainties involved in its
potential side effects.
A short-term, dramatic example of the effects of atmospheric aerosols on
climate occurred as a consequence of the massive eruption of substances into
the troposphere and stratosphere by the Mount Pinatubo volcano in the
Philippines in 1991. Initially, the lower stratosphere was warmed by the
dominant effect of the large volcanic ash particles, which absorbed some of
the incoming sunlight and subsequently converted it to heat, and by their
interception of outgoing infrared from the surface. Due to their relatively large
size, the ash particles were not long-lived in the stratosphere. The longer-term
effect of the Pinatubo eruption was to significantly decrease air temperatures at
ground level. The stratospheric aerosol that remained suspended after a few
months was formed by the oxidation of the 30 million tonnes of SO2 that the
volcano had blasted directly into the lower parts of this region. The sulfate
aerosol remained there for several years, during which time it efficiently
reflected sunlight back into space. Many regions, including North America,
experienced several cool summers in the early 1990s as a result. Due to the
gradual sedimentation of the aerosol, we returned to 1990–1991 temperatures
by 1995.
Aerosols and Global Warming

The cooling effect of the sulfate aerosol is concentrated almost entirely in the
Northern Hemisphere because most industrial activity takes place in that
half of the globe, so it is there that most emissions occur. The relatively short
lifetime of such sulfate aerosols precludes their spreading to the Southern
Hemisphere; consequently, the concentration of sulfate particulates is much
higher over the Northern Hemisphere. The short lifetime of the sulfate par-
ticles can be understood by considering the processes of their removal from
air. The average diameter of the tropospheric sulfate aerosol particles is about
0.4 ␮m, and their average altitude is about 0.5 km. For particles of this size
and altitude, the expected atmospheric

80
lifetime before gravitational settling to the
Emissions of sulfur dioxide (Tg of S)

surface is several years. However, since the 70
sulfate aerosol droplets are also removed
60
efficiently by rain, their actual lifetime in
the lower troposphere is of the order of 50
days rather than years.
40
The increase of global SO2 emissions
from fossil-fuel combustion over the last 30
century and a half is shown in Figure 6-19. 20
Up to 20% more sulfur dioxide is emitted
by smelting, etc. Presumably the trend in 10
anthropogenic sulfate aerosol production 0
has approximately followed the pattern of 1850 1900 1950 2000
SO2 emissions in Figure 6-19. The initial Year
approximately linear time increase of the
sulfur dioxide emission rate changed to one with a much steeper slope after FIGURE 6-19 Estimated
World War II, a behavior we saw previously for CO2 and CH4. However, the historical emissions of
ratio of global SO2 to CO2 emission rates, expressed as a percentage of sulfur sulfur dioxide from
in the carbon of the fuel, fell from about 2.2% in the 1930s and 1940s to a anthropogenic sources.
constant 1.1% in recent decades, due presumably to the gradual replacement [Source: Adapted from
S. J. Smith, H. Pitcher, and
of coal by oil and natural gas. T. M. L. Wigley, “Global and
As illustrated by the contour diagrams in Figure 6-20, the bulk of the Regional Anthropogenic
anthropogenically produced aerosols in North America is centered above Sulfur Dioxide Emissions,”
the Ohio Valley and directly reflects sunlight mostly above that area. Equal or Global and Planetary Change
even larger effects are observed over southern Europe and portions of China. 29 (2001): 99.]
Indeed, according to some calculations, the cooling effect from aerosols
90˚N
1.0 0.5 1.0

45˚N 1.0
0.5 FIGURE 6-20 The
amount of sunlight
0.5 0.5 reflected into space by
0˚ anthropogenic aerosols by
the direct mechanism, in
units of watts per square
meter of the Earth’s surface.
45˚S [Source: J. T. Houghton et al.,
Climate Change 1994 —
Radiative Forcing of Climate
Change (Intergovernmental
90˚S Panel on Climate Change)
180˚ 90˚W 0˚ 90˚E 180˚ (Cambridge: Cambridge
BOX 6-4 Cooling over China from Haze
easurements of the amount of sunshine the aerosols, maximum summer temperatures

M reaching the surface in China indicate
a significant decrease over the last half-
in heavily polluted eastern China have fallen
by about 0.6°C per decade. Similar effects are
century (Figure 1). The blockage of solar observed in the Brazilian Amazon region, due
intensity results from the aerosols in the air to soot and ash emitted into the local air
above the region produced mainly from the from forest and grass fires lit to clear land,
sulfur dioxide emitted by burning coal. As a and in the African country of Zambia, due to
consequence of the increasing presence of grass fires.
2
Percentage change
–1
–2
–3
–4
1950 1960 1970 1980 1990 2000
Year
FIGURE 1 Change in the amount of sunlight reaching China relative to the average, over
50 years. [Source: F. Pearce, “Pollution Is Plunging Us into Darkness,” New Scientist (14 December
2002):6.]
outweighs the heating effect due to greenhouse gases for some regions in
these areas.
It is not clear how the amount of tropospheric sulfate aerosol will change
in the future. Emissions of sulfur dioxide from power production in North
America and western Europe are now more tightly controlled in order to
combat acid rain, so the SO2/CO2 ratio in emissions from these areas should
decline. However, the anthropogenic sulfate aerosol concentrations over
southern Europe and parts of Russia and China are considerably higher than
the current maximum values in North America and will not be affected by
these legislative controls (see Box 6-4). The only substantial domestic energy
source currently available to China for its rapid industrialization is coal, so

the SO2 emissions from this source and from India may well continue to rise
(Chapter 3).
Aerosols also result from the oxidation of the gas dimethyl sulfide
(DMS), (CH3)2S, which is produced by marine phytoplankton and subse-
quently released into the air over oceans. Once in the troposphere, DMS
undergoes oxidation, some of it to SO2, which then can oxidize to sulfuric
acid, and some to methanesulfonic acid, CH3SO3H. Both of these acids
form aerosol particles, which in turn lead to the formation of water droplets
and hence clouds over the oceans. The particles and droplets both deflect
incoming light from the Sun. Some scientists believe that increased emis-
sions of dimethyl sulfide from the oceans will occur when seawater warms as
a result of the enhancement of the greenhouse effect and that this negative
feedback will temper global warming.
Although the sulfate aerosol has a short lifetime, new supplies of it are
constantly being formed from the sulfur dioxide pollution that pours into
the atmosphere on a daily basis. Consequently, there is a steady-state
amount of the aerosol in the troposphere; sulfur dioxide emissions keep post-
poning the full effects of global warming induced by the rise in greenhouse
gas concentrations.
Global Warming to Date

Allocation of Warming to Natural
and Anthropogenic Factors
The best estimates of global warming or cooling in 2005 arising from the var-
ious factors is summarized by the bar graphs in Figure 6-21; the effect of each
factor is expressed as a percentage of the total anthropogenic effect. The
order of the greenhouse gases in terms of the amount of extra warming they
have produced is
CO2 7 CH4 7 O3 7 CFCs 7 N2O

The value in Figure 6-21 for CFCs includes the cooling of the stratosphere
induced by their destruction of ozone, and that for methane includes the
warming of the stratosphere produced from the additional water vapor
formed there by its decomposition. The cooling labeled surface albedo is the
net result of cooling due to changes in land use minus warming arising from
the deposition of sunlight-absorbing black soot on snow and ice. Overall, the
cooling from anthropogenic aerosols currently cancels about 40% of the net
warming from all greenhouse gases. However, the aerosol effect—which is
the sum of that from the direct and indirect effects on cloud albedo—has by
far the largest uncertainty of any of the factors in Figure 6-21.
(percentage of anthropogenic warming)

100
80
Global warming
60
40
20
–20
Global cooling
FIGURE 6-21 Contribu-

–40
tions to global warming
and cooling produced by
various factors, expressed –60
as percentages of the total
anthropogenic warming.
[Data source: Intergovernmen-
–80
tal Panel on Climate Change,
Climate Change 2007: The –100
Physical Science Basis. CO2 CH4 Tropospheric CFCs N2O Surface Aerosols Total Solar
O3 albedo anthropogenic
Summary for Policymakers
(February, 2007).]
Greenhouse gas emissions from airplanes traveling long distances high in

the troposphere are particularly effective in promoting global warming. They
emit, into the low-density air in which they fly, the carbon dioxide and water
vapor that result from the combustion of their hydrocarbon fuel. Because the
air temperature there is so low, the IR absorbed by this CO2 and H2O is
unlikely to be re-emitted; instead, it warms the surrounding air and therefore
enhances the greenhouse effect.
Global Warming: Geography

The year-to-year variations in the average worldwide surface temperature
from 1880 to the present are shown in Figure 6-2. The increases in tempera-
ture were not evenly spread around the globe, however, as indicated by Figure
6-22, which shows the changes in average global temperatures in the
2001–2005 period, relative to the 1951–1980 average. In Figure 6-22, the
darker the shade of green, the greater the increase in temperature; the few
areas shown in gray underwent decreases in temperature. In general, air
FIGURE 6-22 Changes,

in degrees Celsius, in the
mean surface temperature
in 2001–2005 relative to
the 1951–1980 mean.
The dotted regions
indicate areas for which
data is insufficient.
[Source: J. Hansen et al.,
0.8 0.4 0.2 0.2 0.4 0.8 1.2 1.6 2.1 “Global Temperature Change,”
Proceedings of the National
Temperature change (C)
Academy of Science 103
(2006): 14288.]
temperatures over land areas have increased more than those over the seas.
Sulfate aerosols keep the eastern portions of the United States and Canada
cooler than they would be otherwise.
The Arctic region has warmed most of all, with the consequence that its
sea ice is disappearing. The melting produces a positive feedback effect: Since
ice reflects sunlight more efficiently than does liquid water, the increasing
amount of sunlight absorbed as the ice is replaced by open water increases
surface water and surface air temperatures, thereby inducing even more melt-
ing. However, scientists have recently found that evaporation of the open
water has produced more cloud cover in the region, which is a negative feed-
back effect that partially negates the positive one since the clouds reflect sun-
light and thereby increase the albedo.
The increased lowering of air temperatures due to higher sulfate aerosol
levels does not permanently cancel out all the warming due to greenhouse
gases because of the very different atmospheric lifetimes of the particles as
compared to the gases. The tropospheric aerosols last only a few days, so they
do not accumulate with time and their effect is short term. In contrast,
today’s emissions of carbon dioxide into the atmosphere will exert effects for
decades or centuries to come: CO2 emissions are cumulative over the medium
term. This is also true for CFCs and nitrous oxide, which are also important
greenhouse gases, but it is less so for methane since its half-life is only about
one decade. Thus, although sulfate-producing SO2 emissions can temporarily
cancel the effects of CO2 emissions, eventually the cumulative effects of the
carbon dioxide and the other greenhouse gases win out.
In summary, global warming has been experienced by most areas in the

last half-century. Most of the warming is due to emissions of carbon dioxide
into the atmosphere, with lesser amounts of warming from increased levels of
methane, tropospheric ozone, nitrous oxide, and the introduction of CFCs.
The increased water vapor in the atmosphere resulting from the warming by
these gases has itself produced at least as much additional warming. The
increased emissions of sulfur dioxide that accompany fossil-fuel combustion
have produced aerosols that cancel out some but not all of the warming pro-
duced by the greenhouse gases.
Global Circulation Models

In continuing research that began in the 1980s, scientists have attempted by
computer modeling to predict the impact of past and present increases in
atmospheric gases and particles on the future climate of the planet. There
are some uncertainties in such an endeavor, including the fact that we don’t
yet fully understand all the sources and sinks of the greenhouse gases or the
net effect of aerosols. Probably the most important problem remaining with
these global circulation models is their treatment of clouds. In particular, is
the net feedback from the increased cloudiness expected for a warmed
atmosphere negative, positive, or zero? Clouds operate both to cool and to
heat the atmosphere. They cool it by reflecting incoming light back to
space; we experience this dramatically when the Sun goes behind the clouds
on a warm, sunny day and we immediately feel the air cooling. We also
know that the water droplets in clouds absorb infrared light emitted from
below them.
• Low-lying clouds are warm, so they re-emit almost all the energy absorbed
in random directions, rather than converting it to heat and thereby warming
the air in their immediate surroundings. Since some of the IR emitted by these
low clouds is directed downward, the surface is warmed. The fact that the IR is
all re-emitted, however, means that these clouds don’t warm the atmosphere
much by this effect. Thus the net effect over a full day of low-lying clouds is to
cool the Earth, because their reflection of incoming sunlight is dominant.
• In contrast, high-lying clouds absorb outgoing IR but don’t re-emit much
of it since they are cold; all the absorbed IR is converted to heat, warming the
nearby air. Thus the net effect of high-lying clouds is to warm the Earth, since
their conversion of outgoing IR into heat is more important than their reflec-
tion of incoming sunlight.
Because we don’t accurately know whether global warming will produce more
additional low-lying or high-lying clouds, it is uncertain whether the feed-
back from this factor will be positive or negative.
It is not absolutely certain that all or indeed any part of the observed
temperature increases in the last 100 years are attributable to the
anthropogenically induced enhancement of the greenhouse effect. How-

ever, natural, century-long global warming or cooling trends as large as the
half-a-degree-Celsius we have recently experienced appear only once or
twice a millennium. There is an 80–90% likelihood that the increase in the
twentieth century was not a wholly natural climatic fluctuation. Further-
more, on the basis of computer simulations such as that discussed above,
the UN-sponsored Intergovernmental Panel on Climate Change (IPCC)
concluded in its 2007 report that “most of the observed increase in globally
averaged temperatures since the mid-twentieth-century is very likely due to
the observed increase in anthropogenic greenhouse gas concentrations.”
Some skeptics have pointed out that the evidence indicating that global
warming has begun is based on air temperatures at the Earth’s surface only,
and that satellite data indicate that the lower troposphere as a whole has
cooled rather than warmed. However, other scientists claim that this cooling
is spurious and apparently arises from problems in merging data from two
different satellites with slightly different calibrations and other artifacts of
uncertainties in the data.
Other Signs of Global Warming

In addition to a rise in average global surface air temperature, there have been
a number of other shifts that indicate that the climate indeed is changing:
• Winters have become shorter, by about 11 days. In the Northern Hemisphere,
spring has been arriving sooner and autumn has been starting later. Over the last
three decades, the advent of spring—as observed by the appearance of buds, the
unfolding of leaves, and the flowering of plants—has advanced by an average of
six days in Europe, while the start of autumn—as defined by the date at which
leaves change color and begin to fall—has been delayed by about five days. In
Alaska and northwestern Canada, average temperatures have risen one degree
per decade recently, resulting in an earlier date for the last frost in the spring and
significant thawing of the permafrost. Consequently, in many regions there are
fewer “frost days” now than there used to be—19 fewer in the western United
States and 3 fewer in the eastern part. The response of plants is driven by the
increase in average daily air temperatures. Indeed, the range boundaries of some
plants have increased toward the poles, and phenologies (season-dependent
behavior) have shown an earlier start for spring for the great majority of plants
and animals. The earlier springtime disappearance of mountain snow packs as
well as higher temperatures in spring and summer have led to a substantial
increase in the number, duration, and intensities of wildfires in the western
United States since the mid-1980s.
• The Earth’s ice cover is shrinking fast. Glaciers, polar icecaps, and polar sea
ice are melting and disappearing at unprecedented rates as a consequence of
global warming. For example, the remaining glaciers in Glacier National Park
in the U.S. Rocky Mountains could disappear in 30 years if current melting

rates continue. About 10% of the world’s winter snow cover has disappeared
since the late 1960s. Sea ice in the Arctic has not only decreased in area, by
about 9% per decade recently, but it has also thinned dramatically. Warmer
weather has also delayed the seasonal formation of sea ice. All these changes
have caused a sharp decline in some populations of Antarctic penguins and
Arctic caribou.
• Warming water is killing much of the coral in ocean reefs and threatening sea
life. Coral reefs in tropical waters nurture and protect fish and attract scuba
divers. As water warms, corals “bleach” themselves by expelling the algae
that give them color and provide nutrition. Over 95% of the coral is already
dead in some parts of the Seychelles Islands. Thus far, reefs in the central
Pacific Ocean have escaped bleaching, and it is just beginning in the
Caribbean. The death of the coral reefs not only affects the tourist trade but
also threatens fishing for species that depend on the reefs for food. Beaches
will erode if the reefs break up and no longer provide protection.
• Mosquito-borne diseases have reached higher altitudes. Because of warmer
temperatures, mosquitoes are now able to survive in regions where they for-
merly were not viable. As a result, mosquitoes have carried malaria to higher
mountain regions in parts of Africa and dengue fever to new regions in
Central America. Outbreaks of malaria have occurred in Texas, Florida,
Michigan, New York, New Jersey, and even southern Ontario in the last
decade. Warmer weather and changing precipitation patterns allowed the
West Nile virus, another mosquito-borne disease, to become established
in the New York City area in the late 1990s and in southern Canada and
virtually all the contiguous United States by the early 2000s.
• Rising sea levels are threatening to engulf Pacific islands. Warming of the air
eventually leads to a rise in sea levels, for reasons that will be discussed in
Chapter 7. The change in average sea level from 1870 to the present is illus-
trated in Figure 6-23. The rise since 1930 amounts to over 15 cm, a sharp rise
in the rate of increase for this process compared to the past.
• Precipitation has increased in most areas. An important aspect of climate is the
amount of precipitation—rain and snow—that falls at various locations on
Earth. In the twentieth century, the total annual precipitation in the Northern
Hemisphere increased, with most mid- and high-latitude regions of eastern
North and South America, Europe, and Asia becoming somewhat wetter.
However, many areas just north and south of the Equator, especially in Africa
and parts of southern Asia, became much drier, producing more intense and
longer droughts, with disastrous consequences for food production there. An
overall increase in global precipitation is expected, since warming of the air
warms the surface waters of lakes and oceans, and warmer water evaporates faster
and thereby increases the water content of the atmosphere.
Average sea level difference, 1961–1990 (mm) +100
+50 FIGURE 6-23 Changes

to the global average sea
level, relative to the
0
1961–1990 average. The
smoothed curve (black)
–50 represents decadal aver-
ages, whereas the white
circles show yearly values.
–100 The green shaded area
represents the uncertainty
–150 interval.
[Source: Intergovernmental
Panel on Climate Change,
Climate Change 2007: The
1850 1900 1950 2000
Physical Science Basis.
Year Summary for Policymakers
(February, 2007).]
• Extreme weather is becoming more common. The frequency of extreme

and violent weather events has increased in many areas of the world. Such
events include stronger blizzards and storms with heavy snow and freezing rain in
northern areas but record heat waves, hurricanes, and drought in others. For
example, the number of heat waves lasting three days or longer almost doubled
in the United States between 1949 and 1995. The heat wave in Europe in the
summer of 2003 was a tragic example of the phenomenon. Moreover, the fre-
quency of storms with heavy or extreme precipitation increased in many non-
tropical regions in the last half-century. The economic damage caused by storms,
including hurricanes, has increased markedly over the last two decades.
Review Questions
1. Sketch a plot showing the main trends in global 4. Explain what is meant by the terms symmetric
air temperature over the last century and a half. and antisymmetric bond-stretching vibrations and by
bending vibrations.
2. What is the wavelength range, in ␮m, for
infrared light? In what portion of this range does 5. Explain the relationship between the frequency
the Earth receive IR from the Sun? What are the of vibrations in a molecule and the frequencies of
wavelength limits for the thermal IR range? light it will absorb.
3. Explain in terms of the mechanism involved 6. Why don’t N2 and O2 absorb thermal IR?
what is meant by the greenhouse effect. Explain Why don’t we consider CO and NO to be trace
what is meant by the enhancement of the green- gases that could contribute to enhancing the
house effect. greenhouse effect?
7. What are the two main anthropogenic sources increased temperature an example of feedback? If
of carbon dioxide in the atmosphere? What is its so, is it positive or negative feedback? Would an
main sink? What is fixed carbon? increase in the rate and amount of photosynthesis
with increasing temperatures and CO2 levels be a
8. Is water vapor a greenhouse gas? If so, why is it
case of positive or negative feedback?
not usually present on lists of such substances?
16. Explain in chemical terms what is meant
9. Explain what is meant by positive and negative
by nitrification and denitrification. What are the
feedback. Give an example of each as it affects
conditions under which nitrous oxide production
global warming.
is enhanced as a by-product of these two
10. What is meant by the term atmospheric window processes?
as applied to the emission of IR from the Earth’s
17. What are the main sources and sinks for N2O
surface? What is the range of wavelengths of this
in the atmosphere?
window?
18. Are the proposed CFC replacements
11. What is meant by the residence time of a gas in
themselves greenhouse gases? Why is their
air? How is it related to the gas’s rate R of
emission considered to be less of a problem in
input/output and to its total concentration C?
enhancing the greenhouse effect than was that of
12. What are four important trace gases that the CFCs themselves?
contribute to the greenhouse effect?
19. By which two mechanisms does light interact
13. What are the six most important sources of with atmospheric particles?
methane?
20. Explain how sulfate aerosols in the
14. What are the three most important sinks for troposphere affect the air temperature at the
methane in the atmosphere? Which one of them Earth’s surface by both the direct and indirect
is dominant? What is meant by the term clathrate mechanisms.
compound?
21. List four important signs, other than increases
15. Is the enhancement of the greenhouse effect in average air temperature, that global warming is
by release of methane from clathrates due to occurring.

See the discussion of focus areas and the principles (b) List four of the twelve principles of green
of green chemistry in the Introduction before chemistry that are addressed by the green
attempting these questions. chemistry developed by Los Alamos and
SC Liquids.
1. The development of supercritical carbon
dioxide for removal of photoresist (SCORR) won 2. What environmental advantages does the
a Presidential Green Chemistry Challenge Award. SCORR process offer versus conventional methods
(a) Into which of the three focus areas for these for photoresist removal?
Additional Problems
1. The common tropospheric pollutant gases SO2 account for two-thirds of the total, had to be
and NO2 have molecular structures which, like reduced if the atmospheric concentration of
that of CO2, have the central atom connected to this gas was to be stabilized in 1992.
two oxygen atoms, but, unlike CO2, they are
5. As mentioned in the text, the fraction F of
nonlinear. The wavelengths for their vibrations
light that is absorbed by any gas in air is logarith-
are given in the table below. (a) Which of the
mically related to the concentration C of the gas
vibrations are capable of absorbing infrared energy?
and the distance d through which the light travels;
(b) Based on the wavelengths for the IR-absorbing
this relationship is called the Beer–Lambert law:
vibrations and the spectrum in Figure 6-7, decide
which, if any, vibrations could contribute much loge(1 F) KCd
to global warming. (c) What lifetime characteristic
Here K is a proportionality constant. Show by
of these gases would limit their role in global
simple trial calculations that for concentrations
warming?
near zero (e.g., where KCd 0.001), F is related
Symmetric Antisymmetric almost linearly to C, whereas for larger KCd values
Gas stretch stretch Bending (e.g., near 2), doubling the concentration does not
nearly double the light absorption.
SO2 8.7 ␮m 7.3 ␮m 19.3 ␮m
6. The vapor pressure P of a liquid rises exponen-
NO2 7.6 ␮m 6.2 ␮m 13.3 ␮m tially when it is heated according to the equation
2. (a) How can the fact that nitrous oxide has ln(P2 / P1) H / R (1/ T1 1 / T2)
three vibrations that absorb infrared light be used
Here P2 and P1 are the vapor pressures of the
to prove that its linear structure is NNO rather
liquid at the Kelvin temperatures T2 and T1 after
than NON? (b) Would methane molecules absorb
and before the temperature increase, R is the gas
IR during the vibration in which all four C ¬ H
constant 8.3 J/K mol, and H is the liquid’s
bonds stretched or contracted in phase?
enthalpy of vaporization, which for water is
3. Anthropogenic carbon dioxide emissions into 44 kJ/mol. Calculate the percentage increase
the atmosphere amounted to 178 Gt from January in the vapor pressure of water that occurs if the
1990 to December 1997. Calculate the fraction of temperature is raised from 15°C to 18°C. Give
this emitted carbon dioxide that remained in the several reasons why the amount of outgoing
air, given that in that same eight-year period, thermal infrared in water’s absorption bands may
the carbon dioxide concentration in air rose by not be increased by exactly the percentage you
11.1 ppm. Note that the molar masses of C, O, calculate if the average surface air temperature
and air, respectively, are 12.0, 16.0, and 29.0 g, is increased to 18°C.
that the mass of the atmosphere is 5.1 1021 g,
7. Suppose that some climatic crisis inspired
and that 1 Gt is 1015 g.
the Earth’s population to switch to energy systems
4. The total amount of methane in the atmosphere that did not emit carbon dioxide and that the
in 1992 was about 5000 Tg and was then increasing transition occurred within a decade. What would
by about 0.6% annually due to the fact that the be the immediate effect of this change on the
annual input rate exceeded the annual destruction Earth’s average air temperature, given that both
rate of 530 Tg/yr. Calculate the percentage by carbon dioxide and sulfur dioxide emissions from
which anthropogenic releases of methane, which fossil fuels would have rapidly declined?
8. Explain why CHF2Cl (HCFC-22) has more density as n-octane: 0.702 g/mL. Calculate the vol-
IR absorption bands with a greater range of IR ume of CO2 produced by driving 100 miles on the
wavelengths absorbed, and absorbs IR much more highway in a mid-size sedan compared to an
efficiently on a per molecule basis, than CH4, the SUV, given their highway fuel efficiencies of 33 and
hydrocarbon from which it is derived. 19 mpg, respectively. Note that 1 gal 3.785 L.
9. Calculate the volume of CO2 produced at 1 atm 10. Given that the 2002 concentration of CH4 in
and 20.0°C from the complete combustion of 1.00 L the atmosphere was 1.77 ppm, calculate the total
of gasoline. Although gasoline is a mixture of mass of CH4 in the atmosphere in 2002. Note that
hydrocarbons (as described in Chapter 7), for the the total mass of the atmosphere is 5.1 1018 kg
purposes of this calculation consider gasoline to and the average molar mass of the atmosphere is
have the chemical formula C8H18 and the same 29.0 g/mol.
Further Readings
1. J. T. Houghton et al., Climate Change 2001: The 8. P. Bousquet et al., “Contribution of Anthro-
Scientific Basis (Cambridge: Cambridge University pogenic and Natural Sources to Atmospheric
Press, 2001). (Published for the Intergovernmental Methane Variability,” Nature 443 (2006):
Panel on Climate Change.) 439–443.
2. E. Claussen, ed., Climate Change: Science, 9. C. Parmesan and G. Yohe, “A Globally
Strategies, and Solutions (Arlington, VA: Pew Coherent Fingerprint of Climate Change Impacts
Center on Global Climate Change, 2001). Across Natural Systems,” Nature 421 (2003):
37–42.
3. D. Rind, “The Sun’s Role in Climate
Variations,” Science 296 (2002): 673–677. 10. L. D. D. Harvey, Global Warming: The Hard
Science (New York: Prentice-Hall, 2000).
4. V. Ramanathan et al., “Aerosols, Climate, and
the Hydrological Cycle,” Science 294 (2001): 11. T. Flannery, The Weather Makers (Toronto:
2119–2124. Harper-Collins, 2005).
5. F. W. Zwiers and A. J. Weaver, “The Causes of 12. A. Gore, An Inconvenient Truth (Emmaus, PA:
20th Century Warming,” Science 290 (2000): Rodale, 2006).
2081–2137.
13. O. Morton, “Is This What It Takes to Save
6. J. Hansen et al., “Global Temperature Change,” the World?” Nature 447 (2007): 132.
Proceedings of the National Academy of Science 103
14. B. Lomberg, “The Skeptical Environmental-
(2006): 14288–14293.
ist” (Cambridge: Cambridge University Press,
7. D. F. Ferretti et al., “Unexpected Changes 2001), Chapter 24.
to the Global Methane Budget over the Past
2000 Years,” Science 309 (2005): 1714–1716.
C H A P T E R
7
FOSSIL-FUEL ENERGY,
CO2 EMISSIONS, AND
GLOBAL WARMING
topics are used:
 Percentage composition; stoichiometry
 Combustion; heat of combustion
 Structural chemistry of hydrocarbons (see Appendix)
 Acidity; weak acids; pH
 Phase diagrams; condensation of liquids; sublimation
of solids; distillation
 Catalysis
 Density
 Polymerization

 Greenhouse effect and greenhouse gases;
aerosols (Chapter 6)
 Sinks (Chapter 6)
 ppm concentration scale for gases (Chapter 1)
 Clathrates (Chapter 6)
 Albedo (Chapter 6)
Introduction
As we saw in Chapter 6, the Earth’s weather has probably already been
affected by the enhancement of the greenhouse effect due to increasing
atmospheric concentrations of carbon dioxide and other gases. A continu-
ing buildup of CO2 in the air leads to the conclusion that we are in store for
261
262 Chapter 7 Fossil-Fuel Energy, CO2 Emissions, and Global Warming
further increases in global air temperatures and other changes to our cli-
mate. In this chapter, we shall inquire into predictions of the likely trends
in energy usage and consequently of carbon dioxide emissions that will
occur for the rest of the twenty-first century. The nature of fossil fuels and
their role in generating CO2 are then analyzed, and the prospect of burying
the emissions as they are generated is then explored. We finish by consider-
ing the predictions of the consequences to the climate, and of ramifications
to civilization that follow from it, if greenhouse gas emissions continue
unabated or with only weak controls.
Energy Reserves and Usage

Ever since the Industrial Revolution, the worldwide use of commercial
energy—that sold to users and usually derived on a large scale from fossil-fuel
combustion, hydroelectricity, and nuclear power, as opposed to the biomass
collected and used by individual families—has risen almost every year; the
current annual global growth rate is about 2%. The period of the most rapid
increase began after World War II, when global commercial energy consump-
tion was only about one-tenth the current level.
Because the amounts are so huge, it is useful to discuss global quantities
of energy in terms of the large energy unit EJ, an exajoule, which is 1018 joules.
The total amount of commercial energy consumed by humans currently
amounts to about 400 EJ annually, with the United States consuming about
100 EJ of that total.
Determinants of Growth in Energy Use

Although increases in energy usage are sometimes thought to be mainly tied
to population growth, this is a dominant factor only for less developed coun-
tries, for which energy use per capita is small anyway. The usage of commer-
cial energy by a country depends on many factors, including its population,
geography, and climate, as well as on the cost of energy. However, the most
important factor in total energy usage appears to be the gross domestic
product (GDP) of the country. In industrialized societies, about 11 megajoules
(11 million joules) of energy are currently needed on average to produce one
(U.S.) dollar’s worth of goods and services. Interestingly, the energy-to-GDP
ratio for many developing countries, including China, has about the same
value. The ratio for India is somewhat less than those for developed coun-
tries, and those for nondeveloped countries are lower still.
In the past, it has been found that although the energy-to-GDP ratio
usually rises when a country begins to industrialize, it then drops gradually as
the infrastructure becomes more substantial and efficient. For example, the
ratio for the United States dropped by 44% from 1970 to 2000.
The fantastic rise in global energy usage in the second half of the twen-
tieth century was due mainly to industrial expansion and to increases in the
standard of living in the now-developed countries. The energy consump-

tion in these countries continues to expand, though now only slowly. Per
capita energy use in the United States currently amounts to 10,000 J/sec
(i.e., 10,000 watts, the equivalent of one hundred 100-W light bulbs burn-
ing continuously), about twice that in the European Union and Japan, and
about five times the world average.
However, economic growth in the developing countries—which contain
three-quarters of the world’s population—is rising more quickly and with it
their total energy consumption. Thus, although per capita energy usage in
China is only half the global average, it is rising. The developing countries
collectively used only 30% of the world’s commercial energy in 1993, but
they are expected to consume more than half of it starting sometime in the
next decade. According to the International Energy Agency, between 1994
and 2010 the rate of increase for the developing countries collectively is
expected to be 4% annually, which, if compounded, would produce a dou-
bling over that period. For developed countries, the annual rise over the same
period is expected to be 1.5%, amounting to 28% if compounded over that
period. The overall global increase is expected to continue to be about 2%
annually over the next few decades.
P R O B L E M 7-1
Any quantity V whose value increases in a time period t by a percentage of its
previous value exhibits exponential growth according to the equation
V V0 ekt
where V0 is the initial value and k is the fractional increase in each time
period. Given that this equation will apply to the growth in energy usage if it
increases by the same percentage each year, derive a general formula relating
the number of years required for energy usage to double as a function of the
annual fractional increase k. What is the doubling time when 4% annual
growth (i.e., k 0.04) is in operation? What about 3%, 1.5%, and 1.0%
annual growth rates? If k 0.02, how many years does it take for the energy
use to increase 10-fold? If energy usage grew by a factor of 10 over 50 years,
what was the annual compounded rate of growth in this period?
The usage of energy involves its transformation from one form to another,
eventually resulting in its degradation to waste heat; as such, it does not
pose any global environmental problem per se. However, there are usually
side effects associated with energy production and/or consumption that are
serious environmental issues, as we shall see in the rest of this chapter and in
the next.
The most serious long-range global environmental problem associated
with energy use is the release into the atmosphere of carbon dioxide, CO2,
when fossil fuels are combusted to produce heat. Indeed, the rest of this chapter
is devoted to exploring this problem and its possible solutions, as well as to

the nature and properties of fossil fuels, namely coal, petroleum, and natural
gas. Carbon dioxide is produced when any carbon-containing substance
undergoes complete combustion:
C in substance O2 9: CO2
As we saw in Chapter 6, CO2 is an important greenhouse gas, and the increase
in its atmospheric concentration is responsible for the largest fraction of global
warming of any anthropogenic factor.
Developed countries have accounted for about three-quarters of all car-
bon dioxide emissions from fossil-fuel combustion and cement manufacture
since the beginning of the Industrial Revolution. The emissions from these
sources from various countries in the more recent period (1980–2004) are
illustrated by the bands in Figure 7-1. Notice that:
• The United States was the biggest emitter country, though recent data
indicate China overtook it in 2007.
• The emission from the developed countries, taken together and defined
by the top of the band for “Other developed countries,” has been rising
slowly, as has their total energy usage, discussed previously, and now amounts
to about 60% of the total.
• Emissions from the countries of the former Soviet Union decreased sig-
nificantly in the early 1990s, after the fall of communism; the decrease in the
8000
7000
CO2 emissions (Mt of carbon per year)
6000
5000 Other developing countries India
China
4000
Former Soviet Union countries
3000 Other developed countries
Japan
2000 EU
FIGURE 7-1 CO2 emis-
sions from fossil-fuel 1000
combustion for different USA
countries and regions since
1980. [Source: M. Raupach 0
1980 1984 1988 1992 1996 2000 2004
et al., Proceedings of the
National Academy of Sciences
Year
104 (2007): 10288.]
1990s roughly matched the increase in emissions from developing countries

over that period.
• Emissions from China have risen sharply recently, with a spike that began
in 2002.
Almost all the increase in CO2 emissions discussed above arose from
increases in usage of energy derived from fossil fuels. However, the ratio of
carbon dioxide to energy varies among countries and over time because of dif-
ferences in the fraction of energy produced by combustion and, as discussed
later in the chapter, because different fossil fuels produce very different
amounts of the gas per joule. Because of the importance of CO2, the term
carbon intensity, defined as the ratio of CO2 emissions per dollar of GDP, has
become widely discussed by policymakers.
The global carbon intensity declined over the last half of the twentieth
century, especially over its last two decades, when it declined by about one-
quarter. However, as the solid green line in Figure 7-2 indicates, the global
intensity remained approximately constant from 2000 to at least 2005.
Currently, the production of one dollar’s worth of goods and services results,
on average, in the emission of about 730 g of carbon dioxide into the atmos-
phere. Carbon intensities are usually expressed as the carbon content alone of
the emitted CO2, or about 200 g of carbon per dollar in the present case.
(Notice that the curves in Figure 7-2 are not absolute, but relative to their
year 2000 values.)
1.5
1.4
1.3 FIGURE 7-2 Global CO2

Carbon intensity emissions (heavy black
1.2 curve; includes both fossil-
fuel combustion and
1.1 cement production) and
Relative value
important factors that

1.0 CO2 emissions
influence it. Dashed green
curve = population; thin
0.9 black curve = per capita
GDP; solid green curve =
Per capita GDP
0.8 carbon intensity of GDP;
Population heavy black curve = CO2
0.7 emissions. Note that all
parameters are normalized
0.6 to year 2000 values.
[Source: M. Raupach (Global
0.5 Carbon Project), Carbon in the
1980 1985 1990 1995 2000 2005
Earth System: Dynamics and
Year Vulnerabilities, Beijing,
November, 2006.]
P R O B L E M 7-2
Show that the carbon content of 730 g of CO2 is 199 g.
Although they had very similar carbon intensity values in the early 2000s,
the intensities for the world’s two largest economies—the United States and
China—evolved quite differently over time, as illustrated by the solid green
curves in Figures 7-3a and 7-3b. American carbon intensity has fallen gradu-
ally and almost continuously, whereas that of China fell precipitously once
major industrialization began, then reached a minimum in about 2000 and
rose significantly at least in the half-decade that followed. Presumably, much
of the decrease in the U.S. intensity is due to its continuing conversion from a
manufacturing to a knowledge economy, whereas the increase in China arises
from its development as an energy-intensive economy that produces large
quantities of manufactured goods.
2.0
(a) United States
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
Relative values
0.2
0
2.0
1.8 (b) China
1.6
1.4
1.2
FIGURE 7-3 CO2 emis- 1.0
sions and important factors
0.8
that influence it, from
(a) the United States and 0.6
(b) China. See Figure 7-2 0.4
for curve identification.
0.2
[Source: M. Raupach (Global
Carbon Project), Carbon in the 0
1980 1985 1990 1995 2000 2005
Earth System: Dynamics and
Vulnerabilities, Beijing, Year
November, 2006.]
The driving forces behind the changes over the last few decades in global
and regional CO2 emissions can be understood by considering the various
curves in Figures 7-2 and 7-3; all factors in these graphs are normalized to their
year 2000 values. The continuous rise in world population over time is indi-
cated by the dashed green line in Figure 7-2. As the world economy developed,
the average GDP per person also rose, as shown by the thin black curve. The
product of these two quantities is the global GDP, which rose in a faster-than-
linear fashion (not shown) since each of these factors was rising more or less
linearly with time. However, in the period until about 2000, the carbon inten-
sity of the global GDP (solid green line in Figure 7-2) declined almost linearly
with time, so the total carbon dioxide emission rate—which is a product of the
three factors—rose only gradually and more or less linearly in that period
(heavy black curve in Figure 7-2). From 2000 to 2005 at least, since the carbon
intensity did not fall, the emission rate of carbon dioxide rose dramatically.
CO2 emission rate population per capita GDP carbon intensity
The corresponding emission curve for the United States (Figure 7-3a)
involves the same combination of factors, with post-2000 emissions steady
due to the continuing decline in carbon intensity. In contrast, the continuing
strong rise in per capita GDP in China, combined with the increasing carbon
intensity, has produced sharply increasing emissions (Figure 7-3b).
Another way of measuring the carbon dioxide emissions from different
countries is to consider the per capita releases of this gas into the atmosphere.
Currently the emissions of carbon dioxide amount to about 4 tonnes per per-
son per year when averaged over the global population; this factor is usually
expressed as 1 tonne of carbon, and it is this reference to carbon that will be
used henceforth. The global average carbon emission remained remarkably
steady, at about 1.1 tonnes, since rising to this value in the early 1970s,
although it has increased slightly in recent years.
People in developed countries have much higher annual average emissions
than do those in developing countries: 3 versus 0.5 tonnes of carbon per person.
The United States leads in both total and per capita CO2 emissions, according
to the bar graph in Figure 7-4, where we have listed in order the top 20 carbon
dioxide emitter countries as of 2003. The black bars indicate the country’s per-
centage of total global emissions, and the green bars show the per capita emis-
sions. Notice that, compared to the compact European countries and Japan,
the United States, Canada, and Australia have the highest per capita CO2
emission rates, in part due to the high transportation requirements of these vast
lands. It is also true that, in these three countries, fossil-fuel energy is much
cheaper than in European countries. The other developed countries have
remarkably similar per capita annual carbon emissions—about 2 tonnes—
which perhaps is the value currently developing countries will reach once they
are fully developed. The per capita carbon emissions from the United States,
the European Union (EU), and the world in total remained remarkably
25
6
Per capita emission (metric tonnes)

Percentage of global emissions
20 5
4
15
3
10
2
5
1
FIGURE 7-4 Total (black
bars) and per capita (green 0 0
U.S.
China
Russia
India
Japan
Germany
Canada
U.K.
South Korea
Italy
Mexico
Iran
France
South Africa
Australia
Ukraine
Spain
Poland
Saudi Arabia
Brazil
bars) emissions of carbon
dioxide by top 20 emitter
countries in 2003.
[Source: Data from Carbon
Dioxide Information Analysis
Center.]
constant over the last few decades of the twentieth century, the increases in
GNP being matched by decreases in intensity of both energy and carbon.
Because populations of different countries vary so much, their green-
house gas emissions per capita or per dollar of GNP are no guide to their total
emissions. Thus in Figure 7-4, we see that China and India make substantial
contributions to the total global emissions since their populations are so
large, even though their per capita emission rates are still quite modest. Both
countries generate most of their electricity by burning coal. China’s total
CO2 emissions since the turn of the millennium have exceeded even its rapid
growth of the 1980s and early 1990s. India’s emissions have been growing
almost linearly, currently by about 3–4% annually since 1980, though it still
has the lowest per capita emissions of any of the top 20 emitter countries.
Patterns of Growth in CO2 Concentrations

Because carbon dioxide has such a long lifetime in the atmosphere—a cen-
tury or more on average—the gas accumulates in air. Thus almost all the CO2
emissions from the 1990s, for example, that did not find a temporary sink will
remain in the air for decades to come, adding to the bulk of the emissions
from the 1980s, 1970s, and previous years. The actual carbon dioxide mole-
cules that constitute this additional mass will change from year to year, as
some CO2 molecules leave the temporary sinks and enter the atmosphere
while an equal number from the air enter one or another temporary sink.
Linearly increasing Sharply increasing

concentration concentration
ns
io
iss FIGURE 7-5 CO2 con-
em centration related to its
O2 emission level. (a) Constant
C
sing emissions of CO2 produce
Constant CO2 emissions rea a linearly increasing
inc concentration of the gas.
arly (b) Linearly increasing
ne
Li emissions produce a
quadratically increasing
(a) (b) concentration of the gas.
The growth pattern of the CO2 concentration in air is determined

mainly by the pattern of CO2 emissions. Suppose, for example, that the same
amount of carbon dioxide emissions were added to the air each year and did
not find a temporary sink (Figure 7-5a, black line). The total amount of CO2
in air—and hence its concentration—would then annually increase by a con-
stant amount. The carbon dioxide concentration increases linearly with time
in this case (Figure 7-5a, green line). If the world could hold its carbon diox-
ide emissions constant at the year 2000 value, then the CO2 concentration
would presumably increase linearly, by the current 2-ppm yearly increment,
and would consequently become about 500 ppm in 2060. Currently, global
CO2 emissions are growing slowly, increasing by only about 1% annually
(see Figure 6-8), so the atmospheric carbon dioxide concentration is growing
almost linearly (Figure 6-8 inset).
Another scenario, which at times has been more realistic than the situa-
tion just described, is that the CO2 emissions were not the same each year but
themselves increased linearly, that is, by a constant amount k each year. Thus,
if the emissions one year amounted to A, the next year they were A k, and
the following year A 2k, etc. (Figure 7-5b, black line). In this case, if the
fraction of the gas that enters the oceanic sink each year is constant, the
growth in CO2 concentration will be quadratic, much sharper than linear:
The resulting plot of CO2 concentration curves upward, as illustrated in Fig-
ure 7-5b (green curve). Indeed, in the decades preceding the mid-1970s, the
CO2 concentration (Figure 6-8 inset) did increase quadratically since carbon
dioxide emissions were increasing rapidly (Figure 6-9). However, since then,
the CO2 concentration has increased in an approximately linear manner
with time, reflecting the slower rate of increase in emissions in this period,
among other factors—including the fact that the fraction of emissions that
find a temporary sink varies with time (as was discussed in Chapter 6).
Fossil Fuels
As mentioned above, most commercial energy in the world is produced cur-
rently by the burning of fossil fuels. In this section, we discuss the nature and
future supplies of these fuels and compare their differing abilities to produce
the greenhouse gas carbon dioxide. Later in the chapter, we shall see that the
main problem of fossil-fuel usage in the present century is the CO2 emissions
that result from its combustion rather than a shortage in supply.
Fossil Fuels: Coal

The main fossil-fuel reserve is coal, which is available in abundance in many
regions of the world, including developing countries, and which is cheap to
mine and transport. Five countries—the United States, Russia, China, India,
and Australia—have 75% of the world’s coal reserves. At today’s rate of con-
sumption, coal reserves are estimated to last another 200 years, much longer
than oil or gas (see below). Indeed, some observers believe the world will
return to a greater reliance on coal as the major fossil fuel later in this century.
The 2100 coal-fired power plants in the world are collectively responsible for
about a third of all anthropogenic CO2 emissions. Currently, coal produces
about half the electric power in the United States and 80% of that in China.
Although it is a mixture, to a first approximation coal is graphitic car-
bon, C. It was formed from the tiny proportion of ancient plant matter that
was covered over by water and could not be recycled back to CO2 at that
time. This also accounts for the buildup of O2 in the atmosphere. Coal was
formed from the highly aromatic, polymeric component of land-based woody
plants called lignin; an approximate formula for lignin is C3H3O. Over long
periods of time during which the material was subjected to high pressures and
temperatures, both water and carbon dioxide were lost. The material poly-
merized further in the process to yield the very carbon-rich, hard material
known as coal. Unfortunately, during its formation the coal also incorporated
measurable quantities of virtually every naturally occurring element, so that
when it is burned, it emits not only CO2 and H2O but also substantial quan-
tities of many air pollutants—notably sulfur dioxide, fluoride, uranium and
other radioactive metals, and heavy metals including mercury. Thus coal has a
reputation for being a “dirty fuel.” The removal of some of these impurities,
especially sulfur, by various modern technologies was discussed in Chapter 3.
The burning of coal domestically in stoves and furnaces produces a great
deal of soot, and it therefore has been largely discontinued in developed coun-
tries. However, coal is still used in most developed and developing countries
for electric power production. When burned in such plants, the soot problem
is readily solved, although emissions of sulfur and nitrogen dioxides and of
mercury require more sophisticated and expensive equipment to control, also
discussed in Chapter 3 and the online case study associated with Chapter 8.
Fossil Fuels 271
The heat produced in the combustion of the fossil fuel is used to gener-
ate high-pressure steam, which in turn is used to turn turbines and thereby
produce electricity. As discussed below, however, the ratio of CO2 to energy
produced from coal is substantially greater than for the other fossil
fuels. Coal can also be used to produce alternative fuels—as discussed in
Chapter 8—but unfortunately, the conversion processes are not very energy
efficient. Although the emission of carbon dioxide is not reduced by such
conversions, they do allow the removal of sulfur dioxide and other pollu-
tants and so are “clean” ways to use coal.
To a first approximation, the amount of heat released when a carbon-
containing substance burns is directly proportional to the amount of oxygen
it consumes. From this principle, we can compare different fossil fuels by the
amount of CO2 released when they are burned to produce a given amount of
energy.
Consider the reactions of coal (mainly carbon), oil (essentially polymers
of CH2), and natural gas (essentially CH4) with atmospheric oxygen and
written so that the amount of carbon dioxide produced is identical in
each case:
C O2 9: CO2
CH2 1.5 O2 9: CO2 H2O
CH4 2 O2 9: CO2 2 H2O
It follows from the stoichiometry of these reactions that, per mole of O2 con-
sumed and thus approximately per joule of energy produced, natural gas gen-
erates less carbon dioxide than does oil, which in turn is superior to coal, in a
ratio of 1:1.33:2. (The actual ratio is computed in Problem 7-3.)
P R O B L E M 7-3
Given the following thermochemical data, determine the actual ratio of CO2
per joule of heat released upon the combustion of methane, CH2, and ele-
mental carbon (graphite). Hf values in kJ mol1: CH4, 74.9; CO2(g),
393.5; H2O(l), 285.8; C(graphite), 0.0; CH2, 20.6.
P R O B L E M 7-4
The relative amounts of oxygen required to oxidize organic compounds to
carbon dioxide and water can be deduced from calculating the change in the
oxidation number (state) of the carbon atom in going from the fuel molecule
to the product. Show that the ratio of oxygen required to combust C, CH2,
and CH4 stands in the ratio of 2:3:4 according to such a calculation.
Fossil Fuels: Natural Gas

Petroleum and natural gas are essentially mixtures of
hydrocarbons. They originated as the small fraction of
marine organisms and plant matter that were buried and
therefore cut off from the oxygen that was required for
their complete oxidation. The high temperatures and
Impermeable pressures to which this buried material was later subjected
rock decomposed it further, into liquid and gaseous hydrocar-
bons. Like petroleum, natural gas deposits are found in
Gas geological formations in which the gas mixture has been
trapped by a mass of impermeable rock. Drilling a hole
down through the rock releases the gas in a steady flow to
Oil the surface (Figure 7-6).
In terms of its hydrocarbon component, natural gas as
it exits from the ground consists predominantly (60–90%)
FIGURE 7-6 Releasing
natural gas deposits from of methane, CH4. The other component alkanes—ethane,
the Earth. propane, and the two butane isomers—are gases present to varying extents
depending upon the geographic origin of the deposit. (See Appendix I if
you are unfamiliar with the terminology and numbering systems of organic
molecules.)
Methane’s boiling point is so low (–164°C) that it does not readily con-
dense into a liquid, even at moderately high pressures. In contrast, the other
gaseous alkanes possess substantially higher boiling points. This makes it
possible to largely remove the other alkanes from natural gas by lowering
the mixture’s temperature and thereby condensing these other hydrocarbons
to liquids.
Sulfur compounds are also important impurities in natural gas, as previ-
ously mentioned: Some deposits contain more H2S than CH4! The hydro-
gen sulfide is removed from the gas by the Claus reaction, as discussed in
Chapter 3. After processing to remove the other alkanes and the sulfur com-
pounds, the natural gas—which now is mainly methane—is transported
under pressure by pipeline to consumers.
Unfortunately, as we have discussed in Chapter 6, a small fraction of the
methane being transported from its source to the consumer is lost to the
atmosphere when natural gas pipelines leak; the greenhouse-enhancing effect
of this methane could override some of the advantage methane has in pro-
ducing less CO2 per joule upon combustion compared to oil and especially
compared to coal (see Additional Problem 3).
The enormous quantity of natural gas held in methane hydrates (clathrates)
in ocean sediments and permafrost, as mentioned in Chapter 6, would double
the fossil-fuel reserves if they could be tapped. The technology to extract the
clathrates, many of which are in dilute form and mixed with sediments that
lie far below the seabed, does not yet exist.
Fossil Fuels 273
Natural Gas and Propane Fuels

In the developed world, natural gas is used extensively as a fuel. It consists
mainly of methane but contains small amounts of ethane and propane. Nor-
mally the gas is transported by pipelines from its source to domestic consumers,
who use it for cooking and heating, and to some utilities, which burn it instead
of coal or oil in power plants to produce electricity.
CH4(g) 2 O2(g) 9: CO2(g) 2 H2O(l) H 890 kJ mol1
Unfortunately, where pipelines do not exist, the natural gas that is produced
as a by-product of petroleum production at oil wells, etc. is simply wasted by
venting or flaring it off, thereby adding to the atmospheric burden of green-
house gases.
Highly compressed natural gas (CNG) is used to power some vehicles,
especially in Canada, Italy, Argentina, the United States, New Zealand, and
Russia. Due to the cost of converting a gasoline engine to accept natural gas
as the fuel, the current use of CNG in vehicles is mainly restricted to taxis
and commercial trucks that are in almost constant service. For such vehicles,
the additional capital cost of converting the fuel system is much less in the
long run than are the savings from the lower cost of the fuel. Because the
compressed gas must be maintained at very high pressures to keep its storage
volume reasonable, heavy fuel tanks with thick walls are required. In order to
keep the weight and size of the tank to reasonable values, the driving range
(before refilling) of CNG vehicles is usually considerably shorter than that of
gasoline-powered vehicles.
Compressed natural gas has both environmental advantages and disad-
vantages as a vehicular fuel when compared to gasoline. Since methane
molecules contain no carbon chains, neither organic particulates nor reactive
hydrocarbons are formed or emitted into air as a result of its combustion; how-
ever, a small amount of each pollutant type is formed from the ethane and
propane component of commercial natural gas. Overall, regional air quality is
improved by the use of natural gas rather than gasoline or diesel oil. However,
the release of methane gas from pipelines during its transmission or from
tailpipes of vehicles due to its incomplete combustion could lead to increased
global warming since methane is a potent greenhouse gas. A massive conver-
sion in North America to CNG as a vehicular fuel would be limited by supply
problems for the gas, which is now used extensively for domestic heating and
cooking and increasingly as the fuel in new electric power plants.
Some interesting proposals have been made recently to improve the
performance of natural gas as a vehicular fuel. More efficient burning of the
methane results if a small amount—about 15% by volume—of hydrogen gas
is added to it. Alternatively, a smaller storage volume for methane results if
it is liquefied rather than simply compressed, but more energy is expended in
the process.
Similar but somewhat less serious considerations apply to propane, C3H8,

also a main component of liquified petroleum gas (LPG), in its use as a gaso-
line replacement in vehicles. The heat energy produced per gram of propane
combusted, 50.3 kJ, is not quite as high as that of 55.6 kJ for methane. The
heat released per gram by burning gasoline depends on the composition of the
particular blend under consideration, but it is generally slightly less than that
of propane. Both LPG and propane are readily liquefied under pressure, so
they can be stored much more efficiently than can natural gas.
Fossil Fuels: Petroleum

Petroleum, or crude oil, is a complex mixture of thousands of compounds,
most of which are hydrocarbons; the proportions of the compounds vary from
one oil field to another. The most abundant type of hydrocarbon usually is the
alkane series, which can be generically designated by the formula CnH2n2. In
petroleum, the alkane molecules vary greatly, from the simple methane, CH4
(i.e., n 1), to molecules having almost 100 carbons. Most of the alkane
molecules in crude oil are of two structural types: One type is simply a long,
continuous chain of carbons; the other has one main chain and only short
branches—e.g., 3-methylhexane.
Petroleum also contains substantial amounts of cycloalkanes, mainly
those with five or six carbons per ring, such as the C6H12 systems methyl-
cyclopentane and cyclohexane:
CH3
methylcyclopentane cyclohexane
Petroleum contains some aromatic hydrocarbons, principally benzene

and its simple derivatives in which one or two hydrogen atoms have been
replaced by methyl or ethyl groups. Recall from Chapter 4 that toluene is
benzene with one hydrogen replaced by one methyl group and that the
xylenes are the three isomers having two methyl groups.
P R O B L E M 7-5
Deduce the structures of all the trimethylated benzenes. [Hint: For each of the
three dimethylated benzenes, draw all the structures corresponding to placement of a
third methyl group. Inspect each pair of structures you draw to eliminate duplicates.]
It is the component of petroleum containing these aromatic hydro-

carbons that is most toxic to shellfish and other fish when an oil spill
occurs in an ocean, whether from an oil tanker or from an offshore oil well.
Higher-molecular-weight hydrocarbons form sticky, tar-like blobs that adhere
to birds, sea mammals, rocks, and other objects that the oil encounters.
Fossil Fuels 275
Petroleum is found in certain rock formations in the ground and is pumped

to the surface in oil wells. As it exits from the ground, crude oil is not a very
useful substance because it is a mixture of so many compounds. To gain util-
ity, it must first be separated into components, each of which has several
particular uses.
The liquid compounds that are present in crude oil consist of hydrocar-
bons containing from 5 to about 20 carbon atoms each. Although no attempt
is usually made to isolate individual compounds from the mixture, crude oil is
separated into a number of fractions—different liquid solutions whose com-
ponents all boil within a relatively small temperature range. This separation
of oil into fractions is accomplished by a process called distillation, which
involves the vaporization by boiling of a liquid mixture, followed by the cool-
ing of the vapor in order to cause its condensation back to the liquid state; it
is described in Box 7-1. Because of the different boiling points of the com-
pounds, it is possible to separate the mixture into components. Each day, a
total of about 10 billion liters of crude oil are distilled by this procedure in
hundreds of petroleum refineries located around the world.
In addition to hydrocarbons, petroleum also contains some sulfur (up to
4%) in the form of compounds: hydrogen sulfide gas, H2S, and organic sulfur
compounds that are alcohol and ether analogs in which an S atom has replaced
the oxygen. These substances are much more readily removed from oil than
is the sulfur from coal, making petroleum products inherently cleaner. Diesel
fuel distilled from petroleum contains a higher percentage of residual sulfur
than does gasoline, and the residue from the distillation contains the highest
sulfur concentration of all—as well as most of the metals vanadium and
nickel from the original crude oil, usually at levels of several parts per million.
Sulfur that is present in fuels generally is converted during the fuel’s combus-
tion into sulfur dioxide, which is a serious pollutant if released into the air
(Chapter 3). Some organic compounds of nitrogen also occur in petroleum
and are the source of the “fuel NO” (Chapter 3) formed when gasoline and
diesel oil burn.
Petroleum and fuels made from it, such as gasoline and diesel oil, have
the great advantage that they are energy-dense liquids that are convenient,
relatively safe to use, and relatively cheap to produce. Virtually all nonelec-
trical transportation systems in both the developed and developing worlds are
based on cheap petroleum fuels. The possibility of switching to alternative
fuels for transportation is discussed in detail in Chapter 8. It will be much
more difficult to switch from oil to other chemical feedstocks for the produc-
tion of pharmaceuticals and polymers once oil runs out.
Although it took nature about half a billion years to create the world’s
supply of petroleum, humans will probably have used almost all of it during
the 200-year period that started just before the end of the nineteenth century.
Indeed, the production of petroleum in the lower 48 states of the United
States has already peaked. In commerce, petroleum is measured in barrels,
each of which is equivalent to 159 liters, or 42 U.S. gallons. Current annual
BOX 7-1 Petroleum Refining: Fractional Distillation
s we noted in the text, fractional distilla- from the remainder, which continues to rise in
A tion separates crude oil into a number of
fractions having molecules of similar sizes.
the tower. This first fraction of the petroleum,
called gas oil, is a rather viscous liquid when
The crude oil mixture is first continuously fed cooled to room temperatures and finds com-
through pipes that pass through a furnace that mercial use as lubricating oils.
heats the oil to 360°–400°C. Even higher Another series of collection trays and an
temperatures are not employed because of the output pipe are located somewhat higher in the
tendency of the oil to decompose under such tower, where the temperature has cooled suffi-
conditions. At the temperatures that are used, ciently, to about 300°C, to allow hydrocarbons
most of the oil is converted to a gas. The por- in the C16 to C18 range to condense and be
tion of the oil that is not vaporized is a hot liq- collected. This second fraction, used as diesel
uid, called the bottoms or the residuum, which fuel and industrial heating oil, is called middle
contains the heaviest molecules found in oil. distillates. The final fraction, called kerosene or
It is drawn off and subsequently separated into heavy naphtha, which contains primarily hydro-
components that are used as solid products carbons with 12 to 16 carbons, is collected by
such as waxes and asphalt, or it is used for trays near the top of the tower, where tempera-
making the form of carbon called coke that tures have cooled to about 150°–275°C. The
is employed in steel production. It is also kerosene fraction is used as diesel and jet fuels
possible, by reducing the pressure to almost and as oil for home heating.
a vacuum, to boil the bottoms fraction of There is no particular reason why the frac-
crude oil and, by various techniques, to split tions described above, with these particular
the vaporized long molecules of this fraction boiling point ranges, should be the only ones
into shorter ones, for use in gasoline and collected. In fact, different petroleum distilla-
diesel fuel. tion towers collect different fractions by using
The vaporized oil is injected into a vertical different collection temperatures, not just
distillation or fractionating tower, which is sev- those we have described. The decision as to
eral meters in diameter and up to 30 m high. exactly which fractions are to be collected is
The temperatures in the tower decrease as the made by considering the end uses for the vari-
hot gases move higher and higher; thus the ous products.
vapor cools as it rises (see Figure 1). Since they At the top of the tower, the remaining
correspond to compounds with high boiling uncondensed vapor contains hydrocarbons
points and hence high condensation tempera- consisting primarily of molecules having 1 to
tures, the first gaseous molecules to recon- 12 carbon atoms each. This vapor is cooled
dense to liquids as the vapor rises through the almost to normal outdoor temperatures in a
tower are those with 17 or 18 or more carbon separate unit, a procedure which condenses
atoms. By means of a series of collection trays the molecules with 5 to 12 carbons to the
situated in the tower at positions where the liquid known as straight-run gasoline or light
temperature falls to an average of about about naphtha. This fraction, which constitutes about
350°C, this liquid fraction of the oil can be one-fifth of the original oil, is the basis of
collected and drained off, thereby separating it the gasoline used to power motor vehicles.
Fossil Fuels 277
FIGURE 1 Petroleum fractions in a refining tower.
Alkanes having more than about 12 carbons C4 alkanes (butanes) are used as components
cannot be used in gasoline since they do not both of gasolines and of liquefied petroleum
evaporate in the engine sufficiently to burn gas. Unfortunately, the C1 to C3 gases are
properly. sometimes ignited and simply “flared off” into
The C1 to C4 gases—namely methane, the air if facilities for their condensation or
ethane, propane, and butane—that remain transportation do not exist at the petroleum
uncondensed at the top of the tower can be refining site.
collected and used for the purposes previously In summary, the fractionating tower sepa-
described for components of natural gas. The rates crude petroleum into a number of useful
BOX 7-1 Petroleum Refining: Fractional Distillation (continued)
materials, each of which is a mixture of hydro- in some cases, but they are usually found
carbons in which the different constituents mainly in the bottoms.
have approximately the same number of car-
bon atoms and which all boil within a small PROBLEM 1
range relative to the larger range of the crude
oil. For many applications, a further separa- Explain the process by which crude oil is con-
tion of a fraction into subfractions, each converted to usable fractions.
sisting of a smaller set of hydrocarbons, is
accomplished subsequently. PROBLEM 2
In addition to hydrocarbons, crude oil also How are gasoline and kerosene different? How
contains small quantities of compounds that are they alike?
contain other elements. The most predomi-
nant of these elements is sulfur, which occurs
PROBLEM 3
in oil to the extent of 0.5–6%, depending
upon the origin of the material. Metals such as Why can both gasoline and kerosene be used
vanadium, nickel, and iron also are present, at as fuels?
a total concentration of more than 1000 ppm
world oil production amounts to about 4 trillion (4 1012) liters, or 27 billion

barrels. Much of the proven oil reserves are located in the Middle East.
Although it is commonly said that we are “running out” of oil and gas,
this will probably not occur globally in the short-to-medium term. Improve-
ments in the technology of petroleum extraction allow greater and greater
proportions of the oil in a given deposit to be extracted. The initial extrac-
tion of oil from a reserve usually proceeds without difficulty. However, later
on, the remaining oil occurs mostly in pores as droplets that are larger than
the connecting necks of the porous formation; hence it will not flow because
of surface tension. In secondary extraction, surfactants, water, or pressurized
carbon dioxide can be used to lower the surface tension and drive additional
oil from the reserve. In tertiary extraction, steam is injected to lower the
viscosity of the remaining oil and allow it to be pumped. As the more acces-
sible supplies dry up and the price of oil rises, such extraction processes are
becoming more economically viable. Indeed, most major oilfields are now
undergoing at least secondary extraction.
Some analysts believe that global oil production will peak sometime
between 2005 and 2015, whereas others argue that this will not happen until
at least 2030. A 2006 survey of petroleum geologists found that most believe
the peak will occur between 2020 and 2040. A recent estimation of the
manner in which oil production is expected to vary with time is shown as a
modified bell curve in Figure 7-7. Notice that production of conventional oil
Fossil Fuels 279
35
HO – Heavy oil Peak production in
2008 at 84 MMbbls/day
30 DW – Oil from
Production (billion barrels/year)
deep-water drilling
25 P – Oil from polar DW
sources
NGL – Liquids
20 derived from
natural gas sources Middle East NGL
15
P
Other
10 HO
FIGURE 7-7 Historical
and projected oil produc-
5 Russia
tion for 1930–2050 from
Europe
U.S. various geographic areas.
0 [Source: C. J. Campbell, The
1930 1950 1970 1990 2010 2030 2050
Coming Global Oil Crisis,
Year 2004. www.hubbertpeak.com/
campbell]
outside the Persian Gulf area (curve above “Other”) probably peaked a few
years ago. Indeed, U.S. production reached a maximum in 1972. The zones at
the top of the graph represent nonconventional sources of oil (including those
from deep-water drilling), liquid hydrocarbons obtained from natural gas, and
heavy oil from tar sands etc.; the latter sources are expected to play an increas-
ingly important role in oil supplies in future decades.
Very-long-chain hydrocarbons from oil shales, a type of sedimentary rock,
and tar sands, which is sandstone or porous rock impregnated with very
viscous crude oil, could extend the petroleum supply. Indeed, the potential
for oil from tar sands in Alberta, Canada, exceeds the oil reserves of Saudi
Arabia! However, there are currently high economic, energy, and environ-
mental costs for exploiting these potential reserves in a large-scale manner.
For example, about 2 tonnes of the asphalt-like mixture of sand and tar in
northern Alberta’s heavy-oil deposits are required to produce one barrel of
oil. Energy in the form of natural gas must then be expended to separate the
oil from the sands and to split the long-chain hydrocarbon molecules of
the tar into shorter ones for use in gasoline (see Additional Problem 4). The
extraction process also consumes several times as much fresh water as the vol-
ume of oil produced, and there are already concerns that the supply of water
will not be sufficient for all the planned expansions of production.
Gasoline
Regular gasoline contains predominantly C5 to C11 hydrocarbons; diesel fuel
contains mainly hydrocarbons with 9–11 carbon atoms. Generally speaking,
the more carbon atoms in the alkane, the higher its boiling point and the
lower its vapor pressure—and hence the lesser its tendency to vaporize—at
a given temperature. For this reason, gasoline destined for warm summer
conditions is formulated with smaller amounts of the smaller, more easily
vaporized alkanes such as butanes and pentanes than is that prepared for
winters in cold climates. The presence of volatile hydrocarbons in gasoline is
vital in cold climates so that automobile engines can be started.
Gasoline that consists primarily of straight-chain alkanes and cycloalka-
nes has poor combustion characteristics when burned in internal combustion
engines. A mixture of air and vaporized gasoline of this type tends to ignite
spontaneously in the engine’s cylinder before it is completely compressed and
sparked, so the engine “knocks,” with a resulting loss of power. Consequently,
all gasoline is formulated to contain substances that will prevent knocking.
In contrast to unbranched alkanes, highly branched ones such as the
octane isomer 2,2,4-trimethylpentane, “isooctane” (illustrated below), have
excellent burning characteristics. Unfortunately, they do not occur naturally
in significant amounts in crude oil. The ability of a gasoline to generate
power without engine knocking is measured by its octane number. To define
the scale, isooctane is given the octane number of 100, and n-heptane is
arbitrarily assigned a value of zero.
CH3 CH3
H3C C CH2 CH CH3
CH3
2,2,4-trimethylpentane (“isooctane”)
Gasoline that has been produced simply by distillation of crude oil has an
octane number of about 50, much too low for use in modern vehicles. How-
ever, when added to gasoline in small amounts, the compounds tetramethyl-
lead, Pb(CH3)4, and its ethyl equivalent prevent engine knocking and hence
greatly boost the octane number of gasoline. For decades, they were added
worldwide to gasoline consisting predominantly of unbranched alkanes and
cycloalkanes. However, these additives have largely been phased out now in
most developed countries owing to environmental concerns about lead, a
topic discussed in Chapter 15.
In some European countries and in Canada, lead compounds were
replaced by small quantities of an organic compound of manganese called
MMT, which stands for methylcyclopentadienyl manganese tricarbonyl. The use
of MMT has been controversial for health reasons, since manganese concen-
trations rise in air and soil as a result, and for technological reasons, since
some car manufacturers claim it degrades emissions components on vehicles.
Until 1995, MMT was banned in the United States; even though this ban
was revoked, its use there is very small.
The alternative to using lead or manganese additives to boost octane rat-
ings is to blend into gasoline significant quantities of highly branched alkanes,
Fossil Fuels 281
Octane Numbers of Common Gasoline

TABLE 7-1 Additives
Compound Octane Number
Benzene 106
Toluene 118
p-Xylene (1,4-dimethylbenzene) 116
Methanol 116
Ethanol 112
MTBE 116
BTX, or other organic substances such as MTBE (discussed later), which

themselves have high octane numbers. A list of the common additives is
shown in Table 7-1. Collectively, the benzene toluene xylene component
in gasoline is called BTX.
CH3 CH3
CH3
benzene toluene p-xylene
Gasoline often also contains some trimethylated benzenes and ethylbenzene;

the mixture is then called BTEX. Currently, most unleaded gasoline sold in the
United States contains significant quantities of BTX (as high as 40% content
in the past), ethanol (especially in the Midwest), or MTBE to boost the octane
number. Unfortunately, the BTX hydrocarbons are more reactive than the
alkanes that they replace in causing photochemical air pollution, so in a sense
the lead pollution has been reduced at the price of producing more smog. In
addition, the use of BTX in unleaded gasoline in countries, such as Great
Britain, where few cars were equipped with catalytic converters resulted in the
past in an increase in the BTX concentrations in outdoor air. Benzene in par-
ticular is a worrisome air pollutant since at higher levels it has been linked to
increases in the incidence of leukemia (see Chapter 4).
The reformulated gasoline used in the second half of the 1990s in North
America contained a maximum of 1% benzene and 25% (volume) aromatics
in total, with a minimum of 2% oxygen (by mass). The second phase of
reformulated gasoline, which entered the U.S. market in 2000, reduces the
benzene and BTX components even further and lowers the sulfur content to
30 ppm. The EU planned to cut the maximum level of benzene in gasoline by
75% effective 2005.
The use of alcohols and compounds derived from them as additives or as

“oxygenated” motor fuels in their own right is discussed in Chapter 8.
Sequestration of CO2
In the future, CO2 might be removed chemically from the exhaust gases of
major point sources that would otherwise release it into the atmosphere, such
as power plants that burn fossil fuels and that collectively are responsible for
one-quarter to one-third of total emissions. The carbon dioxide gas so recov-
ered would then be sequestered—i.e., deposited in an underground or ocean
location that would prevent its release into the air. For example, the CO2
could be sequestered by burial in the deep oceans, where it would dissolve, or
in very deep aquifers under land or the seas, or in empty oil and natural gas
wells or coal seams. The total amount of carbon dioxide that will be produced
by fossil-fuel combustion over this century will amount to more than one tril-
lion tonnes, so vast amounts of storage would be required (Problem 7-6).
P R O B L E M 7-6
Calculate the volume, and from it the length in kilometers, of each side of a
cube of liquid or solid carbon dioxide whose density is the same as that of
water, i.e., 1 g/cm3, and whose mass is a trillion (1012) tonnes.
Since it is not economically feasible to transport and store emission gases

from power plants, the dilute carbon dioxide (usually 12–14% by volume) in
the gas mixture must be captured and concentrated. The energy input
required for the CO2-concentrating phase of carbon sequestration schemes
would represent a substantial fraction, from one-third to one-half, of the out-
put of the power plant to which it is connected; therefore more fuel would be
combusted and more air pollutants produced. The equipment required to
capture and concentrate CO2 is very large, since huge volumes of air are
involved. The capture/concentration of the gas accounts for about three-
quarters of the cost of the entire sequestration process and currently is esti-
mated to cost about $100 per tonne of carbon. Nevertheless, some observers
feel it would still be cheaper to sequester carbon from fossil fuels than to
convert to a renewable-fuel economy.
The capture of carbon dioxide is generally accomplished by passing the
cooled (to about 50°C) emission gas through an aqueous solvent containing
15–30% by mass of an amine, R2NH (or RNH2), which combines with the
CO2 to produce an anion, in a process analogous to that between the gas and
water:
R2NH CO2 Δ R2N9CO2 H
H2O CO2 Δ HCO3 H
Fossil Fuels 283
Over time, the amine solution becomes saturated with the gas since all the
amine molecules become tied up with CO2. Heat is then used to reverse this
reaction (at about 120°C), thereby producing a concentrated stream of car-
bon dioxide for later disposal and regenerating the amine solution after it has
been cooled sufficiently. The amines commonly employed in this chemical
absorption technology are monoethanolamine and diethanolamine, since they
can absorb high loads of the gas and require relatively little heating to release
it later. With these amines, over 95% recovery of CO2 can be achieved. A
strong base such as sodium hydroxide could be used to absorb the CO2, but
the bicarbonate salt it produces requires much more heat to later decompose
it and release its carbon dioxide. Current research centers on finding a sol-
vent that would bind the CO2 efficiently but less tightly and therefore require
less energy to decompose it later when concentrated.
Nitrogen and sulfur oxides must be removed from the emission gas before
it interacts with the solvent, since otherwise they would react with and
degrade the amine. Heating the solution to liberate the CO2 and regenerate
the amine solvent and compressing the gas once it is produced are the most
energy-intensive steps of the process. In addition, enormous amounts of the
solution must be transported from place to place. The decomposition of some
of the amine, producing ammonia and salts, inevitably occurs during the
repurification cycles.
Carbon dioxide can also be chemically absorbed by certain metal oxides,
which will release the gas when heated. For example, calcium oxide, CaO,
can quickly remove CO2 from hot emission gases by formation of calcium
carbonate, CaCO3:
CaO(s) CO2(g) Δ CaCO3(s)
Subsequent heating of the solid to about 900°C, once it has been largely con-
verted to the carbonate, reverses the reaction and produces concentrated
CO2 and regenerates CaO. Unfortunately, calcium oxide deactivates rela-
tively quickly over many absorption/deabsorption cycles, so fresh oxide must
constantly be added to maintain the absorptive activity of the solid.
Three other techniques are available by which carbon dioxide can be
stripped from exhaust gases:
• Membrane separation Polymeric membranes that allow CO2 to pass
through them, while the other gases are excluded, can be employed to recover
about 85% of the carbon dioxide. This technology has been used for many
decades in the oil industry, since it is more economical than chemical absorp-
tion when the concentration of carbon dioxide in the source gas is relatively
high. There is currently much research and development under way in devising
membranes that will be efficient and economical for power plant emissions.
• Physical adsorption Certain solids, such as some zeolites and activated
carbon, that have large surface areas will adsorb CO2 from the gas mixture
and later release it upon heating. Methanol and glycols are also used as
solvents to capture carbon dioxide from concentrated emission gases.
• Cryogenic separation Since CO2 has a higher condensation tempera-
ture than nitrogen or oxygen, it can be isolated as a liquid by condensing the
gas mixture at a very low temperature under high pressure. However, the
energy requirement for this technique is approximately double that of chem-
ical absorption using amines.
One way to circumvent the high expense and energy consumption
required to isolate and concentrate the CO2 from conventional power plants
is by oxycombustion. In this technique, currently under development, the
fossil fuel is burned not in air but rather in oxygen gas, O2. If the stoichio-
metric amount of oxygen is supplied, the exhaust gas from oxycombustion
will consist entirely of carbon dioxide and require no isolation step. (By con-
trast, since air is only 19% oxygen by volume, the maximum level of CO2
when air is used for combustion is also only 19%.) Of course, the original iso-
lation of oxygen from air requires energy, and the combustion facilities must
be redesigned to be able to use pure oxygen. In practice, since combustion in
pure O2 produces a flame too hot (3500°C) for power plant materials, it is
diluted with some of the CO2 from the combustion to reduce the flame tem-
perature. The output gas from oxycombustion is compressed and dried of the
water vapor produced during combustion. It can then be transported by
pipeline as a dense supercritical fluid (see Chapter 6).
Another scheme proposed for the future involves the conversion of a fos-
sil fuel, either coal or natural gas, to hydrogen gas, H2, which would be
employed as the fuel, either in a power plant or in a vehicle, in a reaction that
generates no additional carbon dioxide. In essence, the fuel value of the coal
or natural gas is transferred to hydrogen by the gasification process. Such
techniques for generating H2 for use as a fuel are described in detail in Chap-
ter 8; in general, the process corresponds to the reaction
carbon-hydrogen fuel water 9: CO2 H2

The high concentration of pressurized CO2 in the gas mixture (in principle,
50% by volume) allows for a more economical isolation of the gas, in this case
using a liquid glycol solvent, than its capture from emission gases in a con-
ventional power plant. Alternatively, a membrane that allows only hydrogen
to pass through it could be employed to produce a gas stream largely com-
posed of CO2. Prototype power plants in which methane is first converted to
hydrogen and carbon dioxide, with the latter extracted and pumped into an
underground oil field, are planned for Scotland and California. The Future-
Gen project of the U.S. Department of Energy involves the construction of a
“zero-emission” coal-gasification power plant that will capture and store all
the carbon dioxide it produces.
Fossil Fuels 285
The transfer of the energy value from a fossil fuel to hydrogen eliminates
the impractical task of isolating the carbon dioxide and collecting it when the
fuel itself is used to power vehicles and to heat or cool buildings, applications
that currently account for more than two-thirds of its emissions. Other indus-
trial processes in which carbon dioxide at relatively high concentration can be
separated by membrane techniques include natural gas purification and fer-
mentation plants. The concentration of CO2 in emission gases from cement
plants, which produce the gas by heating calcium carbonate to release calcium
oxide, reaches 15–30% and should be susceptible to more economical capture
methods than those used for the more diluted emissions from power plants.
A number of different methods and locations for storing carbon dioxide
have been proposed and are under current investigation, as discussed in the
following sections.
Deep Ocean Disposal of CO2

Various schemes for delivering carbon dioxide in massive amounts to the seas
and depositing it there as such are labeled ocean acidic in Figure 7-8 and have
Mineral
105 carbonates
Ocean
neutral
Characteristic storage time (years)
104 Annual
emission
Underground
EOR
injection
103
Ocean
acidic
102 Soil
Woody carbon
biomass
10 Leaf
litter FIGURE 7-8 Capacities
and storage times for vari-
ous CO2 sequestration
technologies. [Source:
1 10 100 1000 10,000 100,000 1,000,000
Adapted from K. S. Lackner, “A
Carbon storage capacity (Gt) Guide to CO2 Sequestration,”
Science 300 (2003): 1677.]
the potential to store many hundreds of gigatonnes of carbon dioxide for

many hundreds of years. The schemes are referred to as acidic because dissolv-
ing carbon dioxide gas directly in seawater produces carbonic acid, H2CO3, a
weak acid that would increase the acidity of the ocean in the near vicinity:
CO2(g) H2O(aq) Δ H2CO3(aq)
H2CO3(aq) Δ H HCO3
Adding large amounts of carbon dioxide would lower the pH of ocean water
by tenths of a unit, although much larger decreases of several pH units would
occur near the points of injection.
Carbon dioxide destined for ocean storage could be transported by a
pipeline, originating either from the shore or from a ship stationed above the
disposal site, extending to the depth required (Figure 7-9). Even relatively
shallow injection of the gas in the ocean, at 200–400-m depth, would pro-
duce a satisfactory result, provided that the seafloor there is slanted suffi-
ciently to allow the dense, CO2-rich water to be transported by gravity to
greater depths. Simulations show that most of the gas would return to the sur-
face and enter the atmosphere within a few decades if the CO2-rich water was
simply diluted by mixing with surrounding water, rather than sinking. Over a
Carbon dioxide Deep-sea

pumping station pumping station
Pipeline
Unminable
coal beds
CO2 2000 m
bubbles
Depleted oil or
Mined salt dome gas reserves
CO2 droplet
plume
4000 m
Deep aquifer
Carbon dioxide lake
FIGURE 7-9 Potential sequestration sites for carbon dioxide. [Source: Redrawn from Scientific
American (Feb. 2000): 72–79.]
Fossil Fuels 287
period of centuries, excess carbon dioxide would eventually return to the

atmosphere, but presumably by that time alternative energy sources would
have replaced fossil fuels and the atmospheric CO2 problem would then be
less serious.
A phase diagram for CO2 is illustrated in Figure 7-10a. Below about
500 m deep, water pressure would force pure carbon dioxide to be a compress-
ible liquid, which above 2700 m is less dense than water and would float
upward. Below that depth, it is denser than water and would sink.
However, since ocean temperatures are less than 9°C, the liquid or con-
centrated gas below 500 m could combine with water to form a solid, ice-like
clathrate hydrate, CO2 6 H2O, that, if fully formed, would be denser than
seawater and would sink to the deep ocean. Thus lakes of liquid and/or
clathrate carbon dioxide could form on the seafloor. Figure 7-10b illustrates
an experiment in which a beaker of liquid carbon dioxide was placed almost
4 km deep off Monterey Bay, California.
Direct disposal of CO2 to the deep ocean would require a pipeline to pen-
etrate to a depth of 3000 to 5000 m, producing a pool of liquified carbon diox-
ide, denser than seawater at this depth (see Figure 7-10b). Some—perhaps
just the surface—or all of the liquid carbon dioxide would convert to the
solid clathrate. The pool of liquid carbon dioxide would, probably over
centuries, dissolve into the surrounding water. Unfortunately, sea life under
(a)
(b)
0
2
Pressure (MPa)
4 Gas
Liquid
6
Hydrate
8
10
0 4 8 12 16
Temperature (C)
FIGURE 7-10 (a) Phase diagram for carbon dioxide. The green line shows the phase bound-
ary between gaseous and liquid CO2. The shaded area indicates the conditions under which
the hydrate is stable if sufficient CO2 is present. (b) Liquid carbon dioxide overflowing from a
beaker placed on the seafloor at 3650-m depth. A mass of transparent hydrate formed at the
upper interface, sank to the bottom of the beaker, and pushed out some of the liquid CO2.
[Source: P. G. Brewer et al., “Direct Experiments on the Ocean Disposal of Fossil Fuel CO2,” Science 284
(1999): 943.]
this pool would be exterminated. There is also some fear that earthquakes or
asteroid impact could destabilize the pool, resulting in the release of massive
amounts of carbon dioxide gas into the air above.
Near the seafloor, dissolved carbon dioxide could eventually react with
the solid calcium carbonate, CaCO3, in sediments formed from seashells etc.
to produce soluble calcium bicarbonate, Ca(HCO3)2:
CO2(g) H2O(aq) CaCO3(s) 9: Ca(HCO3)2(aq)
(This reaction is discussed in detail in Chapter 11.) For practical purposes,
the CO2, now chemically trapped in the bicarbonate form, would remain
indefinitely in the dissolved state.
In an alternative scheme, labeled ocean neutral in Figure 7-8, calcium car-
bonate or some other suitable substance such as calcium silicate (a cheap,
abundant mineral) would be reacted with carbon dioxide to transform it to
solid silicon dioxide, SiO2, and aqueous calcium bicarbonate, which could be
drained into ocean depths:
2 CO2 H2O CaSiO3 9: SiO2 (s) Ca(HCO3)2(aq)
Acidity problems associated with direct carbon dioxide dissolution in sea-
water are avoided in this way.
Huge amounts of limestone or calcium silicate would be required for this
form of sequestration, but the potential for CO2 storage by this method is very
great and the storage time of the gas is many thousands of years (Figure 7-8).
In addition, it may be possible to react power plant emissions directly with
a mineral, thereby avoiding the energy-expensive step of extracting and
concentrating the carbon dioxide.
P R O B L E M 7-7
Calculate the mass, in tonnes, of calcium carbonate that is required to react
with each tonne of carbon dioxide.
Alternatively, surface rocks containing alkaline silicates could be

crushed and then reacted with carbon dioxide to produce insoluble solid car-
bonates that could simply be buried in the ground. Unfortunately, direct
carbonation reactions involving CO2 are slow unless the mineral is heated,
a step that is costly in money and energy. In one indirect scheme, magnesium
silicate rock is reacted with hydrochloric acid, HCl, to produce silicon diox-
ide and magnesium chloride, MgCl2. Reaction of this salt with carbonic acid
produces insoluble magnesium carbonate, MgCO3, and re-forms the hydro-
gen chloride, which, in principle, can be recycled:
Mg2SiO4 4 HCl 9: 2 MgCl2 2 H2O SiO2
MgCl2 H2CO3 9: MgCO3 2 HCl
Fossil Fuels 289
There are still energy costs and additional CO2 production associated with
such procedures, however.
An alternative scheme proposed recently for carbon dioxide storage is to
inject it into sediments under the seafloor. Because it would be under high
pressure and at low temperature, it would exist there as a dense liquid or
would combine with the water in the sediments to form the solid hydrate.
Although expensive, this injection process could be useful for power plants in
coastal locations.
Deep Underground Storage of CO2

There have been suggestions that the CO2 output from power plants could
be pumped deep underground into cracks and pores in common alkaline
rocks such as calcium aluminosilicates; there, the rocks could react with the
gas, in microorganism-catalyzed processes, to produce calcium carbonate
and thereby store the CO2. Such carbonate minerals are known to be pres-
ent in deep caves in Hawaii and elsewhere, so the process could well be
feasible if the reactions occur quickly enough. Recently, Norway has started
to pump concentrated CO2 gas into sandstone rocks located a kilometer
below the North Sea; the pores in the rock were left empty by extraction of
natural gas from them in the past. The CO2 could react with the rock and
thus be immobilized.
In the short run, the easiest route to begin sequestration of carbon diox-
ide is probably to inject it into reservoirs containing crude oil or natural gas.
However, the total capacity for carbon dioxide storage by such enhanced oil
recovery, labeled EOR in Figure 7-8, is less than 100 Gt. This technology is
already used to enhance the recovery of oil in some fields, though currently
most of the CO2 is again recovered and reused.
In an interesting international project currently under way, 5000 tonnes
a day of liquefied CO2 are sent through a 325-km-long pipeline from a coal
gasification plant in North Dakota to an oilfield in Weyburn, Saskatchewan.
The gas is injected through pipes 1500 m underground, allowing more oil to
be extracted from the field and sequestering most of the carbon dioxide in the
brine of the oil reservoir. In 2004, after the project had been under way for
four years, about 3.5 million tonnes of compressed carbon dioxide gas (of a
projected 20 million tonnes eventually) had been sequestered at Weyburn.
The injected CO2 that accompanies the oil extracted from the field is cap-
tured and re-injected underground. Monitoring of the site found no significant
amount of the gas to be escaping through the rocks and soil of the area. Any
injected carbon dioxide escaping from the area could be identified by
the characteristic low 13CⲐ12C isotope ratio of the North Dakota fossil-fuel
source; artificial tracer gases were also added to the injected gas to further
monitor potential emissions from the site. Analysis of the fluid that accompa-
nies oil produced in this way revealed that the carbon dioxide has been
dissolving in the reservoir brine and has been trapped by some of the miner-
als in the reservoir. A similar sequestration project is planned for Norway,
where carbon dioxide emissions from a plant that produces methanol from
natural gas would be piped to offshore oil fields and injected into undersea
reservoirs to help force oil to the seabed surface.
Depleted oil and gas reservoirs could be used to store carbon dioxide (Fig-
ure 7-9). These underground caverns are known to be stable, since they have
held their original materials for millions of years. Carbon dioxide storage in
coal seams that lie too far underground to be mined may also be feasible.
Pumping CO2 into the coal helps it release adsorbed methane, which can
then be pumped to the surface and used. Several hundred gigatonnes of car-
bon dioxide could be sequestered in coal.
Much larger in volume and capacity than oil and gas reservoirs are saline
aquifers, large formations of porous rocks that are saturated with salty water
and that lie far underground, well below fresh-water supplies. Carbon dioxide
injected into such an aquifer initially remains a compressed gas or a supercrit-
ical liquid, but some slowly dissolves in the sometimes very alkaline brine
(Figure 7-9). The brine is contained mainly in small pore spaces occupying
about 10% of the volume of the porous rock. If carbon dioxide is to be stored
underground, a depth of more than a kilometer is required so that its density
is comparable to that of water. Even so, it is likely to rise to the top of what-
ever geological formation encloses it and to spread laterally. Consequently,
the caprock overlying the formation must be one that is secure if significant
amounts of CO2 are not to migrate upward through the soil and into the
atmosphere over time. The stability of each aquifer to potential seismic activ-
ity and gas leakage must be individually assessed before it is used.
The Norwegian energy company Statoil has already demonstrated the
feasibility of this approach by annually storing about a million tonnes of car-
bon dioxide (a 9% impurity that must be removed from their crude natural
gas) in a saline aquifer that lies 1000 m under the floor of the North Sea.
Interestingly, Statoil found it cheaper to sequester CO2 this way than to pay
the $50 per tonne carbon tax the Norwegian government has instituted. The
North Sea aquifers are sufficiently large to absorb all emissions of carbon
dioxide produced by Europe for many hundreds of years. Experiments to store
carbon dioxide in saline aquifers are under way in several locations in the
world, including Texas and Japan. In the United States, large saline aquifers
are found in the states lying just below the lower Great Lakes, in southern
Florida, in northeastern Texas, and in the northern midwestern states.
Removing CO2 from the Atmosphere

A potential technique for extracting some of the carbon dioxide that is already
dispersed into the atmosphere and depositing it in ocean depths is the iron
fertilization proposal. Experiments indicate that large portions of the seas,
Fossil Fuels 291
especially the tropical Pacific and the Southern Ocean (which surrounds
Antarctica), lack plankton because they are very iron-deficient. Artificially
adding iron to these areas would result in massive blooms of plankton, some of
which, in the Southern Ocean at least, would descend into the deep oceans,
thereby locking away the carbon dioxide used in photosynthetic activity.
Experiments are under way to test the feasibility of this approach. In particular,
scientists have yet to determine whether much of the additional plankton
would enter the animal food chain and ultimately be converted back to carbon
dioxide. In addition, some scientists have pointed out that the decomposition
of the phytoplankton consumes oxygen and encourages bacteria that produce
methane and nitrous oxide, thereby increasing the concentration of these
greenhouse gases in air upon their release from the oceans. Other side effects of
fertilization could produce additional negative environmental consequences.
Carbon dioxide can also be removed from the atmosphere by growing
plants specifically for this purpose. Some utility companies and some coun-
tries have proposed a scheme by which they are given credit to offset some of
their CO2 emissions by planting forests that would absorb and temporarily
sequester carbon dioxide as they grew. However, this scheme is controversial.
For example, the release of CO2 from soil into the air that occurs when
ground is cleared for growing trees can exceed the total carbon dioxide
absorbed by the new trees for a decade or more. In addition, the carbon stored
in trees would be released back into the atmosphere if the wood burned or
rotted. The conversion by pyrolysis, the decomposition of material by heat in
the absence of oxygen, of wood or other biomass into charcoal or biochar
produces a form of carbon that is much more durable.
In another proposal, carbon dioxide from a power plant would be used to
grow vast amounts of algae, which then could be used as fuel for combustion.
Several prototype facilities of this kind have been constructed. The exhaust
from small power plants is led through clear tubes in which fast-growing algae
are produced in an aqueous environment using sunlight to drive photosyn-
thesis. The algae harvested from the process are dried for combustion or
converted into biodiesel and ethanol fuels (see Chapter 8).
A few scientists have proposed removing carbon dioxide chemically from
ambient air, for example, from high-speed winds used to turn wind turbines,
using chemicals such as amines, already discussed, or some other chemical
absorber. The practicality of chemically extracting carbon dioxide from air, in
which its concentration is only 0.04%, compared to about 13% in power
plant emissions, is yet to be determined.
Reducing CO2 Emissions by Improving Energy Efficiency

Some writers have noted that much of the current energy expended in both
industrial and domestic scenes could be saved by adopting the most efficient
technologies for each purpose. For example, the use of low-wattage compact
fluorescent light bulbs instead of incandescent bulbs would significantly reduce

the amount of electrical energy used for lighting in homes; the payback period—
until the much higher capital cost of these bulbs is more than met by savings in
electrical costs—is a few years. Similarly, automobiles could be made much
more energy efficient and thus use less gasoline to travel a given distance.
However, improving energy efficiency would not necessarily lead to a
reduction in the demand for energy and a reduction in carbon dioxide emis-
sions. The reason is that if energy-consuming equipment is made more effi-
cient, the monetary cost for performing a given task drops, and there follows
a natural tendency to use the equipment more, since it is so cheap to operate.
For example, if you buy a very energy-efficient car, you will be able to afford
to take more trips in it since each one would be cheaper than with a “gas guz-
zler.” Thus some policymakers believe that because of this rebound effect,
energy savings and CO2 reductions from efficiency would not be achieved in
the long run by making energy-consuming devices more efficient. Increased
efficiency would have to be accompanied by price increases on the fuel, pre-
sumably in the form of taxes, for it to reduce overall consumption.
Reducing Methane Emissions

Although our focus so far has been on reducing emissions of carbon dioxide
to the atmosphere, global warming can also be combated by decreasing the
amount of methane that is released. The major opportunities for methane
reduction are
• better maintenance of natural gas pipelines so as to reduce their leakage,
a practice already under way in Russia;
• capture and combustion of the methane released by landfills, underground
coal mines, and oil production; and
• changes in the techniques of rice production, by draining the field a few
days before the plants flower, the point at which maximum emissions begin.
Energy and Carbon Dioxide Emissions

in the Future
Growth in Energy Use
Since the Industrial Revolution, the rate of emission of CO2 to the atmo-
sphere has climbed hand-in-hand with the expansion of commercial energy
use, since so much of the latter (currently 78%) is obtained from fossil-fuel
sources. Barring an unforeseen, massive development of nuclear energy or
renewable fuels or carbon sequestration, CO2 emission rates are expected to
match commercial energy production rate increases as the developing world
undergoes industrialization and as the economies of developed countries
continue to expand. Indeed, a 2003 assessment by the European Union
predicts that, over the first three decades of this century, carbon dioxide emis-
sions will rise globally by an annual average of 2.1%, due to a 1.8% annual
increase in energy usage. The fraction of fossil-fuel energy obtained from coal
is expected to increase over this period—due to higher and higher prices for
oil and natural gas as they become more scarce—thereby increasing the car-
bon intensity of the fuel mix. The report predicts a cumulative increase in
energy use for the United States of 50% and for the EU of 18%. According
to the report, energy use by developing countries will triple (corresponding to
4% annual compounded growth), with the consequence that they will be
responsible for 58% of CO2 emissions by 2030, though they will still trail
most industrialized countries in emissions per capita. If developing countries
can implement the renewable energy technologies (discussed in Chapter 8)
in constructing their economies, they would avoid the heavy fossil-fuel
dependence and intense carbon dioxide emissions characteristic of all
currently developed countries.
IPCC Scenarios for CO2 Emissions and Concentrations

In its 2001 report, the U.N.’s International Panel on Climate Change (IPCC)
described a number of very different scenarios for greenhouse gas emissions
for the rest of the century. The magnitude of the emissions predicted at cen-
tury’s end vary dramatically: 5, 13.5, 20, and 29 Gt of carbon annually, the
range spanning from 0.6 to 3.5 times the current value of about 8 Gt C/year.
The carbon dioxide concentrations projected for 2100 for the IPCC scenar-
ios range from 500 to more than 900 ppm, compared to today’s 373- and the
preindustrial 280-ppm levels.
Even with constant carbon dioxide emissions at current levels or a few
percentage points lower, the carbon dioxide concentration in the atmosphere
will continue to grow. Some policymakers have promoted the idea that,
through international agreements or allocation schemes, the world should
control future CO2 emissions so that the atmospheric level of the gas never
exceeds some specific concentration. Although there is no consensus on the
most appropriate target, for our discussion we shall use 550 ppm. This value is
twice the preindustrial value—in other words, a situation in which human
actions have doubled the natural atmospheric carbon dioxide concentration.
One way in which global CO2 emissions could rise and fall with time in
order to eventually achieve the 550-ppm concentration target is shown by
the curve in Figure 7-11a. Figure 7-11b shows how the corresponding atmo-
spheric CO2 concentration would change with time for this emission scenario.
The scenario was developed assuming that international agreement on CO2
emissions can be achieved in the relatively near future. Consequently, it
assumes modest growth in CO2 releases until about 2060, at which point
a decline would set in. The temperature increase—which tracks the CO2
concentration curve closely—by 2100 would be just under 2°C (relative to
that for the year 2000). The rise in sea levels would be reduced by about
(a)
12
Anthropogenic emissions (Gt C/year)

11
10
9
8
7
6
5
4
3
2
1
0
2000 2050 2100 2150 2200 2250 2300
Year
(b)
600
550
CO2 concentration (ppm)
500
450
400
FIGURE 7-11 Approxi- 350

mate (a) annual CO2 emis-
sion rates and (b) resultant
2000 2050 2100 2150 2200 2250 2300
atmospheric CO2 concen-
trations to meet a 550-ppm Year
stabilization target.
one-third if we embark soon on the scenario to never exceed the 550-ppm

concentration of carbon dioxide.
An alternative scenario to the one shown by the curves in Figures 7-11a
and 7-11b, in which effective CO2 controls are not implemented until several
decades later, would eventually require a sharper decline in emissions and
would reach the 550-ppm limit sooner. Such alternative proposals allow more
time to further develop replacement technologies, such as the solar energy
techniques discussed in Chapter 8, before we begin to end our reliance on fos-
sil fuels. Such scenarios require the world to generate more emissions-free
power than today’s total power consumption by about mid-century, a major
challenge to achieve. By the end of the century, almost all power would have
to be emissions-free. It is not possible to defer emission reductions indefinitely
if the 550-ppm concentration target is to be achieved.
Green Chemistry: Polylactic Acid—The Production of

Biodegradable Polymers from Renewable Resources;
Reducing the Need for Petroleum and the Impact on
the Environment
Our everyday lives are permeated by the chemicals in products such as phar-
maceuticals, plastics, pesticides, personal hygiene products, cleaners, fibers,
dyes, paints, clothes, building materials, computer chips, packaging, and
food. The vast majority of these chemicals are ultimately made from oil, con-
suming approximately 2.7% of the production of this natural resource. The
compounds that are isolated from oil and used to produce chemicals are
known as chemical feedstocks. Approximately 60 billion kg of these feedstocks
are employed to create 27 billion kg of polymers (many are loosely referred to
as plastics) each year. Some of the more familiar polymers (as will be discussed
in Chapter 16) that are produced from crude oil include polyethylene tereph-
thalate (PET), which is used to make plastic beverage bottles and fibers for
clothes; polyethylene, which is used to produce plastic grocery and trash
bags; and polystyrene, which we discussed in the green chemistry section in
Chapter 1. Trade names of polymers, such as Dacron, Teflon, Styrofoam, and
Kevlar, represent polymers that are part of our everyday lexicon.
Approximately 2 billion kg of PET are produced each year. PET is one of
the main targets for the recycling of plastics, yet less than one-quarter of this
total is recycled in the United States; the rest is landfilled or incinerated. Even
when PET is recycled, it generally can’t be reused as beverage bottles; it is
downward recycled into polyester fiber products such as carpets, T-shirts, fleece
jackets, sleeping bags, and car trunk linings, or into thermoformed sheet prod-
ucts such as laundry scoops, nonfood containers, and containers for fruits.
When we use oil to produce items that we dispose of or incinerate
(including the use of oil as a fuel), we are consuming a resource that has taken
nature millions of years to produce. Petroleum is a finite, nonrenewable
resource. Although there are still considerable oil reserves, at the rate of our
current use we will deplete the supply of cheap, readily accessible oil within
the next 30 to 40 years. We must learn to use renewable resources such as bio-
mass rather than petroleum to produce chemical feedstocks.
Scientists at NatureWorks LLC (formerly Cargill Dow LLC) have devel-
oped a method for producing a polymer called polylactic acid (PLA) from
renewable resources—such as corn (called maize in the UK and elsewhere)
and sugar beets—for which they won a Presidential Green Chemistry
Challenge Award in 2002. NatureWorks produces PLA at a plant in Blair,
Nebraska. Ultimately, the goal is to utilize waste biomass as the source of this
polymer. As in the steps shown in Figure 7-12, the corn is milled into
starches, which are then reacted with water to yield glucose, which is then
converted to lactic acid by natural fermentation. This naturally occurring
compound is then converted to its dimer, followed by polymerization
to PLA.
H 99OH
HO99 H HO O
milled hydrolysis fermentation
corn starches 99 lactic acid
H 99 OH
H3C OH
H 99 OH
OH dimerization
d-glucose
O H3C
H3C O
O H
melt polymerization H3C
9
( O9 CH9 C 9
)n O
polylactic acid
H O
FIGURE 7-12 The synthesis of polylactic acid.
The environmental advantages of PLA over petroleum-based polymer

include the following:
• It is made from annually renewable resources (corn, sugar beets, and
eventually waste biomass).
• Production of PLA consumes 20–50% less fossil-fuel resources than do
petroleum-based polymers.
• It uses natural fermentation to produce lactic acid. No organic solvents or
other hazardous substances are used.
• It uses catalysts, resulting in reduced energy and resource consumption.
• High yields of over 95% are obtained.
• The use of recycle streams help to reduce waste.
• PLA can be recycled—converted back to its monomer via hydrolysis,
then repolymerized to produce virgin polymer (i.e., closed-loop recycling).
• PLA can be composted (it is biodegradable); complete degradation
occurs in a few weeks under normal composting conditions.
Another environmental consideration of PLA is that the plants, such as

corn, used to produce the polymer consume atmospheric carbon dioxide, thus
The Extent and Potential Consequences of Future Global Warming 297
reducing the concentrations of this greenhouse gas. When PLA biodegrades,

it releases this carbon dioxide back into the atmosphere in amounts approxi-
mately equal to the carbon dioxide absorbed by the plants used to produce it,
thus making PLA in theory carbon neutral. However, fossil fuels are required
during the production of PLA. Life cycle assessment studies (see Chapter 16)
indicate that PLA requires 25–55% less fossil-fuel-supplied energy than do
petrochemical polymers.
PLA can be used to produce products that are currently made from
petroleum-based polymers such as cups; rigid food containers; food wrappers
and bags; bags for refuse; furnishings for homes and offices (carpet tile, uphol-
stery, awnings, and industrial wall panels); and fibers for clothing, pillows,
and diapers. Small purveyors of natural foods have been using PLA packaging
for several years. In 2005 PLA received a significant boost when Wal-Mart
announced plans to use 114 million PLA containers a year. According to the
company, this will save 800,000 barrels of oil annually.
Biodegradable polymers produced from renewable resources help to
reduce our consumption of oil and have the potential to offer significant
environmental and economic advantages over petroleum-based polymers.
However, we must remember that even production of chemicals from annu-
ally renewable resources such as biomass does not offer a complete solution to
energy and environmental problems. Growing crops, whether they are used
to produce food or chemicals, require fertilizers and pesticides. Energy is
needed to plant, cultivate, and harvest; to produce, transport, and apply fer-
tilizers and pesticides; to make and run tractors; to transport seeds, biomass,
monomers, and polymers. Use of land to produce crops for chemicals, and
more significantly for bio-based fuels, also removes land that could be used to
produce food and feed, and it increases the price for food.
The Extent and Potential Consequences

of Future Global Warming
As we saw in Chapter 6, the Earth’s weather has probably already been
affected by the enhancement of the greenhouse effect due to increasing
atmospheric concentrations of carbon dioxide and other gases. The continu-
ing buildup of CO2 in the air leads to the conclusion that we are in store for
further increases in global air temperatures and other changes to our climate.
In this section, we shall summarize what projections tell us qualitatively
about the climate changes to expect in the coming decades and some of their
consequences for human health.
Those of us who currently suffer through severe winters each year may
look forward to the warmer climate associated with the enhanced greenhouse
effect. After all, in the eleventh and twelfth centuries, an increase of a few
tenths of a degree in the northern temperate zone was sufficient for farming
to occur on the coast of Greenland, for vineyards to flourish extensively in
England, and for the Vikings to travel the North Atlantic and settle in
Newfoundland.
However, the climate changes predicted for the twenty-first century and
beyond do not present a uniformly pleasant prospect. The rate of change in
our climate, which to date has been modest, will be dramatic by the middle of
the century. Indeed, the rapid rate of global change will probably be the great-
est problem with which humanity will have to contend. A more gradual tran-
sition, even to the same end result, would be much easier to handle, not only
for humans but for all living organisms on the planet.
It is very difficult for scientists to model the climate—even with the assis-
tance of the fastest computers in the world—in order to make definitive state-
ments about what changes will occur in particular regions in the future. We
know that there will be substantial changes in the climate, but we are unable
to specify exactly what they will be.
Predictions for Climate Change by 2100

The significant changes in the Earth’s climate that have occurred in the past
half-century, that are predicted to continue over the twenty-first century, and
that are likely to have been at least partially caused by anthropogenic effects,
as judged by the IPCC in its 2007 report, are summarized in Table 7-2.
According to sophisticated computer simulations of the future climate
reported by the IPCC, the rise in the average global air temperature by 2100
(compared to 1990) could be as small as 1.4°C or as large as 4.0°C. As in the
twentieth century, more warming will occur at night than during the day.
The magnitude of the temperature increase will depend greatly on whether
emissions (including those of sulfur dioxide) are controlled or not. At a min-
imum, however, the world will warm more than twice as fast in this century
as it did in the last. Part of the rather large range of the prediction is due to
uncertainty about exactly how sensitive the climate is to carbon dioxide.
Indeed, research reported in 2003 indicates that aerosols have accounted for
more greenhouse warming in the past than previously thought; conse-
quently, scientists may have significantly underestimated the sensitivity of
temperature to CO2, in which case the predicted increases will have to be
revised upward.
An increase of a few degrees in temperature may seem small, but our cur-
rent average air temperature is less than 6°C warmer than that in the coldest
periods of the ice ages! Snow cover and sea-ice area will continue to decline.
There may well be enough melting of ice in the Arctic region for the North-
west Passage to be used for commercial transport, since the warming of all
Arctic regions in winter is projected to be much greater than the global aver-
age. Indeed, the Arctic regions of Alaska and western Canada warmed at the
rate of 0.3–0.4°C per decade in the 1961–2004 period. The Arctic (Southern)
Ocean will probably become ice-free in the summer, a situation that has not
Recent Trends and Projections for Extreme Weather Events

TABLE 7-2 That Have Undergone Recent Change
Likelihood That
Trend Occurred in Likelihood of Future
Late 20th Century Likelihood of a Human Trends Based on
Phenomenon and (Typically Post Contribution to Projections for
Direction of Trend 1960) Observed Trend 21st Century
Warmer days and Very likely Likely Virtually certain

fewer cold days and
nights over most
land areas
Warmer and more Very likely Likely (nights) Virtually certain
frequent hot days
and nights over
most land areas
Warm spells/heat Likely More likely than not Very likely
waves. Frequency
increases over
most land areas
Heavy precipitation Likely More likely than not Very likely
events. Frequency
(or proportion of
total rainfall from
heavy falls) increases
over most areas
Area affected by Likely in many More likely than not Likely
droughts increases regions since 1970s
Intense tropical Likely in some More likely than not Likely
cyclone activity regions since 1970
increases
Increased incidence Likely More likely than not Likely
of extremely high
sea level (excludes
tsunamis)
Source: IPCC, Climate Change 2007: The Physical Science Basis. Summary for Policymakers:
www.ipcc.ch
occurred for at least a million years. A similar situation is occurring over the
land; because of global warming, the land is snow-covered for a shorter dura-
tion in winter and has a much higher albedo than the soil and vegetation
exposed in the spring. In addition, most of the region of permafrost—land in
northern Canada, Alaska, Siberia, and northern Scandinavia that stays frozen
year-round—will likely melt to a depth of 3 m or more during this century.
The total amount of global rainfall is projected to increase, since more
water will evaporate at the higher surface temperatures. The global average
precipitation increases by about 2% for every Centigrade degree rise in tem-
perature. Although the world overall will become more humid, some areas
will become drier. To make matters worse, most areas of the world that cur-
rently suffer from drought are predicted to become even drier. Continental
interiors at mid-latitudes will have continuing risk of drought in summer due
to continued drying of the soil, the increased rate of evaporation from higher
air temperatures being greater than the increase in the rate of precipitation.
Subtropical areas will experience less precipitation, and equatorial and high-
latitude regions will experience more, continuing the twentieth-century
trends.
An increase in the average atmospheric temperature means that the air
and water at the Earth’s surface would contain more energy and that more
extreme weather disturbances could result, the effect of global warming that
will affect many of us the most. The number of days having intense rain
showers or very high temperatures will both increase. Storm wind intensities
and heavy downpours will increase in some tropical areas.
Predictions About Sea Levels

Although air and land surfaces are quick to warm with an increase in average
global temperature, the same is not true of seawater. It takes many centuries
for an increase in air temperature to gradually make its way down deeper and
deeper into the ocean. For this reason, the rise in sea levels resulting from any
particular amount of global warming is largely delayed for many years. Con-
sequently, even if atmospheric carbon dioxide levels did not increase at all
beyond today’s values and no further global warming occurred, sea levels
would continue to rise for centuries to come, as lower layers of the oceans
became heated—and expanded—by air that has already been warmed.
Sea levels are predicted to rise by about half a meter by 2100—in addi-
tion to the 10–25-cm rise experienced over the last 100 years—though there
is a large uncertainty in this value. About half of the predicted rise in sea level
is due to the melting of glaciers, and the other half arises from the thermal
expansion of seawater. The expansion occurs because the density of water
decreases gradually as water warms beyond 4°C, the temperature at which it
reaches its maximum density, as illustrated in Figure 7-13. Since density is
mass divided by volume, and since the mass of a given sample of water can-
not change, the volume it occupies must increase if its density decreases.
Thus, as seawater warms (beyond 4°C), the volume occupied by a gram or
kilogram of it increases; the only way that this can occur is if the top of the
water—the sea level—increases.
Scientists predict that the Greenland

Ice Sheet may eventually melt entirely due
to global warming, raising ocean levels by 1.00
about seven meters, but they are uncertain
as to the fate of the Antarctic Ice Sheet.
However, complete melting will require
millennia to complete. Parts of both ice 0.998
Density (g/mL)
sheets sit above sea level on land. Conse-
quently, the transfer, by the melting of
their surface ice and the resulting draining 0.996
of liquid water into the oceans, causes an
increase in sea levels, as does the transfer
into the oceans of icebergs broken off 0.994
from the ice sheets. The collapse of ice
shelves, which are the extensions into the
sea of glaciers, such as the Larsen-B shelf
0.992
in the Antarctic that collapsed in the 0 10 20 30
early 2000s, allows glaciers that had been Temperature (˚C)
blocked to migrate more quickly toward
open water.
Although an increase of half a meter in sea level does not seem very large, FIGURE 7-13 Density
there are countries, like Bangladesh and the small island nation of Tuvalu in of liquid water versus
temperature.
the South Pacific, in which much of the population currently lives on land
that would be flooded by a rise in sea level of this amount. Damage from trop-
ical storms would increase because of these higher sea levels.
In the long term, the most dramatic—though unlikely—effect of sub-
stantial global warming would be a change in the circulation patterns of
water in the Atlantic Ocean. Currently, warm surface waters flow northward
from the tropics into the North Atlantic, bringing heat to Europe and to a
lesser extent to eastern North America. Some scientists have speculated that
a rapid rise in temperature and rainfall levels could weaken or even eliminate
this circulation pattern, as historical geological records indicate has hap-
pened in the past.
Climate Predictions for Specific Regions

It is much harder for scientists to make specific, reliable predictions for indi-
vidual regions than for the globe as a whole. The climate changes that seem
likely for the various continents, according to the 2007 IPCC report, are sum-
marized in Table 7-3.
The higher latitudes of the Northern Hemisphere are expected to expe-
rience temperature increases substantially greater than the global average.
Warming over some land areas, including the United States and Canada,
should be noticeably faster than the average rate for the globe.
Significant Impacts of Climate Change That Will Likely Occur in the

TABLE 7-3 Continents in the Twenty-First Century
Arctic Significant retreat of ice; disrupted habitats of polar megafauna; accelerated loss
of ice from Greenland Ice Sheet and mountain glaciers; shifting of fisheries;
replacement of most tundra by boreal forest; greater exposure to UV radiation
North America Reduced springtime snowpack; changing river flows; shifting ecosystems, with
loss of niche environments; rising sea level and increased intensity and energy
of Atlantic hurricanes increase coastal flooding and storm damage; more
frequent and intense heat waves and wildfires; improved agriculture and forest
productivity for a few decades
Europe More intense winter precipitation, river flooding, and other hazards; increased
summer heat waves and melting of mountain glaciers; greater water stress in
southern regions; intensifying regional climatic differences; greater biotic stress,
causing shifts in flora; tourism shift from Mediterranean region
Central and Widespread melting of permafrost, disrupting transportation and buildings;
Northern Asia greater swampiness and ecosystem stress from warming; increased release of
methane; coastal erosion due to sea ice retreat
Central America Greater likelihood of intense rainfall and more powerful hurricanes; increased
and West Indies coral bleaching; some inundation from sea-level rise; biodiversity loss
Southern Asia Sea-level rise and more intense cyclones increase flooding of deltas and coastal
plains; major loss of mangroves and coral reefs; melting of mountain glaciers
reduces vital river flows; increased pressure on water resources with rising
population and need for irrigation; possible monsoon perturbation
Pacific and small Inundation of low-lying coral islands as sea level rises; salinization of aquifers;
islands widespread coral bleaching; more powerful typhoons and possible
intensification of ENSC extremes
Global oceans Made more acidic by increasing CO2 concentration; deep overturning
circulation possibly reduced by warming and freshening in North Atlantic
Africa Declining agricultural yields and diminished food security; increased occurrence
of drought and stresses on water supplies; disruption of ecosystems and loss of
biodiversity, including some major species; some coastal inundation
South America Disruption of tropical forests and significant loss of biodiversity; melting glaciers
reduce water supplies; increased moisture stress in agricultural regions; more
frequent occurrence of intense periods of rain, leading to more flash floods
Australia and Substantial loss of coral along Great Barrier Reef; significant diminishment of
New Zealand water resources; coastal inundation of some settled areas; increased fire risk;
some early benefits to agriculture
Antarctica and Increasing risk of significant ice loss from West Antarctic Ice Sheet, risking much
Southern Ocean higher sea level in centuries ahead; accelerating loss of sea ice, disrupting
marine life and penguins
Source: Scientific Expert Group Report on Climate Change and Sustainable Development, Confronting Climate Change,
United Nations Foundation (2007): www.confrontingclimatechange.org.
In the U.S. Midwest and the area just north of it in Canada, as well as in
southern Europe, the soil will probably become much less moist because of
increased rates of evaporation in the warmer air and ground. This could affect
the continued suitability of these areas for the growing of grain. High-latitude
regions, however, could experience increased productivity, at least where the
soil is suitable for agriculture. In areas that become drier, the positive CO2
fertilization effect on plants will cancel some of the negative effects of
decreased rainfall. There will be longer frost-free growing seasons at northern
latitudes but increased chances that heat stress will affect crops grown there.
Food production in temperate areas will probably also be affected by the
attack of insects that in the past have been largely killed off during the
winters but that could survive and flourish under warmer conditions.
Temperature and moisture changes will occur quickly compared to those
that have taken place in the past, and consequently some ecosystems will be
destabilized. Coastal ecosystems such as coral reefs are particularly at risk.
The species composition of forests is likely to change, especially in regions far
removed from the Equator. For example, the hardwood forest in eastern
North America may be at risk of extinction if climate zones shift more
quickly than their migration can keep up with. The boreal forest of central
Canada could be eliminated by fire by 2050; indeed, the frequency of fires in
these woodlands is already climbing.
Predicted Effects on Human Health

Many scientists have concluded that human health will be affected adversely
by global warming. There will probably be more extreme heat waves in sum-
mers but fewer prolonged cold snaps in winters. The expected doubling in the
annual number of very hot days in temperate zones will affect people who are
especially vulnerable to extreme heat, such as the very young, the very old,
and those with chronic respiratory diseases, heart disease, or high blood pres-
sure. This will be particularly acute for poor people, who have less access to
air conditioning. The heat wave in the summer of 2003 in Europe resulted in
the death of at least 10,000 people in France alone.
Domestic violence and civil disturbances could also increase, as they
tend to occur more frequently in hot weather. On the other hand, there
would probably be a decrease in cold-related illnesses because of the milder
winters. Air quality in summer will probably degrade further, as the back-
ground concentration of ground-level ozone will probably increase substan-
tially. Higher CO2 concentrations and warmer weather will increase the
production and release of pollen by plants such as ragweed, thus exacerbating
allergic responses.
Less directly, global warming may extend the range of insects carrying
diseases such as malaria into regions where people have developed no immu-
nity, and it may intensify transmission in regions where such diseases are
already prevalent. It has been predicted that malaria could claim an addi-
tional million victims annually if the temperature rise is sufficient to allow
parasite-bearing mosquitoes to spread into areas not now affected. In North
America, suitable habitat for the mosquitoes is being lost, so fortunately it
should not be as much of a problem for Americans and Canadians. A differ-
ent type of mosquito carries the dengue and yellow fever viruses, and its
range could increase with warming, thereby spreading these diseases. There
is also evidence that cholera rates increase with warming of ocean surface
waters, because coastal blooms of algae are breeding grounds for the disease,
and they increase with water temperature. Some experts in disease control
discount these predictions, arguing that other effects such as increased rain-
fall could well negate or even reverse the effects on disease rates of increases
in air temperature.
Animal health could also be affected by the spreading of disease by para-
sites. In addition, some species, such as polar bears and caribou, that live in
very cold regions could be at risk of extinction from habitat changes that
threaten their hunting practices.
International Agreements on Greenhouse Gas Emissions

Faced with the prospect that increased CO2 emissions over the next century
could result in a significant increase in global air temperature, with its result-
ant modifications of climate, some governments and organizations have been
debating how future emissions can be minimized while still allowing eco-
nomic growth to occur.
The first agreement on greenhouse gas emissions was reached at the Rio
Environmental Summit meeting in 1992; each developed country was to
ensure that its CO2 emission rate in 2000 would be no greater than that in
1990. This target was met, in fact, by very few countries; by 2000, most were
emitting at levels well above their targets.
The second agreement was reached in negotiations held at Kyoto, Japan,
in 1997. Thirty-nine industrialized nations agreed to decrease their collective
CO2-equivalent emissions by 5.2%, compared to 1990 levels, by 2008–2012.
The greenhouse gases affected by the Kyoto Accord are carbon dioxide,
methane, nitrous oxide, hydrofluorocarbons, perfluorocarbons, and sulfur
hexafluoride.
Under the agreement, the United States was due to cut its emissions to
7% less than its 1990 level, Canada and Japan by 6%, and the European
Union collectively by 8% (with wide variations for individual countries
within this unit). Some countries, such as Australia, were permitted to
increase their emissions beyond 1990 levels. Emissions by developing coun-
tries were not controlled by the Kyoto Accord, since they were not significant
players in emitting greenhouse gases in the past and therefore did not con-
tribute much to current global warming.
If countries were to achieve their Kyoto agreement levels, the annual per
capita CO2 emissions in 2010 in developed countries would have decreased
from 3.1 tonnes of carbon in 1997 to 2.8 tonnes, whereas, because of economic
development, emissions from developing countries would probably have risen
from 0.5 to 0.7 tonne. The CO2 concentration in air would have been a little
over 1 ppm less than would have otherwise resulted. However, the United
States and Australia subsequently withdrew from the agreement. As an alter-
native to cutting greenhouse gas emissions in line with the Kyoto treaty, the
U.S. government proposed in 2003 to reduce the carbon intensity of the U.S.
economy by 18% by 2012. Nevertheless, some U.S. states—California and sev-
eral of those in New England—have decided on their own to limit greenhouse
gas emissions. However, the extent to which most other countries will meet
their targets by 2012 is in doubt. Canada, for example, had increased its emis-
sions by 30% in 2006 rather than decreased them compared to 1990 levels.
The existing increase, by one-third, of the atmospheric CO2 level, as well
as the temperature increase and climate modification that this probably
caused, resulted in large part from the industrialization and increased stan-
dard of living in developed countries. Without a significant change in the
methods by which energy is produced and stored, and/or implementation of
carbon sequestration on a massive scale, these same nations will continue to
require about the same rate of CO2 emissions in the future in order to main-
tain their economic growth.
Rather than utilizing a procedure in which countries have CO2 emission
targets that are negotiated at international meetings, schemes have been dis-
cussed that are based on allocations that could be traded between countries
on the open market. In a manner similar to the way in which SO2 emission
rights currently are traded in the United States, countries that need to emit
more than their collective CO2 allocations could purchase unused alloca-
tions from countries with an excess. A bonus of this scheme is that it pro-
vides an incentive to develop and invest in cleaner technologies, since
avoiding CO2 emissions could be cheaper than purchasing additional
rights—especially in the future, when few nations will have excess emission
capacity and the price of emission rights will rise.
The question of how CO2 allocations can be made fairly in order to ini-
tiate the free-market CO2 emission-trading scheme is a perplexing one. In
the simplest scheme, each country would be assigned an allocation based
strictly upon its (current) population. For example, if it was concluded that
the current average annual emission of 1 tonne of carbon as CO2 per capita
could be sustained indefinitely, then this quantity would be allocated to a
country for each of its residents. If it was decided to cut back current global
emission levels, e.g., by one-quarter, then only 0.75 tonne per capita per year
would be allocated etc.
An immediate consequence of the per capita allocation method would
be the annual transfer of substantial funds from all developed countries to
developing and undeveloped ones, since, according to the data in Figure 7-4,
the former all exceed the 1-tonne average, by factors ranging from 2 to 5.
Although this method would provide external funding so that developing
countries could establish efficient energy infrastructures, it would likely not
prove popular in developed countries, since their energy costs would rise.
One alternative allocation scheme is based on how much energy is
required for industrial production by a country and how efficiently it uses
energy. Thus a country’s carbon dioxide allocation would be directly pro-
portional to its GDP. This allocation method rewards compact, energy-
efficient developed countries at the expense of those—both developed and
developing—that emit more CO2 per unit of GDP. However, such a scheme
would permit continued economic growth by developing countries, since
their CO2 allocations would track their economic growth. The global ratio
of allowed carbon dioxide to dollar of GDP would have to decline with time
if global emissions are to be controlled, since global GDP rises by several
percent per year. Interestingly, the CO2/$ GNP ratio is more independent of
the level of economic development than is the ratio based upon population;
e.g., China emits about 1.0 kg of carbon dioxide for each dollar of production,
compared to 0.9 kg for the United States, 0.5 kg for Japan, 1.0 kg for
Germany, and 0.7 kg for India.
Some policymakers believe that carbon taxes, i.e., taxes based on the
amount of carbon contained in a fuel rather than upon its total mass,
should be instituted as a disincentive to use fossil fuels, especially coal,
since it generates more CO2 per joule of energy produced than does natu-
ral gas. In fact, the hydrogen-to-carbon ratio of the average global fuel
mix has been continuously increasing over the last century and a half, as
we moved from economies whose energy source was dominated by wood
(H/C ratio of about 0.1) to coal (1.0 ratio) to oil (about 2.0) and now to
natural gas (4.0); this is the same direction as moving to lower CO2/energy
ratios, as implied above. Carbon taxes could be phased in over a period of
decades, starting at a low price that would gradually increase, thereby
giving time for low-carbon-emission technologies to be further developed
and implemented.
We conclude by commenting on the paradox that faces humanity today
concerning the enhancement of the greenhouse effect. On the one hand,
there exists the slight possibility that doubling or quadrupling the CO2 con-
centration will have no measurable effect on climate and that efforts to
prevent such an increase not only would be an economic burden for both the
developed and the developing worlds, but would perhaps be unnecessary. On
the other hand, if the predictions of scientists who model the Earth’s climate
turn out to be realistic, but we do nothing to prevent further buildup of the
gases, both present and future generations will collectively suffer from rapid
and perhaps cataclysmic changes to the Earth’s climate.
Review Questions
1. Define the term commercial energy. On what 14. What is meant by the term CNG? What are
factors does the magnitude of its use in a country the advantages and disadvantages to fueling
depend? vehicles with CNG?
2. What is the equation relating exponential 15. What is meant by the term carbon
growth to the annual increase in a quantity? sequestration?
3. Define the term carbon intensity. Describe how 16. Name three techniques whereby carbon
the carbon intensity has changed over the last few dioxide could be stripped from power plant
decades (a) globally, (b) for the United States, and emission gases.
(c) for China.
17. Define oxycombustion and state its
4. How does the rate of CO2 emissions by a coun- advantages.
try depend on its population, its carbon intensity,
18. Explain the difference between “ocean acidic”
and its GDP?
and “ocean neutral” techniques of storing CO2 in
5. Explain why the concentration of CO2 in air is oceans.
expected to rise linearly with time if its rate of
19. Define enhanced oil recovery and explain its
emission remains a constant.
relationship to the underground storage of carbon
6. What are the ultimate origins of coal, oil, and dioxide.
natural gas? Which fuel is in greatest reserve
20. Explain why sea levels are expected to rise as
abundance?
global air temperatures increase.
7. What is the most important class of hydrocar-
21. List some of the consequences, including
bons present in crude oil?
those affecting human health, that may occur
8. What is meant by the BTX fraction of gasoline? as a consequence of global warming in the
Is it toxic? future. Why might soil in some areas be too
dry for agriculture even though more rain falls
9. What is meant by engine knocking?
on it?
10. How is the octane number rating scale for fuels
22. What is the Kyoto Accord? What gases
defined?
are limited in their emissions under it? Would
11. List several ways in which the octane number the Kyoto agreement have halted global
of fuels can be increased by the addition of other warming?
compounds to straight-chain alkane mixtures.
23. Describe the scheme whereby a nation’s
12. What is the main component of natural gas? allocation of carbon dioxide emission could
Write out the balanced chemical equation illus- be traded on a market. Describe two schemes
trating its combustion. by which initial allocations could
be made.
13. Why is natural gas considered to be an envi-
ronmentally superior fuel to oil or coal? What 24. What is a carbon tax and what are the argu-
phenomenon involved in its transmission by ments in favor of it? Why do you think many
pipeline might offset this advantage? people oppose it?

See the discussion of focus areas and the principles of 2. What are the environmental advantages of
green chemistry in the Introduction before attempt- using PLA in place of petroleum-based polymers?
ing these questions.
3. Why does the use of biodegradable polymers
1. The formation of polylactic acid (PLA) from (to replace petroleum-based polymers) not offer
biomass developed by NatureWorks LLC won a complete solutions to energy and environmental
Presidential Green Chemistry Challenge Award. problems?
(b) List three of the twelve principles of green
chemistry that are addressed by the green chemistry
developed by NatureWorks LLC.
Additional Problems
1. Using a ruler and calculator, estimate from the amount of O2 they consume. Assume the empirical
Figure 7-1 the fraction of CO2 emissions in 2004 formula for oil is CH2.]
compared to 1990 (a) from the United States and
4. Canada has massive supplies of heavy oil in tar
(b) collectively from China, India, and other
sands, which are being used to make gasoline by
developing countries. Did the fraction of emissions
combining them with natural gas. Assume that the
from EU countries increase or decrease over that
empirical formulas of these three fuels are CH,
period?
CH2, and CH4, respectively, and that gasoline is
2. List several reasons that you think proponents made by hydrogenating the tar with hydrogen pro-
of carbon dioxide allocations based strictly on a duced from natural gas in its reaction with water to
country’s population would advance in support of produce CO2 and H2. Combine the hydrogenation
their position. What objections can be raised to and hydrogen production equations so as to use all
their position? Repeat this exercise for an alloca- the H2, thereby deducing the overall reaction of
tion scheme based on current GDP. CH and CH4 with steam to produce gasoline and
carbon dioxide.
3. The replacement by natural gas of oil or coal
used in power plants has been proposed as a mecha- 5. Given that the density of dry ice (solid CO2) is
nism by which CO2 emissions can be reduced. 1.56 g/cm3, calculate the diameter in meters of a
However, much of the advantage of switching to dry-ice ball that would be produced from the
gas can be offset since methane escaping into the 5 metric tonnes of CO2 produced on average by
atmosphere from gas pipelines is 23 times as each person in developed countries each year.
effective, on a molecule-per-molecule basis, in
6. A sign was spotted outside a farmers’ market
causing global warming as is carbon dioxide.
with the slogan: “Help Stop Climate Change: Buy
Calculate the maximum percentage of CH4 that
Local Produce.” Explain whether taking the advice
can escape if replacement of oil by natural gas is to
of this sign could indeed “help stop climate
reduce the rate of global warming. [Hint: Recall that
change.”
the heat energy outputs of the fuels are proportional to
7. Using a ruler and calculator, estimate from Fig- (b) from natural gas liquids. What is the fraction
ure 7-7 the fractions of petroleum that are pre- of oil of all kinds produced in 2050 relative to that
dicted by 2050 to originate (a) from heavy oil, and of 2008?
Further Readings
1. A. Witze, “That’s Oil, Folks,” Nature 445 (2007): 4. E. Rubin et al., IPCC Special Report: Carbon
14–17. Dioxide Capture and Storage: www.ipcc.ch/activity/
srccs/index.htm
2. J. L. Sarmiento and N. Gruber, “Sinks for
Anthropogenic Carbon,” Physics Today 55 5. R. H. Socolow, “Can We Bury Global Warming?”
(Aug. 2002): 30–36. Scientific American (July 2005): 49–55.
3. H. H. Khoo and R. B. H. Tan, “Life Cycle 6. H. Inhaber and H. Saunders, “Road to
Investigation of CO2 Recovery and Sequestration,” Nowhere,” The Sciences (November/December
Environmental Science and Technology 40 (2006): 1994): 20–25. (Argues that energy conservation
4016–4024. leads to increased consumption.)
C H A P T E R
8
RENEWABLE ENERGY,
ALTERNATIVE FUELS, AND
THE HYDROGEN ECONOMY

topics are used:
 Ideal gas law
 Thermochemistry calculations
 Electronic structure of atoms
 Electrochemistry: oxidation numbers; redox
half-reactions; batteries; electrolysis
 Crystalline versus amorphous solids
 Basic organic chemistry structures: alcohols, ethers,
carboxylic acids, esters, sugars, carbohydrates
 Vapor pressure of liquids
 Distillation

 Greenhouse gases (carbon dioxide, methane,
nitrous oxide) (Chapter 6)
 Anaerobic decomposition; clathrates (Chapter 6)
 Fossil fuels (Chapter 7)
 Light absorption as energy; photons (Chapter 1)
 Air pollution: photochemical smog, particulates,
gaseous pollutants (Chapters 3 and 5)
 Catalytic converters; thermal NO (Chapter 3)
311
312 Chapter 8 Renewable Energy, Alternative Fuels, and the Hydrogen Economy
Introduction
In Chapters 3– 7, we have seen how
the atmosphere has been affected by
emissions into it of pollutant gases
such as sulfur and nitrogen oxides and
greenhouse gases such as carbon diox-
ide and methane. The emphasis in this
chapter is on alternative technologies
under development that could reduce
the anthropogenic production of such
gases in the future while still allowing
economic growth to occur. We begin by
considering some possible solutions to
the further buildup of atmospheric
CO2 by a partial switchover from fossil
fuels to renewable energy, especially
A wind farm in Scotland. solar power. We then make an exten-
(Image State) sive survey of the various alternative fuels, including biofuels and hydrogen,
that may be more “greenhouse friendly” than those used at present and that
also would be effective in reducing air pollution. The generation of energy by
nuclear power is discussed in Chapter 9.
Renewable Energy
The Sun sends enough energy to the Earth to supply all of our conceivable
energy requirements, about 10,000 times more than we use now and will in
the future, if only we could trap it efficiently. In addition to being plentiful
and reliable, it is renewable energy—energy that will not run out and whose
capture and use do not result in the direct emission of greenhouse gases or
other pollutants.
The world currently uses about 12 terawatts (TW, 1012 watts) of power,
about 85% of which is generated by the burning of fossil fuels. Since 1 watt
is 1 joule per second, and since there are 3.2 107 seconds in a year, our
annual power consumption is about 3.8 1020 J, 380 EJ. Given that an
average light bulb is rated at 60 W, we are using the equivalent of 200 billion
light bulbs at a time, an average of about 35 per person, nonstop. Of course,
this figure is an average for people in developed and developing countries; if
we redo the calculation for North Americans, we are using about 200 60-W
light bulbs for every man, woman, and child!
The pie chart in Figure 8-1 illustrates the sources of the world’s commer-
cial energy in 2004; the percentages for energy used to generate electricity are
shown in parentheses. Clearly, most renewable energy currently is generated
by burning biomass and by hydroelectricity, with the latter used to generate
electricity. An assessment in 2003 by the European Union (EU) for energy use
in the year 2030 predicts that renewable Oil

energy, including wind, geothermal, and 35.03%
the direct forms of solar energy, will not (7%)
keep pace with rising energy demand.
Because people from rural regions of
Asia and Africa will burn less firewood,
due both to their migration to cities
and to disappearing forests, renewable
energy collectively will drop from the Coal
current 13% (only 2% of which is not 24.59%
from biomass) to only 8% of the global (40%)
Gas
supply. 20.44%
(19%)
Hydroelectric Power
Of all the forms of renewable energy,
hydroelectric power is by far the most Nuclear 6.33%
(16%)
important. Worldwide, it constitutes Hydro, other 1.73%
over 80% of renewable energy (other Traditional biomass (16%)
than that based upon biomass) and 2% 8.48% Small hydro 0.41%
of global commercial energy. Modern biomass 1.91% Solar 0.53%
Hydroelectric power is an indirect Geothermal 0.23% Wind 0.32%
form of solar energy. In the hydrological
cycle, the Sun’s energy evaporates water New renewables 3.40%
from oceans, lakes, rivers, and the soil Renewables 13.61% (18%)
and transports the H2O molecules
upward in the atmosphere via winds. After the water molecules condense to FIGURE 8-1 Sources of
raindrops, they still possess considerable potential energy owing to their ele- primary world energy
vation, only a portion of which is dissipated if they fall onto land or a water supply in 2004.
[Source: J. Goldemberg,
body that lies above sea level. We can harness some of its remaining poten- “Ethanol for a Sustainable
tial energy by forcing the downward-flowing water to turn turbines and Future,” Science 315 (2007):
thereby generate electricity. 808–810.]
Although there are small hydroelectric installations that use the flow of
a river, most large-scale facilities use dams and waterfalls, where the water
pressure—and hence the power yield—is much greater. In particular, the
energy imparted to a turbine by falling water is directly proportional not only
to the volume of the water but also to the height from which it falls. For this
reason, new hydroelectric projects usually involve the construction of a high
dam along the path of a flowing river. Water then collects behind the dam
and its level rises to a considerable height. The water that is allowed to flow
over the top of the dam falls a considerable distance before encountering the
turbines positioned near the bottom. Unfortunately, the collection of water
behind the dam floods considerable areas of land, creating a lake with envi-
ronmental problems such as those discussed below.
If all sites worldwide were exploited, the total amount of energy obtain-
able from hydroelectric sources would be about 100 EJ per year; about 20% of
this total is obtained currently. Most of the sites that require little modifica-
tion to use, and that are located within a reasonable distance of centers that
use considerable electric power, have already been exploited; to use a com-
mon expression, most of the “low-hanging fruit” has already been picked.
However, there are many river systems in developing countries, especially
Africa, where considerable new hydroelectric power is currently being devel-
oped by the construction of dams.
Although hydropower is often thought of as pollution-free, there are
environmental and social costs associated with it, especially ones resulting
from the creation of the reservoirs behind dams. The most important of these
costs include
• the displacement of human populations from lands flooded to create

reservoirs;
• the eutrophication of water in reservoirs;
• the release of greenhouse gases, especially methane, from flooded areas;
• the release of mercury into reservoir water and consequently into the fish
that swim in the water and human populations that eat the fish (this topic is dis-
cussed in more detail in the online Case Study Mercury Pollution and the James
Bay Hydroelectric Project (Canada) and in Chapter 15);
• the devastation to fish populations, such as salmon, from the blockage of
their migratory routes by dams; and
• the buildup of silt behind dams, with the result that less silt is carried to
locations farther along the waterway.
Unfortunately, the construction of new hydroelectric projects involving

the damming of river systems, especially in developing countries, often pro-
ceeds without adequate environmental assessment and planning ahead of
time. The World Bank and several other large financiers of such hydroelectric
facilities do insist on an independent assessment of the project’s impacts
before they provide financial assistance.
The largest hydroelectric project in the world is the 26-turbine Three
Gorges Dam in China, which, when completed in 2009, will provide 18 MW
of power—equivalent to five large coal-fired power plants—and will have
cost $25 billion to construct. Although about a million people had to be relo-
cated to avoid being flooded by the artificial lake, the dam also controls flood-
ing on the Yangtze River and thereby saves thousand of lives.
The expansion of wetlands that occurs by the deliberate flooding of land
to produce a large, deep reservoir of water generally creates a long lake covering
hundreds or thousands of square kilometers. The Three Gorges Dam will result
in a lake that is 600 km long! The deep water in such lakes is largely anaerobic,
especially if the flooded land was not first cleared of vegetation. The anaerobic
decomposition of the original trees, bushes, etc. on the land produces carbon
dioxide and methane in almost equal volumes, both of which escape from the
surface and enter the atmosphere. The emissions from such reservoirs are signif-
icant. This is particularly true for methane, since it is such a powerful green-
house gas (Chapter 6). Deep, small reservoirs produce and emit much less
methane than do shallow ones that contain large areas of flooded biomass, such
as those in the Brazilian Amazon. Indeed, the combined global warming effect
of the methane and carbon dioxide produced by a large, shallow reservoir
created to generate hydroelectric power can, for many years, exceed that of the
carbon dioxide that would be emitted if a coal-fired power plant were used
instead to generate the same amount of electrical power! Even after the original
vegetation has decayed, new plants that have grown on the shores of the lakes
during the dry season, when water levels recede, are later engulfed by rising
water in the wet season; they eventually decompose, releasing more methane.
Wind Energy
Winds are air flows that result from the tendency of air masses that have
undergone different amounts of heating, and that therefore have developed
unequal pressures, to equalize those pressures. The air flows from regions of
high pressure to those of low pressure. The heating of air results directly or
indirectly from the absorption of sunlight; indeed, about 2% of the Sun’s
energy received on Earth is transformed into wind energy. A large quantity of
such indirect solar energy, about 300 EJ annually, is potentially available as
wind power, although only 0.05% of it currently is being tapped.
Polar areas receive less sunlight and therefore less heat than do the trop-
ics. To compensate for the resulting temperature difference between tropical
and polar regions, winds arise in the air as do currents in the oceans. Warm
air and water are carried toward the poles, whereas cold air and water are
transported in the opposite direction, toward the Equator. However, these
flows do not follow simple trajectories, owing to factors such as the spinning
motion of the Earth around its axis and the effects of local terrain.
The force of the wind can be exploited to do useful work or to generate
electrical energy in the same way that the force of flowing water is used in
hydroelectric power plants. Historically, the strong, sustained winds in cen-
tral North America were exploited by windmills to pump water and later to
generate small amounts of electricity on individual farms until the middle of
the twentieth century. Of course, windmills have been in use in Europe—
especially in Holland—for centuries.
In recent decades, the large-scale generation of electricity by huge, high-
tech windmills gathered in “wind farms” has become feasible. Wind power is
currently the world’s fastest-growing source of energy. Figure 8-2 (green curve)
illustrates the increasing rate of annual wind-power installations in recent
years. In 2001 alone, global wind-power capacity grew by one-third and
12,000
Wind
10,000 Solar-cell
1500
Solar-cell power (MW/year)

Wind power (MW/year)
8000
6000 1000
Scale
4000
500
FIGURE 8-2 Annual pro- 2000 Scale
duction of wind energy
and solar-cell energy.
[Source: Redrawn from 0 0
1980 1985 1990 1995 2000 2005
L. R. Brown et al., Vital Signs
2006–2007 (New York: W. W. Year
Norton, 2007).]
has been rising at about 25% per year, compounded, since then. As a conse-
quence, overall in the period 1995–2005, it rose 12-fold. As of 2005, about
60,000 megawatts (MW) of wind power had been installed. Large growth in
wind-power installations has occurred in Germany (currently the world leader
in wind power, with 40% of installed power), Spain, the United States (which
was the leader in the 1990s), India, and Denmark (which generates more than
one-fifth of its electricity this way). This technology could be useful in many
other parts of the world as well. A 2003 EU report predicts that 4% of the
world’s energy will be produced by wind power in 2030.
Technically, six times the 2001 world electricity output could be pro-
duced from wind, but only 0.5% was actually produced globally in this way
in 2005, although 3% of Europe’s electricity was produced in this way. A
landmass the size of China would be needed to satisfy world electricity
demand from wind alone. More realistically, wind power could be expanded
to provide up to perhaps one-fifth of the world’s electricity.
If price is not taken into account, then the country with the highest
potential for wind power is the United States. About 90% of the U.S. poten-
tial for wind power lies in 12 states in the Midwest, ranging from North
Dakota to northern Texas (see Figure 8-3), though the demand for electricity
is centered far from most of these areas. Indeed, the United States has enough
potential wind power to supply all its electricity now and in the foreseeable
future. The world’s largest wind farm covers 130 km2 in Oregon and
Washington and will eventually involve 460 turbines.
FIGURE 8-3 Percentage

of land area estimated
to have class 3 or higher
wind power in the
contiguous United States.
[Source: “Wind Energy
Percent land area Resource Atlas of the
1–20% 21–50% United States,” Chapter 2:
51–80% 81–100% http://rredc.nrel.gov/
wind/pubs/atlas/maps/
chap2/2-10m.html.]
Wind Speed and Windmill Size

As one would intuitively expect, the greater the velocity, v, of the wind, the
greater the amount of energy a windmill or wind turbine will produce. In
fact, the energy increases very sharply with wind speed. The energy yield
from wind is proportional to v3, i.e., to the third power of the wind speed.
Consequently, a small improvement in velocity produces a large increase
in yield; e.g., an increase from 22 to 26 mph improves the energy yield by
two-thirds!
The cubic dependence of energy on wind speed is the result of two fac-
tors. First, the kinetic energy of the motion of the air mass in the direction of
the wind is proportional to the square of the air speed, since from physics we
know that for any moving body, its kinetic energy is given by mv2/2. Second,
the amount of wind passing over the blades per unit of time increases linearly
in direct proportion to the wind speed. The energy available to the wind tur-
bine is equal to the product of these two factors, so it is proportional to v3.
Hence, much of the energy available to windmills occurs in short bursts of
high velocity due to this strong dependence of energy on wind speed.
The energy the windmill can gather is proportional to the square of its
blade length, since the area the blade sweeps out is proportional to the length
squared. Since wind speeds increase with height above the ground, a tall
turbine is also more efficient for this reason.
Each windmill in a wind farm extracts energy from the flow of air on it,
so the individual windmills must be physically separated from each other to
some extent. For technical reasons, no more than about one-third of the
energy passing by a windmill can be extracted from the flow of air around it.
Potential Wind-Energy Sites

As a consequence of the local terrain, some geographical regions experience
almost constant windy conditions. Geographical areas are commonly divided
into seven classes of potential wind-power density, with class 7 having the
highest potential. Ideal locations for wind farms are those with an almost
constant flow of nonturbulent winds in all seasons. Although wind energy
does rise steeply with wind velocity, locations with sudden gusts of high-speed
wind are not considered favorable. Locations at less than 2-km altitude, with
average wind speeds of at least 5 m/sec, corresponding to 18 km/hr (11 mph),
are generally required for a location to be considered economically feasible.
Some authors use the criterion of annual mean wind speeds Ú 6.9 m/sec
(25 km/hr or 15 mph) measured at 80 m, the tip of the blade height of
modern windmills, as suitable for low-cost wind-power generation. Such sites
are considered to be of class 3 or higher potential wind-energy sites. The
regions of high wind-power potential at reasonable cost are the United States,
Canada, South America, the European countries that are members of the
Organization for Economic Cooperation and Development (OECD), and the
former Soviet Union. The areas with the lowest potential are in Africa,
eastern Europe, and Southeast Asia. In most areas, the potential exceeds the
current electricity usage.
Economic and Environmental Considerations

The most efficient and largest commercial wind turbines currently are the
2-MW units, three times larger than the models of the mid-1990s. Behemoths
with huge, 120-m blades are under development; they will deliver 5 MW.
About 660 North American homes can be supplied with electricity from a
2-MW system on typical hot afternoons, when the power draw peaks due to
air conditioner usage. By contrast, modern coal-fired power plants generate
from 125 MW to 1000 MW, so hundreds of windmills would be required to
replace the power generated by one coal-fired plant.
In terms of energy payback—the amount of time required to generate
the energy used in constructing the unit—that for wind is only 3–4 months.
Carbon dioxide emissions from wind power are the smallest for any power
source (see Figure 8-4).
Of all the forms of renewable energy, wind power is the most economical.
The cost of generating electricity using modern windmill technology—and
feeding it into existing power grids—is now almost competitive with conven-
tional energy sources. In a 2004 report, the lowest-cost wind energy was
quoted as 5¢ (U.S.) per kilowatt hour (kWh, the energy of 1 kilowatt of
power used continuously for 1 hour). This is about the same as that from new
coal-fired plants, almost as low as that

300
generated by natural gas, and less than
Tonnes CO2 per terajoule of electricity

one-tenth of its cost 20 years earlier. As
mentioned above, however, there would
also be significant transmission costs if
wind energy were to be expanded in the 200
midwestern states. If the world switches
eventually to a hydrogen economy, hydro-
gen generation powered by wind in this
area could generate much of the U.S. sup- 100
ply. Currently, the electrolyzers required
for the process are expensive.
Some individual buildings, including
households that are too remote to be con- 0
nected to power lines, generate their own
al
il
as
ro
lta -
s
a
vo oto
ic
in
O
Co
le
yd
W
uc
Ph
electricity using rooftop-mounted wind
H
N
turbines. When all the power generated is
not needed to run the 12-V appliances
etc. within the building, the excess is FIGURE 8-4 CO2 emis-
sions associated with
stored in 12-V batteries, to be drawn upon in times of low or no wind. different energy sources.
There is often public resistance to placing wind turbines in populated [Source: “The Power to
areas because they are unattractive. For this reason, placing them on agri- Choose,” New Scientist,
cultural land or even offshore is becoming popular. A huge new 1000-MW (6 September 1997): 18.]
wind farm, involving more than 300 turbines, is planned for central
Labrador, in eastern Canada. One of the advantages of this project is its
remote location, hundreds of kilometers from habitation, so any perceived
unsightliness is not an issue. The pros and cons of wind power are summa-
rized in Table 8-1.
Coastal daytime summer breezes arise because of the difference in density
between the air over the water and that over the adjacent land. Since sun-
light heats dry land more quickly than it does water, the air over the land also
becomes warmer than that over the lake or sea. Since warm air rises—due to
its lower density (according to the gas law, density is inversely proportional to
Kelvin temperature)—and high above the surface moves out to sea, the
remaining air over the land surface has a lower density and pressure than that
over the sea. Consequently, to equalize pressures, surface air flows from over
the sea to the land mass, creating a cooling sea breeze. At night, the situation
is reversed, since the land cools more quickly than does the water, producing
an outward breeze by the same mechanism.
Consistently breezy offshore shallow areas, such as the sandbanks off the
coasts of Denmark and Ireland, are ideal sites and are now used extensively
for wind farms. Indeed, offshore locations are popular in Europe, and most are
anchored in water 8–10 m deep. A recent study indicated that locations in
New England, on Lake Erie, and off the coast of mid-Atlantic states alone
TABLE 8-1 Pros and Cons of Wind Power
Arguments Against Wind Power Arguments in Favor of Wind Power
Many sites—including offshore ones—are This is also true of many potential new
far from centers of demand, requiring long hydroelectric projects.
transmission lines to be built.
Wind power needs some tax incentives to Conventional and nuclear power plants receive
compete with traditional forms of electricity much larger, though indirect, subsidies.
production.
The construction of windmills at some remote
sites requires roads, forest clearing, and other
destructive infrastructure.
Windmills kill wildlife, especially bats and birds Studies show that very few birds are killed by
of prey. wind turbines, especially compared to the
number killed by cars, cats, etc.
Huge areas of land, and therefore of habitat,
are required to construct enough windmills to
have a substantial effect on electricity supply.
The continuous motion of the blades produces Noise level is comparable to traffic.
low-grade noise pollution nearby.
On-shore wind farms are a form of “visual Sites remote from areas of dense population can
pollution.” be used.
Wind power is usually intermittent, with a low Excess wind energy can be stored mechanically
annual load factor, and requires backup by pumping water to elevated storage facilities
facilities using traditional resources to remain or in batteries and then used when needed to
constantly on-call. produce electricity.
Very little greenhouse gas emissions are
associated with wind energy compared to
fossil-fuel combustion. There is no nuclear
waste to store or potential radiation problems
compared to nuclear power.
could generate up to 20% of the U.S. electricity supply. However, the physi-
cal conditions at some potential offshore locations are rather harsh, and it is
difficult to service broken turbines in open water. West-coast waters off North
America are too deep for such placements, and those in the southeastern
United States are too prone to hurricanes.
In summary, there exists considerable potential for wind energy to supply

a significant fraction of the future electricity supply of many countries at
lower cost to the environment than with any other feasible alternative. The
price for new wind-power supplies is comparable to that of newly constructed
coal- and nuclear-fired power plants and would probably be lower if any real-
istic costs associated with the environmental impact of conventional sources
is assessed in the future. However, there are unresolved problems of efficient
energy storage for many locations having intermittent winds that prevent the
adoption of wind as the main source of electrical energy generation. Indeed,
many power grids are unwilling to rely on wind for more than a small fraction
of their energy supply due to its intermittent nature. However, the develop-
ment of flow batteries, in which the chemicals formed when they are being
charged—e.g., by excess wind capacity—can be removed from the batteries,
stored in containers, and later resupplied during discharge, may help over-
come storage problems.
Biomass
The biomass produced by the worldwide process of photosynthesis constitutes a
form of solar energy. The annual amount of energy currently produced from this
source is about 55 EJ; a much larger amount is potentially available. The use of
wood, crop residues, and dung (dried excrement from plant-consuming animals)
has been a traditional source of energy in undeveloped countries, but its domes-
tic and small-scale use is very polluting to the air and inefficient. Small-scale,
polluting biomass burning is generally phased out in favor of commercial energy
such as fossil fuels and electricity as a country’s economy develops. Nevertheless,
biomass was second only to hydroelectric power in the production of renewable
energy in the United States in the late twentieth century.
Recently, technology has been developed to use biomass in large-scale
installations that do not pollute the air. For example, wood-chip waste can be
burned to produce steam. Alternatively, wood can be gasified, or digested by
bacteria, and converted into alcohol fuels (as discussed later in this chapter).
Fast-growing trees on plantations could be used for this purpose, using land
not suitable or needed for agriculture. Currently, crops such as corn and sug-
arcane are grown to produce ethanol for fuel, but often these facilities con-
sume so much fossil fuel in their operation that little is saved overall in CO2
emissions (also discussed later in the chapter).
Overall, the power density of photosynthesis (about 0.6 W/m2) is too low
for it to supply most of the world’s energy needs. The density is low because
the efficiency of conversion of sunlight to chemical energy in photosynthesis
is very low, no more than 1 – 2%, even in the most productive areas. At
today’s consumption levels, the amount of land required to supply our energy
needs by biomass equals that of all agricultural land currently developed,
more than 10% of Earth’s land surface.
Geothermal Energy
Geothermal energy, though not solar-based, is another form of renewable
energy. It has proven particularly useful in countries that have no fossil-fuel
resources. Geothermal energy is heat that emanates from beneath the Earth’s
surface and results from the radioactive decay of elements and from conduc-
tion from the molten core ( 5000°C) of the Earth. Because of the move-
ment of crustal (tectonic) plates, there are volcanic zones in which the heat
is brought closer than usual to the surface. An example of the heat gradient
with increasing depth for a geothermal zone is compared to that in a non-
geothermal area in Figure 8-5. When deep groundwater circulates within a
geothermal zone, the water is heated by contact with the hot rocks and is
sometimes vaporized. If the hot fluids are trapped in porous rocks under a
layer of impermeable rock, a geothermal reservoir can form.
Geothermal energy is available as steam and/or hot water at temperatures
ranging from 50 to 350°C from reservoirs of hot groundwater. The fluid
generally has to be piped 200–3000 m to the surface to be usable, though in a
few places it exits spontaneously from the ground as “hot springs.” Production
of hot fluid generally declines with time once a reservoir is tapped.
Geothermal energy in the form of moderately hot water (50–150°C) is
most often used directly for space heating of buildings, including greenhouses,
and for aquaculture. High-temperature geothermal energy ( 220°C) in the
form of steam or superheated water is usually found only in volcanic regions
and island chains and is used to generate electrical energy. Hot water of inter-
mediate temperature is used both for heating and for generating electricity.
Temperature (°C) gradient

°C 50° 100° 150° 200° 250°
500
1000
Depth (ft)
1500
FIGURE 8-5 Under- 2000

ground temperature gradi-
ents in a typical area
2500
(dashed line) and in
one having geothermal
3000 Bottom hole
potential (solid green
temperature
curve). [Source: Geothermal 265°C (509°F)
Education Office, at
http://geothermal.marin.org.]
The generation of electricity by geothermal energy can be accomplished

directly if superheated steam is available, since it will drive turbines. The effi-
ciency of heat-to-electricity conversion is not great, however, since the tem-
perature difference between the steam and the cooling water used to
condense the steam is not large, in accordance with the second law of ther-
modynamics discussed later in this chapter. The condensed steam is pumped
down an injection well back into the source to sustain production. If the
geothermal energy is available only as moderately hot water, its energy can be
first transferred to an organic fluid—such as isopentane—whose boiling point
is lower than 100°C, and the hot organic vapor can be used to turn the
turbine. The overall efficiency of such power conversion is less than 12%.
Alternatively, in “flash steam” power plants, high-pressure hot water from the
reservoir undergoes a large drop in pressure in a flash tank, at which point
some of it “flashes” to steam, which is used to drive turbines.
Currently, over 8000 MW of geothermal electrical power has been
installed globally, providing some developing countries with a significant
fraction of their electricity. For example, both the Philippines and Indonesia
generate a significant fraction of their electricity geothermally, in power
plants that are as large as 100 MW. The United States (in California and
Hawaii especially), Mexico, and Indonesia are other leading producers of
geothermal electricity. A map showing the location of potential geothermal
power sites in the United States is presented in Figure 8-6. A recent report
FIGURE 8-6 Regions of

potential sites for geother-
mal energy production
in the United States.
[Source: Geothermal
Direct uses Power plants and direct uses
Education Office, at
http://geothermal.marin.org.]
from MIT concluded that enough geothermal energy could be obtained to

meet the entire electricity needs of the United States by piping water far
underground to be vaporized by contact with hot rocks and using the result-
ant steam to turn turbines.
As expected, the main costs associated with the production of geother-
mal electrical power are capital ones; operating costs are low. High capital
investment is needed for exploring, drilling the wells, and installing electri-
cal generating equipment. The direct capital cost per kilowatt of installed
capacity is about $1500 for large power plants that have a high-quality steam
resource available.
The use of geothermal energy—including the wastewater from geother-
mal power generation—for space heating is widespread; 58 countries world-
wide employ it to some extent, for a total usage of over 12,000 MW. Per
capita, Iceland leads the world in geothermal energy. As a result of the mid-
Atlantic meeting of two tectonic plates deep under the island, geothermal
energy is plentiful. For some years, over 80% of the hot water and heating
in its major city, Reykjavik, has been supplied by hot water tapped from
sources a few hundred meters below the ground and distributed by pipelines.
Deeper geothermal reservoirs, from which steam can be obtained, are
tapped to generate some of the country’s electricity. Eventually, the plan is
to tap more reservoirs and use the excess electricity to produce hydrogen gas
by electrolysis of water. Iceland hopes to become the world’s first economy
based on hydrogen and to have its economy totally free of fossil fuels by
about 2030.
One drawback to geothermal energy is the large quantity of hydrogen
sulfide gas that is often released when the hot fluid is tapped below the Earth’s
surface, especially at deep sites. Emissions of the gas into air are minimized by
scrubbing the fluid. Some carbon dioxide that accompanies the hot fluid from
the ground is released into the air, but the amount is tiny compared to what
would be emitted if the same amount of energy were generated by burning
fossil fuels. At some sites, the hot groundwater contains significant amounts
of dissolved, sometimes acidic, minerals, which can corrode equipment and
deposit scale. In some cases, the minerals contain sellable substances such as
silica and zinc.
The impact of the wastewater on local aquatic life is eliminated if it is
reinjected into the ground after its heat has been extracted. There is also
some danger of land subsidence if reinjection does not occur.
In the past, geothermal energy has been exploited only where unusual
geological features result in the existence of steam or hot water close to the
Earth’s surface. A project under way in Achen, Germany, is attempting to
overcome this limitation by sinking a borehole 2.5 km (1.1 miles) into the
Earth’s crust, where rock temperatures are about 80°C. Cold water will flow
down the outer component of the pipe, being warmed as it descends, and then
be pumped back to the surface through an inner pipe, where it will be used.
Another application of geothermal energy is the use of heat pumps. These

devices draw heat energy from the soil under the ground or from a shallow
underground river and pump it to the surface to supplement heating of build-
ings in winter. In summer, the direction of heat flow is reversed, with energy
being transferred from buildings above the ground to the underground location.
Wave and Tidal Power

Wave power and tidal power can be obtained in many coastal regions of the
world and is competitive economically in niche markets. It is estimated
that about 20 EJ of power is potentially recoverable from waves and tides.
The source of the energy of tides is the gravitational influence of the Sun
and Moon on the water’s mass. In some locations, coastal currents generated
by tides can be exploited to turn submerged turbines mounted on pipes that
fit into holes drilled in the seafloor. Because water is so much denser than air,
slow currents—about 10 km/hour is best—driving such “submerged wind-
mills” efficiently generate electricity.
Tides cause large masses of water to be lifted and then lowered twice a day.
If the tides in a coastal basin are generally high, a gate that can be opened or
closed can be built across the basin. When the tide is coming in, the gate is left
open so the water behind it rises. At high tide, the gate is closed. The dammed
water leaving the basin turns a turbine, generating electricity.
Three tidal power plants are currently in operation, located in France,
Nova Scotia, and Russia. These installations had high capital costs and
can operate only twice daily. Although the energy produced is renewable and
pollution-free, sedimentation occurs behind the dam gates, and tidal mudflats
are often destroyed as a result of the operation.
Wave power at the sea’s surface can be exploited. The machines, based
on an oscillating water column, consist of a chamber that contains trapped air
located just above the water surface. Wave power is generated by using the up-
and-down motion of water that results from waves, which are caused by winds
and thus are an indirect form of wind energy. The rising wave compresses air
trapped in the chamber. The high-pressure air is then released through a valve,
turning a turbine to produce electricity. As the wave recedes, air rushes back
in through another valve, also spinning the turbine. Currently there are thou-
sands of oceanic navigation buoys whose 60-W light bulbs are powered by this
mechanism. Large-scale wave-power facilities are still in the future.
Types of Direct Solar Energy

The direct absorption of energy from sunlight and its subsequent conversion to
more useful forms of energy such as electricity can occur by two mechanisms:
Thermal conversion Sunlight (especially its infrared component, which
accounts for half its energy content) is captured as heat energy by some
absorbing material. (An everday example of such a material is a shiny metal

surface, which becomes very hot when left in sunlight.) Solar energy is an
excellent source of heat at temperatures near or below the boiling point of
water, a category that accounts for up to half of total solar energy usage.
Photoconversion The absorption of photons associated with the ultraviolet,
visible, and near-infrared components of sunlight brings about the excitation to
higher energy levels of electrons in the absorbing material. The excitation sub-
sequently causes a physical or chemical change (rather than a simple degrada-
tion to heat).
An example of passive solar technology—systems that use no continuous
active intervention or additional energy source to operate them—is the use
of solar box cookers in developing countries. In temperate climates, the
design of buildings to absorb and retain (by insulation) a maximum fraction
of the solar energy that falls on them in winter is another example.
Solar water heaters are used extensively in Australia, Israel, the southern
United States, and other hot areas that receive lots of sunshine. They are also
used extensively in China, Germany, Turkey, and Japan. The water heaters
represent the biggest use of active solar technologies, which are defined as
those that employ an additional energy source to operate them. Solar
collectors located on the rooftops of private homes and apartment buildings,
as well as some commercial establishments such as car washes, contain water
that is circulated around a closed system by an electrically driven pump.
Sunlight is absorbed by a black flat-plate collector, which transfers the heat to
the water that flows over it and is bounded on the outside by glass or a plastic
window. The hot water is pumped to an insulated storage tank until it is
required for bathing or laundry or to help heat swimming pool water.
In more elaborate installations, the hot water is passed through a heat
exchanger, which is a system of pipes over which air is passed and thereby
heated by thermal transfer. The hot air can be used immediately in winter to
heat the rooms of the building. If not needed immediately, the heat can be
stored in other materials such as rocks. Usually a backup system, in which water
can be heated electrically or by burning fossil fuel, is incorporated to provide
heat on cloudy days or in high-demand situations.
Using Thermal Conversion to Produce Electricity

By focusing the sunlight reflected by mirrors onto a receiver that contains a
solid or a fluid, very high temperatures can be achieved. The hot fluid can be
used to generate electricity by turning turbines.
As discussed in the next section, the fraction of thermal energy that can
be extracted and converted to electricity from a mass of hot fluid at an absolute
temperature Th is limited by the second law of thermodynamics to be no greater
than (Th Tc)兾Th, where Tc is the final absolute temperature of the cooling
water. Consequently, it is advantageous to use a gas that has been heated to

the highest possible temperature to maximize the amount of energy that is
transformed to electricity rather than just degraded to waste heat. Indeed,
temperatures of 1500°C have been achieved in steam heated by focusing sun-
light. Generally, power plants need gas heated to 1200 – 1350°C at a pressure
of 10 – 30 atm to operate. Simply focusing sunlight on tubes of air cannot
achieve more than 700°C and 1 atm pressure. In one promising design, sun-
light is focused by mirrors onto ceramic pins, which absorb the solar energy
and heat up to 1800°C. Because they have a large surface area, the pins effi-
ciently transfer the heat to air that flows around them. The hot, pressurized air
(rather than steam) is then used to turn turbines and produce electricity.
The solar thermal electricity that results from power plants of this type
may become competitive in price with conventional sources. This is partic-
ularly true if the waste heat, e.g., steam near the boiling point of water, can
also be used for some purpose. This technique of using the waste heat from
a heat-to-electricity conversion for a constructive purpose is called the
cogeneration of energy. (It is a common feature of new power plants fueled
by natural gas.) Unfortunately, power plants based on steam require large
amounts of cooling water to condense the steam back into the liquid state
as part of the system’s cycle (see Figure 8-7); in many areas that have abun-
dant land and sunlight, there is little water available for this purpose. Sci-
entists have also pointed out that if the absorption of sunlight by such
systems occurred on a massive scale, the Earth’s albedo would be altered,
with consequent effects on the climate that are difficult to predict.
High-pressure Generator
boiler Steam
at Th
Fossil fuel in Electricity FIGURE 8-7 The genera-

Steam out
turbine tion of electricity from
air (O2) a steam turbine cycle.
In solar thermal electricity
CO2 To cooling tower generation, the water is
or cold river water heated by the Sun’s rays
Water
rather than by burning
condensate and/or a fossil fuel. Th and Tc refer
cogeneration at Tc to steam and water temper-
CO2 up the stack atures, as discussed in the
text. [Source: Modified from
or sequestered Cooling water
M. I. Hoffert et al., “Advanced
CO2 out Condenser return flow
Technology Paths to Global
Pump Climate Stability: Energy for
a Greenhouse Planet,” Science
298 (2002): 981.]
Another way to use the very-high-temperature heat energy is to drive

a thermochemical process such as the reduction of a metal oxide to the free
metal (and oxygen gas). The metal could then be used to generate electricity
in batteries or to react with water to form hydrogen fuel. In either case, the
product is the metal oxide, which can be recycled for reuse. An example
under development is the dissociation of zinc oxide, ZnO, into metallic zinc
and oxygen at temperatures above 1700°C. Alternatively, the heat could
be used to produce a combination of carbon monoxide and hydrogen from
carbon dioxide and methane.
CO2 CH4 9: 2 H2 2 CO H 248 kJ/mol
Reversal of this highly endothermic reaction produces heat that can be used
to generate electricity etc. without the net emission of greenhouse gases,
since the methane and carbon dioxide products are collected and reused.
Limitations on the Conversion of Energy:

The Second Law of Thermodynamics
In all processes that convert high-temperature heat into electricity, a portion
of the original heat energy is inevitably lost as waste heat at a lower temper-
ature. This loss is partially unavoidable as a consequence of the second law of
thermodynamics and applies to the production of solar thermal electricity as
well as to other energy conversion processes.
According to the second law, entropy (or disorder) must increase—or at
the least be unchanged—when one type of energy is converted into another.
The law tells us that for any body at absolute temperature T that possesses
an amount q of heat, the entropy S is a positive quantity given by the
formula
S q兾T
Since high-quality (low-disorder) energy such as electricity has essentially
zero entropy, clearly one cannot convert 100% of the heat into electricity,
since the change S in entropy associated with the conversion would be neg-
ative. However, if some of the initial heat energy qh at the initial high temper-
ature Th is degraded to a smaller quantity qc at a lower temperature Tc, then
the entropy change S for the process could be positive or zero:
S entropy of energy after conversion entropy of energy before conversion

qc 兾Tc 0 qh 兾Th
For the most complete conversion to electricity possible, S 0; for this sit-
uation the equation can be rearranged to give the new relationship
qc 兾Tc qh 兾Th or qc qh Tc 兾Th
The amount of heat converted to electricity is qh qc, which upon

substitution for qc is equal to
heat converted qh qh Tc 兾Th
qh (1 Tc 兾Th)
qh (Th Tc)兾Th
Thus the maximum fraction of the original heat that can be converted to
electricity is
heat converted兾initial heat (Th Tc)兾Th
In other words, the maximum yield of electricity increases as the difference
in temperatures between the original heat source and the waste heat
increases. Thus if sunlight can be converted to heat at 1500°C (1783 K),
and if the temperature of the waste heat could be held to 27°C (300 K),
the fraction of energy that could be converted to electricity would be
(1783 300)兾1783 0.83
In fact, the efficiencies calculated by the formula are somewhat overesti-
mated when more than one physical phase is involved. For example, associated
with the conversion cycle in traditional power plants is a step that condenses
steam back into liquid water (Figure 8-7), a process in which entropy is
decreased. Consequently, additional energy beyond that calculated must be
degraded to waste heat to compensate.
P R O B L E M 8-1
What is the maximum percentage of heat at 900°C that could be converted
into electricity if the waste heat was produced as steam at 100°C?
P R O B L E M 8-2
Electricity could be obtained by exploiting the thermal gradient between the
surface and the deep waters of the ocean. The maximum gradient, about 20°,
is achieved in tropical waters. What is the maximum percentage of the energy
associated with this gradient that could be converted to electricity if the sur-
face (cooling) water temperature is 25°C?
P R O B L E M 8-3
In order to reach a conversion efficiency of 50%, to what minimum Celsius
temperature must a heat source be raised if the waste heat has a temperature
of 57°C?
Solar Cells
Electricity can be produced directly from solar energy by the photoconver-
sion mechanism. This application exploits the photovoltaic effect, which is
the creation of separated positive and negative charges in a material as a
result of the excitation by light of an electron within the solid from its nor-
mal energy level to a higher, excited state. Both the excited electron and the
location of the site of positive charge (the “hole”) are mobile within the solid,
so an electrical current could be made to flow in the material. The hole
“moves” by means of the transfer of a bonding electron from an atom adjacent
to the initial hole to the atom on which the hole is now located, thereby
moving the position of the positive charge. Successive bonding-electron
transfers of this type allow the hole to continue moving.
The material used for photovoltaic or solar cells is a semiconductor,
which is a solid that has a conducting behavior intermediate between that of
a metal (freely conducting) and an insulator (nonconducting). In semicon-
ductors, the bonds linking the atoms are relatively weak, so the separation in
energy between the bonding and antibonding levels is relatively small (com-
pared to that of an insulator). Consequently, the energy required to excite an
electron from the least stable of the filled, bonding levels to the most stable
of the empty, antibonding levels is small but finite. The most common semi-
conductor used in solar cells is elemental silicon, for which this band gap sep-
arating the energy levels is 124 kJ/mol, which corresponds to infrared light.
Silicon’s light absorption ability extends from the band-gap energy of
124 kJ/mol through to energies associated with the visible region, so most of
the photons of sunlight are absorbed. However, all the photon energy in
excess of the 124 kJ/mol band gap is wasted by being converted into heat
rather than promoting current flow. When this loss of energy is combined
with that wasted by recombination of electrons and holes even in the purest
single crystal silicon, only a maximum of 28% of sunlight’s energy can be con-
verted into electricity. Commercial cells now have efficiencies of 15–20%.
A higher proportion of sunlight energy can be absorbed and utilized if
cell wafers having slightly different absorption characteristics are combined
in a single cell. A triple-junction cell, combining layers of gallium indium
phosphide, gallium arsenide, and germanium, can absorb sunlight with 40%
efficiency but is very expensive to manufacture. Amorphous silicon has a
maximum efficiency of only slightly more than half the value for pure
silicon—because electron–hole combination occurs more readily, converting
more of the energy into heat—but is used extensively because it is so much
less expensive to manufacture and can be produced in thin films.
Each solar cell measures about 10 cm 10 cm 200 ␮m thick and
produces only about 1 W of electricity, so to generate electricity in useful
quantities, many are joined together in a solar array. One problem with the
electricity generated using solar cells is that it is direct current (dc) rather than
the alternating current (ac) that is used in power grids and by most equipment
and appliances. The dc electricity can be converted to ac, although with the
loss of some power (as waste heat).
The cost of producing the solar cells and the problem of storing the elec-
tricity for use at night and on cloudy days are the greatest barriers to their
increased use. As with other applications of solar energy, the capital cost in
creating the infrastructure required to capture and use the “free” energy of the
Sun is substantial. The cost of the encapsulation of cells, the wiring, and the
construction of supporting structures is relatively high since each cell is inef-
ficient; collectively, this adds about as much to the total cost of a power sys-
tem as the cost of the cells themselves. Currently, crystalline solar cells cost
about $4兾W to manufacture, so the system itself costs about $8兾W; since the
average home can be supplied by a 4-kW system, the cost of using cells to
completely power a house is about $32,000. If solar cells could be made 20%
efficient, this power demand could be met by about 20 – 25 m2 of solar panels,
i.e., an area about 5 m 5 m.
Although the solar cells do not generate any carbon dioxide during
their operation, their manufacture does consume significant amounts of
energy and therefore causes substantial CO2 emissions. Indeed, according
to Figure 8-4, photovoltaics are the most CO2-intensive of the various
renewable energy forms. The energy and carbon dioxide payback periods for
solar cells and their infrastructure currently are about three years but
are expected to fall to one to two years when manufacturing techniques
improve further. Once the cells are manufactured, however, their use to
generate power in a home saves about as much carbon dioxide per year as is
emitted from the family car. The Japanese government subsidized solar cells
for tens of thousands of rooftops and, indeed, Japan is now the world’s
largest producer of such cells.
The cost of manufacturing solar cells has continued to fall with time, but
electricity generated in this way is still not close to being competitive with
that produced by conventional methods of power generation. Currently,
90% of cells are made from crystalline silicon and the remaining 10% from
thin-film amorphous silicon. To date, the silicon used for solar cells has been
castoff or excess silicon from the semiconductor electronics industry. How-
ever, this supply will rapidly become inadequate if and when the computer
industry revives from its recession.
Photovoltaic power may become attractive in hot, sunny locations such as
the southwestern United States, where the peak power demand, driven by the
need for air conditioning, coincides in time (summer afternoons) with the peak
solar energy availability. Already, solar-cell power (plus storage) is cheaper than
extending power grid lines a kilometer or more away from an existing network
into a remote region, and it is competitive in cost with the use of diesel gener-
ators for this purpose. Portions of this textbook were written at a seaside loca-
tion that is within sight of an offshore lighthouse powered by solar cells. The
technology is also commonly used in water pumps, remote roadside telephones

and signs, and satellites.
The use of solar cells in developing countries, most of which have sun-
shine in abundance, could obviate the need for the creation of power grids
to carry electricity over long distances from source to user and represents
the greatest potential market for expansion of photovoltaic power. Indeed,
the majority of solar cells made in the United States are exported. Solar-
cell electricity is already used to power water pumps, lights, refrigerators,
and TVs in some developing countries. A mid-1990s survey found that 45%
of new solar cells were used to electrify homes, villages, and water pumps;
36% were used for communications and other industrial applications; and
14% were used for the generation of grid-bound electricity. However, by
2000, more than 50% of new solar cells were connected to grid systems.
As with wind power, world production of solar cells for power production
has soared since the mid-1990s (see black curve in Figure 8-2; note the dif-
ference in scales for the two types of power). Although almost 1700 MW of
solar-cell capacity was shipped in 2005, it represents only 15% of the wind-
turbine power installed that year. Although Germany installed almost half
the global new solar-cell capacity in 2005, the United States may shortly
resume its leadership in this area, since California plans to install 3000 MW
of solar power in the next decade. Japan expects to have 4800 MW installed
by 2010.
Could solar cells be used to supply all of the electricity needs of developed
countries? Using today’s efficiencies and materials, the energy needs of the
United States could be met by a continuous array of solar cells covering a
square of land about 160 km 160 km (100 miles 100 miles). Although
this area of 26,000 km2 does not seem extraordinarily large, it is about a thou-
sand times larger than the total area covered by all the solar cells manufac-
tured through 1998 and would cost trillions of dollars to construct! An area
about 10 times larger—about 0.1% of the Earth’s surface—could supply all
the world’s energy needs.
Conclusions About Solar Energy

In these discussions, some general features concerning the use of solar energy,
as opposed to fossil-fuel and nuclear energy, have emerged, and others have
also been reached by energy analysts. Many of these conclusions apply to all
forms of renewable energy.
The advantages of solar energy appear to be that it
• is free and fantastically abundant;
• has low environmental impact;
• has low operating costs;
• does not require imported oil or large, centralized suppliers and expensive
distribution networks; and
• has high public acceptance as a “natural” form of energy.
The disadvantages of solar energy appear to be that it
• is intermittent in its availability and thus requires that efficient storage or
backup systems be constructed so that power can be supplied continuously;
• is diffuse—it provides a low density of energy per unit of surface collec-
tion area, so large areas of solar collectors are required to harvest the energy
(one kilowatt requires about one square meter, on average);
• requires high capital costs to construct the energy collection and storage
systems, offseting the free nature of the energy itself for many years until the
investment is paid off; and
• receives little or no economic (tax) or regulatory credit from govern-
ments in recognition of the low amount of air pollution and greenhouse gas
emissions it causes relative to fossil-fuel usage.
Alternative Fuels: Alcohols, Ethers, and Esters

For environmental and supply reasons, attention is turning to the develop-
ment of cleaner-burning alternatives to hydrocarbon fuels, especially to
power vehicles. Some of these alternatives are, at least in principle, renew-
able in the sense that their production could be sustained indefinitely into
the future without resulting in the accumulation of additional carbon
dioxide. In the material that follows, we discuss the nature and properties
of the major contenders for alternative fuels. In a later section, we take a
longer-range viewpoint and consider hydrogen, the ultimate “fuel of the
future.”
The organic fuels considered here have the inherent advantage over
hydrogen—and even over natural gas—that they are liquids under normal
temperatures and pressures that burn easily in air to produce considerable
heat; like the gasoline and diesel fuels with which they can be blended or
which they can replace, they are energy-dense fuels. Since they all contain
carbon, however, their combustion releases carbon dioxide.
The alternative fuels for vehicles fall into three classes: alcohols,
ethers, and esters. Because they all contain some oxygen, they generally
produce a little less energy per liter than do gasoline and diesel fuel. How-
ever, their oxygen content results in low emissions of many air pollutants.
NOX emissions from these organic liquids are also lower than from pure
gasoline because the flame temperature is lower and thus less thermal NO
(Chapter 3) is formed.
Ethanol as a Fuel
Ethanol, C2H5OH, also called ethyl alcohol or grain alcohol, is a colorless liq-
uid that has been used as an automobile fuel as far back as the late 1800s;
indeed, Henry Ford designed his original cars to run on ethanol.
As a fuel for vehicles, ethanol can be used “neat,” i.e., in pure form, or as
a component in a solution that includes gasoline. Often these fuels are
referred to by the letter E (for ethanol) followed by a subscript that indicates
the percentage of alcohol in the gasoline–ethanol mix. In North America,
the “gasohol” currently sold is about 10% ethanol and 90% gasoline, i.e., E10.
Ethanol and gasoline are freely soluble in each other, so all possible combina-
tions can be produced. Currently in Brazil, E23 is used by all gasoline-powered
vehicles. Pure ethanol, E100, is used mainly in Brazil, where about one-eighth
of car engines have been designed to use it.
One attractive feature of “oxygenated” transportation fuels such as
ethanol is that they result in lower emissions of many pollutants—specifically
carbon monoxide, alkenes, aromatics, and particulates—compared to emis-
sions from combustion of pure gasoline or diesel fuel, particularly from older
vehicles that do not have catalytic converters. In North America, however,
the turnover of vehicle fleets means that very few cars still on the road emit
much CO. The reduction in urban ozone that would result from the lowered
emissions of carbon monoxide and reactive hydrocarbons would be countered
by increases due to the higher amounts of acetaldehyde (Chapter 5) and
vaporized ethanol that would be emitted. This is particularly true for urban
areas in which ozone formation is NOX-limited rather than hydrocarbon-
limited. However, NOX emissions from engines burning ethanol are lower
than from those burning gasoline. Studies in Rio de Janeiro indicate that
the concentration in air of the important pollutant peroxyacetylnitrate, PAN
(see Chapter 5), which is readily formed from the acetaldehyde emissions, has
increased due to the use of ethanol fuel; since Brazilian cars are not equipped
with catalytic converters, this finding is not directly relevant to the North
American situation. However, measurements in Albuquerque, New Mexico,
have established that the use of ethanol as a gasoline additive increased the
concentrations of pollutants such as PAN in the air of that city. It is curious
that some proponents of ethanol as a fuel point to its ability to reduce CO
emissions, which in fact is important only for cars without catalytic convert-
ers, but downplay the effects of acetaldehyde emissions by stating that they
can always be minimized by use of catalytic converters!
One of the difficulties in using pure ethanol (or pure methanol) as a
vehicular fuel is its low vapor pressure: See Figure 8-8, in which the vapor
pressure of gasoline–ethanol mixtures is plotted against its composition,
with pure gasoline at the left side of the horizontal axis and pure ethanol
at the right. Thus, in cold climates, there is very little vaporized fuel avail-
able with which to start a cold automobile engine. However, a blend of
85% ethanol and 15% gasoline has a high

enough vapor pressure (Figure 8-8) to
overcome the cold start problem; in North
Vapor pressure of liquid

America and Europe, E85-fueled vehicles
are now available.
The E10 blend of ethanol in gasoline is
now widely available in North America.
In order to reduce the evaporation of
volatile organic compounds (VOCs) from
gasoline—since they contribute to the
ozone problem—the United States regu-
lates the maximum vapor pressure of gaso-
line sold during the summer months. To 100% gasoline 0% gasoline
0% alcohol 100% alcohol
achieve the lower overall volatility, the Composition of liquid
amount of (highly volatile) butane in gaso-
line is being reduced and replaced by sub-
stances that have low volatility. Unfortunately, as a minor additive, ethanol FIGURE 8-8 Variation
is quite volatile and actually increases the vapor pressure of gasoline. (The in vapor pressure with
same phenomenon occurs for methanol–gasoline blends.) This behavior can composition for typical
alcohol – gasoline mixtures.
be understood by reference to Figure 8-8. As ethanol is added to gasoline, the
vapor pressure of the mixture rises sharply since the C2 compound behaves
in this hydrocarbon environment much like a low-molecular-weight—and
therefore volatile—hydrocarbon. In contrast, as a pure liquid, ethanol has a
lower vapor pressure than gasoline (see Figure 8-8) since the extensive hydro-
gen bonding between ethanol molecules in this situation provides a “glue”
that makes it difficult to break the molecules apart and vaporize them.
Another disadvantage of ethanol (which is even more valid for methanol)
as a fuel is that the energy it produces per liter combusted is somewhat less
than is generated by an equal quantity of gasoline; to travel the same distance,
fuel tanks for alcohols would have to be larger. In principle, about 1.25 gal of
ethanol are needed to generate the same amount of energy as is obtained with
1 gal of gasoline. In practice, however, the efficiency of the combustion is
greater with the alcohols, so the volume penalty is not this large.
Ethanol Production
Industrially, ethanol is made by catalytically adding water to petroleum-based
ethene, CH2 “ CH2, to produce CH3CH2OH. In contrast, ethanol for fuel is
produced on a massive scale by the fermentation of carbohydrates in plants.
Such bioethanol is produced by the yeast-driven fermentation principally of
glucose, C6H12O6. In North America, most carbohydrate used for ethanol
production is derived from the starch in kernels of corn, although some wheat
and other grains are also used. In Brazil and some other semitropical coun-
tries, sucrose from sugarcane is used. A number of developing countries,
including Thailand and China, are producing ethanol from cassava, a woody
shrub that produces a tuberous root high in starch content. In the fermenta-
tion process, the sunlight-derived energy of the glucose becomes more con-
centrated in the ethanol product, since some of the carbon is released as
carbon dioxide gas:
yeast
C6H12O6 9: 2 CO2 2 C2H5OH
P R O B L E M 8-4
By comparing oxidation numbers, show that the carbon atoms in ethanol are
more reduced—and therefore serve as better fuels when oxidized—than
would the carbon atoms in the glucose molecules from which they originated
before fermentation. Show also that there is no net change in oxidation num-
ber of carbon when going from reactants to products in the fermentation
reaction.
P R O B L E M 8-5
Using the enthalpies of formation listed below, calculate the enthalpy change
for the fermentation reaction of glucose into ethanol and carbon dioxide. Is
the process exothermic or endothermic? From your answers, decide whether
the fuel value of the ethanol product is slightly greater or slightly less than
that of the glucose from which it is created.
Hf values in kJ mol1: C6H12O6(s) 1273.2
C2H5OH(l) 277.8
CO2(g) 393.5
As with all biofuels, the attractions of using ethanol to replace some of

the hydrocarbon component in gasoline are that
• the producing country becomes less reliant on imported petroleum;
• air pollution is reduced; and
• the net amount of CO2 emitted into the air is reduced.
Using biofuels such as ethanol is thought to counterbalance much of the
resulting greenhouse gas emissions because the plants absorb the carbon, used
in photosynthesis, that accounts for much of their mass; the atmosphere is
thereby depleted of some of its CO2. The harvested plant biomass is converted
by fermentation into a fuel, which is combusted, and the carbon is released
back into the air as carbon dioxide in the same amount that the plant had
absorbed to grow. The resulting net change to atmospheric CO2 from growing
and then burning the fuel would be zero. Since the process can be repeated the
next season by growing more biomass in the same field, the fuel would be
renewable. In the case of ethanol, the photosynthesis reaction is
6 CO2(g) 6 H2O(g) 9: C6H12O6 6 O2
The reverse of this reaction is the combustion process for glucose.
Unfortunately, a large quantity of water must be used in fermentation
in order to solubilize the starch from which the glucose is obtained; other-
wise, the yeast dies if it is present in concentrated alcohol. Indeed, the greater
the percentage of alcohol in the mixture, the slower the rate of conversion. A
total inhibition of fermentation occurs when the alcohol solution reaches
about 8–11% ethanol by volume (i.e., about one-tenth of the aqueous
solution). For this reason, only dilute solutions of alcohol can be produced by
fermentation. However, a dilute solution of ethanol in water (equivalent in
alcohol content to that in wine) will not burn.
To be used as a vehicular fuel, almost all the water must be removed from
the ethanol solution produced by fermentation. Consequently, the solution is
distilled to separate the alcohol from the water. Distillation is a very energy-
intensive process, since the watery mixture must be constantly kept at a boil.
What ultimately results from repeated distillations is not pure ethanol but a
solution of 95.6% ethanol and 4.4% water (by volume). The last vestiges of
water cannot be removed by more distillation; however, this removal can be
accomplished by a process involving a molecular sieve that also uses heat
energy when the sieve is dried so that it can be reused. Many of Brazil’s vehi-
cles operate on hydrous ethanol, i.e., 95% C2H5OH.
The crux of the controversy about whether or not bioethanol is a renew-
able fuel is that heat generated by burning a large amount of fuel is needed to
distill the ethanol from the water. In the modern production of ethanol from
corn in the United States and Canada, a nonrenewable fuel—either coal or
natural gas—is burned to generate the heat required in the distillation
process. As a result of this combustion, a large amount of carbon dioxide—a
significant fraction of that produced when the alcohol is later burned as a
fuel—is released into the atmosphere at this stage. However, if, as is done in
Brazil, biomass crop residues (called bagasse in the case of sugarcane) rather
than a fossil fuel are used to power the distillation, the carbon dioxide that
they release upon combustion is reabsorbed by growth of such material the
next season, so there is very little net addition of CO2 into the air from this
step. However, the particulate air pollution from the smoke that can accom-
pany biomass combustion restricts its use.
Many scientists and policymakers have attempted to add up the pluses
and minuses of greenhouse gas release and absorption, as well as of energy
production and consumption, in generating ethanol for fuel in North America;
they have compared these findings to the corresponding values for gasoline
in order to determine whether or not ethanol is truly a renewable fuel. Their
conclusions about whether the overall balances for ethanol relative to gaso-
line are positive or negative depend largely on the assumptions they make,
although all agree that the size of the difference is relatively small. The analy-
ses are complicated by the fact that commercial materials such as corn gluten
feed, corn oil, and dried distiller grains, obtained from the nonstarch compo-
nent of the corn kernels, are co-produced with ethanol in the distillation step
of the corn mash. Presumably, some of the fossil-energy usage and greenhouse
gas emissions in the process ought to be associated with the co-products, rather
than assigning it all to the alcohol, since the co-products displace other sub-
stances on the market that would require energy to produce. Most analyses
conclude that modern North American ethanol production from corn
requires about two-thirds the amount of fossil fuel that would be required to
generate the same amount of energy in the form of gasoline produced from
conventional petroleum sources.
We can conclude, then, that the production and use of ethanol derived
from carbohydrate biomass in North America reduces by about one-third the
amount of fossil fuel per se that is required to produce energy for vehicles.
In essence, the energy of ethanol is derived from a combination of two parts
fossil fuel and one part captured solar energy; thus the production of ethanol
from corn in North America is largely the conversion of natural gas or coal
into a convenient vehicular fuel. Ethanol causes about 86% of the green-
house effect enhancement of the gasoline that it displaces. This greenhouse
gas percentage exceeds that for the fossil fuel it consumes in production
mainly because it includes the contribution from the nitrous oxide gas that is
emitted as a by-product when fertilizers are used to grow the corn; another
contributor is the carbon dioxide released when nitrogenous fertilizers are
made synthetically.
Although bioethanol produced from sugarcane has a better energy bal-
ance than that produced from corn, sugarcane requires considerable water to
grow. Although irrigation is not required in the parts of Brazil where it cur-
rently is produced, growing sugarcane in some other countries is placing a
burden on their water resources.
The rapid recent growth in world production of ethanol is illustrated by
the green curve in Figure 8-9. Currently, massive amounts of bioethanol—
over 16 billion liters annually—for use as vehicular fuel are produced from
sugarcane in Brazil; unfortunately, the resulting air and water pollution and
soil erosion are massive. Smaller quantities of ethanol are obtained from cane
in Zimbabwe and from corn and grain in some midwestern American states
and, recently, in Canada. As of 2005, more than 16 billion liters of ethanol
fuel were also being produced annually from the starch of corn and grain in
the midwestern United States; that amount is expected to more than double
by 2009. About 15% of the corn crop in the United States and about half
the sugarcane crop in Brazil were used to produce bioethanol in 2005. Many
farmers in the United States and Canada have provided major political
40 4
30 3
Billions of liters of biodiesel

Billions of liters of ethanol
20 Scale 2
Ethanol
10 1
Scale FIGURE 8-9 Annual

global ethanol (light green
Biodiesel curve) and biodiesel
(dark green curve)
0 production. [Source: Data
1975 1980 1985 1990 1995 2000 2005
from L. R. Brown et al., Vital
Year Signs 2006–2007 (New York:
W.W. Norton, 2007).]
support for the production and use of ethanol in gasoline, in particular for
the government subsidies required to make it economically competitive with
petroleum.
Can ethanol produced from corn ever replace petroleum worldwide? The
growing area required to do this would be about twice the arable land used for
all food crops today, so clearly the answer is “no.” Indeed, in developed coun-
tries, current energy consumption rates exceed the energy generated in food
crops. Thus alcohol from fermentation of corn is unlikely to become a major
fuel replacement for gasoline.
An emerging technology for biomass ethanol production uses cellulose and
hemicellulose components of plants, rather than starch, as the abundant
feedstock from which sugars are produced and fermented. The hope is that such
cellulostic ethanol can be produced in the future in larger amounts and at
cheaper price in terms of energy and dollars than that obtained from starch
sources. The main components in the woody plants being considered for
cellulostic ethanol are cellulose (35–50%), hemicellulose (25–30%), and lignin
(15–30%). Cellulose is a long polymer of the C6 sugar glucose (see Figure 3-11),
approximate formula (CH2O)n, whereas hemicellulose consists of shorter

polymer chains consisting mainly of sugars such as xylose that contain five,
rather than six, carbon atoms. Lignin is an unfermentable component of the
biomass.
In order to be converted into alcohol, the woody biomass must first be
pretreated in order to break the seal of lignin and to disrupt the crystalline cel-
lulose structure, to enable enzymes to reach and react with the cellulose and
hemicellulose within. A number of different pretreatment techniques, some
of them physical and some chemical (such as treatment with steam or dilute
acid, or ammonia), are available, but all those developed to date are relatively
expensive. Once the pretreatment has liberated the cellulose, enzymes are
available to depolymerize it via hydrolysis to glucose, which then is fermented
to ethanol:
biomass 9: (CH2O)n 9: (CH2O)6 9: ethanol

pretreatment cellulose enzyme glucose fermentation
hydrolysis
Until recently, the enzymes used to hydrolyze cellulose were expensive to

produce, but this problem has now been overcome, leaving pretreatment as
the most expensive step in the sequence. Unfortunately, the C5 sugars that
are the chief product of the depolymerization of hemicellulose are not
fermented to ethanol by naturally occurring enzymes, though genetically
engineered yeasts have now been produced that ferment both C5 and
C6 sugars, albeit producing a very dilute (5%) alcohol solution.
The biomass for bioethanol production could, for example, be
switchgrass—a perennial wild grass that was once widespread in the Great
Plains of the United States—grown for this purpose; agricultural residue,
such as the stalks and other nonkernel parts of corn plants; or wood, waste
paper, or municipal solid waste. However, nitrogen fertilization—with its
accompanying nitrous oxide release—would be required to maintain switch-
grass production. Short-rotation hardwood crops—grown on land that is
currently out of production or on marginal cropland—require substantially
fewer fertilizers and pesticides than do corn and switchgrass; together
with waste from other forestry and agricultural operations, these crops can
produce much more biomass per unit area than corn.
A real advantage to the production of cellulose for bioethanol is the
combustion of the mechanically dewatered lignin component of the biomass
to fuel the distillation process. This greatly reduces the amount of fossil fuel
required to about 8%, and the net greenhouse gas emissions to 12%, of those
involved in the energy-equivalent gasoline cycle. Presumably, substantial
fossil-fuel reductions would also be achieved in producing ethanol from corn
itself if the stalks, cobs, etc., rather than coal and/or natural gas, were used to
fuel the distillation.
Methanol
Methanol, CH3OH, is a colorless liquid that, like ethanol, is somewhat less
dense than water. Although methanol was produced in the past from the
destructive distillation of wood, giving rise to its historical name wood alcohol,
it is now produced mainly from a fossil fuel.
Methanol can be blended with gasoline to produce a fuel that burns more
cleanly than gasoline. In a labeling scheme analogous to that used for
ethanol–gasoline mixtures, blends of methanol are designated by an M rating;
thus M5 corresponds to 5% methanol and 95% gasoline.
One disadvantage to methanol blends is that the pure alcohol is only
soluble to the extent of about 15% in gasoline, corresponding to M15; greater
amounts of methanol form a second layer rather than dissolve. The inadver-
tent presence of water causes this unacceptable phase separation to occur at
an even smaller percentage of methanol. Additives such as tertiary-butyl alcohol
(2-methyl-2-propanol) that are soluble in both methanol and gasoline pre-
vent such separations from occurring. Looking at things from the other direc-
tion, gasoline is moderately soluble in methanol, so fuel blends such as M85
have been tested and are now on sale in limited quantities. Another difficulty
is that methanol cannot be used in conventional automobile engines because
it reacts with and corrodes some engine and fuel tank components.
Some concern has been expressed about the safety of methanol for use
as a vehicular fuel, given its toxicity. Methanol–water solutions have been
widely used as windshield washer liquids in northern climates for many years
without much environmental impact. The use of methanol as a fuel may be
more dangerous, as it would involve a very high concentration of the alcohol.
Ethanol is much less toxic than either methanol or gasoline.
However, alcohols also possess some advantages: They are inherently
high-octane fuels, and indeed, methanol is used to power all the cars at the
Indy 500 races. Methanol has the added advantage that it does not produce a
fireball when a tank-rupturing crash of racing cars occurs: It vaporizes less
rapidly than does gasoline, and, once formed, the vapor disperses more
quickly.
P R O B L E M 8-6
Given that the enthalpies of combustion, per mole, of methanol and ethanol
are 726 and 1367 kJ and that the density of each is 0.79 g/mL, calculate
the heat released by methanol and by ethanol (a) per gram and (b) per mil-
liliter. From your results, comment on the superiority of one alcohol or the
other with respect to energy intensity based on weight and volume. Are these
alcohols superior or inferior to methane as fuels in terms of energy intensity
per gram? (See Problem 7-4 for data.) How do they compare to gasoline, for
which about 43 kJ are released per gram?
The conventional conversion of either coal or natural gas into methanol

begins with the reaction of the fossil fuel with steam to produce a mixture of
CO and H2, often called synthesis gas:
C(s) H2O(g) 9: CO(g) H2(g)
CH4(g) H2O(g) 9: CO(g) 3 H2(g)
In the first process, steam is blown over white-hot coal; in the second, methane
gas is combined with steam that has been heated to about 1000°C. These
methods produce synthesis gas from nonrenewable raw materials. An analo-
gous mixture of hydrogen and carbon monoxide can also be obtained by heat-
ing renewable sources of biomass such as wood or the cellulosic component of
garbage. The wood is first chipped and then gasified. The gaseous product is a
mixture of CO, CO2, and H2. The use of wood gasification to generate
methanol or electricity out of biomass is highly promising, for both produce
useful energy without significant greenhouse gas emissions. The various
processes for synthesis gas and methanol production are summarized in
schematic form in Figure 8-10.
Methanol is synthesized from a 2:1 molar ratio of H2 to CO in the pres-
ence of a catalyst:
catalyst (Cu/ZnO)
2 H2 CO CH3OH
Unfortunately, existing catalysts allow only a partial conversion (about one-

fifth) of the gases into methanol for each pass of the gas mixture over the cat-
alyst, and the processes are energy-intensive and require relatively high
temperatures. Research is under way to develop catalysts that will operate at
lower temperatures and thereby allow higher yields.
Fossil fuels Gasoline
H2O
Biomass Synthesis gas Methanol

H2 and CO
FIGURE 8-10 Scheme for

the production of fuels in a Solar H2 H2 and CO2
hydrogen economy.
P R O B L E M 8-7
The enthalpies of formation of CO(g) and CH3OH(l), respectively, are
110.5 and 239.1 kJ/mol. Calculate the enthalpy of the reaction that forms
methanol from synthesis gas. From your answer, predict whether the equilib-
rium amount of methanol obtained will increase or decrease as the temperature
is lowered. Given your result, comment on the interest in developing low-
temperature catalysts.
The correct 2:1 molar ratio of H2 to CO required for the methanol syn-
thesis reaction above is rarely obtained initially from the raw materials. For
example, the reaction of steam with coal instead gives synthesis gas with a
1:1 ratio, and with natural gas a 3:1 ratio is obtained. The ratio can be
adjusted to the required 2:1 by subjecting the mixture to the water-gas shift
reaction, which is an equilibrium that can be written as
catalyst
0!! CO H2O
CO2 H2 !!3
or as its reverse. Since running the reaction in the direction shown consumes
H2 and produces CO, and the opposite result is obtained by running the reac-
tion in reverse, the initial 3:1 or 1:1 ratio of H2 to CO can be altered to 2:1
by the partial conversion of the excess material, whether it is H2 or CO, into
the other, deficient material.
For example, consider the adjustment of the 3:1 ratio produced by the
reaction of methane with steam to the required 2:1 ratio. Call the initial
molar amount of CO produced a; then the initial amount of H2 is 3a. Since
the hydrogen is initially in excess, some of it must be converted to CO; thus
the appropriate direction for the shift reaction is indeed the forward direction
written above. When this reaction achieves equilibrium, a molar amount x
of hydrogen will have been consumed and an additional molar amount x of
carbon monoxide will have been produced:
CO2 H2 9: CO H2O
from initial reaction: 3a a

at new equilibrium: 3a x ax
The value of x is obtained by requiring that the new, equilibrium ratio of H2

to CO be 2:1:
3a - x 2
=
a + x 1
By algebraic manipulation of this equation, the ratio of x to a can be obtained:

x兾a 1兾3
Thus the fraction x兾3a of the initial amount of H2 from the natural gas that
must be converted to CO is 1兾9.
The two chemical reactions that when combined correspond to the con-
version of methane in the correct 2:1 ratio are shown and added together
below; it has been assumed for simplicity that a 1:
CH4 H2O 9: CO 3 H2
1兾3 H2 1兾3 CO2 9: 1兾3 CO 1兾3 H2O
sum CH4 2兾3 H2O 1兾3 CO2 9: 4兾3 CO 8兾3 H2

When combined with a catalyst, the CO and H2 from the sum of these reac-
tions will yield 4兾3 mole of CH3OH, giving the net overall reaction
CH4 2兾3 H2O 1兾3 CO2 9: 4兾3 CH3OH
P R O B L E M 8-8
In order to synthesize a compound with the empirical formula CH3O (and
no other products) starting from methane and steam, what ratio of H2
to CO would be required? What fraction of the hydrogen gas produced
from the reaction of methane and steam would have to be converted to
carbon monoxide using the water-gas shift reaction to accomplish the
transformation?
Research is currently under way to find how to directly convert methane

into methanol in a much more efficient manner than that described above.
Most of the difficulty stems from the fact that methane is a very unreactive
substance: Its C 9H bond dissociation energy is highest of all the alkanes.
Once one C 9H bond is broken, however, the molecule becomes highly
reactive because the other C 9 H bonds are weakened, and in the presence of
oxygen it tends to oxidize completely to carbon dioxide rather than partially to
a useful intermediate stage such as methanol.
Methanol can also be produced by combining carbon dioxide and
hydrogen gases (see Figure 8-10) in the presence of a suitable catalyst:
catalyst
CO2(g) 3 H2(g) CH3OH(l) H2O(l)
Since this reaction is only slightly exothermic, most of the fuel energy of the
hydrogen is present in the methanol product. Based on equilibrium
considerations, methanol formation would be favored by low temperatures

and high pressures; research has centered on finding a catalyst that will
operate efficiently under such conditions without being deactivated. Low
temperatures also prevent the formation of carbon monoxide rather than
methanol.
Some of the massive quantities of CO2 that are released annually into the
atmosphere could be used as reactants in this process. Indeed, methanol pro-
duced in this manner could be considered a renewable fuel provided that the
hydrogen is produced without the consumption of a fossil fuel, e.g., by solar
energy (see below).
Although methanol can be used as a vehicular fuel on its own, there are
chemical reactions by which it can be converted to gasoline. Similarly, synthe-
sis gas itself can be converted to gasoline, thereby allowing the production of this
fuel from either natural gas or coal (Figure 8-10). Currently, neither of these
processes, nor the production of fuel methanol itself, is sufficiently efficient that
it can compete economically with gasoline produced from crude oil.
Ethers
Methanol can be used to produce dimethyl ether, CH3¬O¬CH3, which
has been tested as a replacement for diesel fuel in trucks and buses:
2 CH3OH 9: CH3OCH3 H2O
This ether is nontoxic and degrades easily in the atmosphere—in fact, it is
used as a propellant in spray cans. Since its molecules contain no C¬C
bonds, soot-based particulate matter is produced in its combustion in only
very small quantities (see Chapters 3 and 5) compared to those obtained from
diesel fuel. The NOX emissions from dimethyl ether combustion are also
lower than usually found for diesel engines.
Methanol is also used to produce the oxygenated gasoline additive
MTBE, which stands for methyl tertiary-butyl ether, the structure of which is
illustrated below:
CH3
&
H3C 9 O9 C 9 CH3
&
CH3
methyl tert-butyl ether (MTBE)
MTBE, octane number 116, is used in some North American and European
unleaded gasoline blends—up to 15%—to increase their overall octane num-
ber and to reduce carbon monoxide (and unburned hydrocarbon) air pollu-
tion; the reason is that, like the alcohols, it is an “oxygenated” fuel that
generates less CO during its combustion than would the hydrocarbons it
replaces. The advantages to using MTBE rather than ethanol as an additive

are that it has a higher octane number and does not evaporate as readily.
However, as with alcohols, its combustion can also produce more aldehydes
and other oxygen-containing air pollutants than result from the hydrocar-
bons it replaces.
The usage of MTBE has become controversial. It has an objectionable
odor resembling turpentine and ether. Another problem associated with
MTBE is its contamination of well water, which has now occurred at many
sites in the United States. The sources of MTBE in well water are leaking
underground fuel tanks; leaking pipelines; and spillage of gasoline at gas sta-
tions, in vehicle accidents, and by homeowners. In contrast to the hydro-
carbon components of gasoline, MTBE is rather soluble in water and therefore
is quite mobile in soil and groundwater. It is also quite resistant to biological
degradation because its carbon chains are very short; its half-life is on the
order of years. Various U.S. states and the U.S. EPA have set action levels for
MTBE in drinking water at a few tens of parts per billion, values that are
exceeded in some supplies and at which the odor of the additive is apparent.
Because of concerns about well-water contamination, California and several
other states have now banned the use of MTBE in gasoline, and its use as
a gasoline additive has dropped sharply, having been replaced by ethanol,
isooctane, and other high-octane substances.
Biodiesel
Another biofuel that has found some application, especially in the United
States and Europe, is the mixture of fatty acid methyl esters, R¬COOCH3,
called biodiesel. This material usually corresponds to an oil—usually derived
from a plant source such as soybeans or rapeseed (canola)—that has been
esterified and can be used in diesel engines. The rapid rise in annual global
biodiesel production began in the late 1990s, as illustrated by the dark green
curve in Figure 8-9; note the difference by a factor of 10 in the scales for
bioethanol and biodiesel.
In principle, the raw vegetable oils could be blended with diesel oil—or
even used neat—as a fuel. Indeed, when diesel engines were introduced in
the early twentieth century, they were fueled with pure peanut oil. However,
due to its high viscosity and impurities—such as free fatty acids, water, and
odorous substances—the raw oil cannot be used in modern diesel engines.
Even refined vegetable oil cannot be used as a general fuel, because of its vis-
cosity and because the polymerization of the unsaturated hydrocarbon com-
ponents of the oils that occurs during combustion produces gums that result
in carbon deposits and thickening of lubricating oil in the engine. One solu-
tion to the viscosity problem, employed by so-called Grease cars that are
fueled with grease from deep-frying, is to heat the oil onboard the vehicle.
More commonly, the virgin vegetable oils are transformed into a less
viscous, less corrosive liquid that is used as the fuel. The main component in
the original oil is triglycerides, which are triesters of various fatty acids with
glycerin, CH2OH¬CHOH¬CH2OH. The transformation converts each
triglyceride molecule into three methyl esters of long-chain fatty acid mole-
cules, which then constitute the fuel, and a molecule of glycerin (also called
glycerol), which is removed from the mixture of fatty acids and sold separately
for other uses. To accomplish the transformation, the triglyceride is reacted
using base or acid catalysis with methanol obtained from natural gas, as
described in detail in the green chemistry section that follows. The use of
methanol, most commercial supplies of which involve its synthesis from
natural gas, makes biodiesel less than 100% renewable, though the great
majority of the carbon atoms in the fuel esters—and hence in its fuel value—
originate with the vegetable oil.
Overall, soybean-derived biodiesel generates over 90% more energy
than is used to produce it, compared to about 25% for corn-based ethanol.
Biodiesel blends produce less carbon monoxide, particulate matter (PM10),
and sulfur dioxide emissions when combusted than does the 100% diesel
fuel that they replace; the reduction in soot and CO arises because it is an
oxygen-containing fuel. There is controversy as to whether biodiesel blends
produce more or less NOX than does pure diesel. Although energy and
fossil-fuel-derived methanol are used in its production, and nitrous oxide
emissions are associated with fertilizers to grow the plants, biodiesel pro-
duced from soybeans on existing agricultural land overall reduces the CO2
equivalent emissions by about 40%. The much greater decrease in CO2
from biodiesel, compared to corn-based ethanol, is due primarily to the
much lower amount of energy required: Soybeans create oil that can be
obtained readily from seed by physical methods, whereas ethanol requires
fuel-intensive distillation. Soybean production also uses much less fertilizer
and releases much less nitrogen, phosphorus, and harmful pesticides into
the environment than does corn production for ethanol. Of course, the two
biofuels are used in different types of vehicles, so a comparison between
them is of limited significance.
The fraction of biodiesel in diesel fuel is designated by a system analogous
to that used for alcohols in gasoline. Thus B5 symbolizes diesel fuel contain-
ing 5% biodiesel by volume, and B100 is pure biodiesel. In the past, the most
common blend was B20—indeed, the U.S. Navy, the largest single user of
biodiesel in the world, uses that blend in all nontactical vehicles—but more
dilute blends such as B2 and B5 are becoming popular. Currently, the largest
manufacturer of biodiesel is Germany, which produced more in 2005 than
the rest of the world combined. The European Union has mandated that all
fuels contain 5.75% biofuels by 2010, which will mean a tripling of their con-
sumption there compared to 2005 levels.
Almost all the biodiesel produced in the United States uses domestic
soybeans (which are about 20% oil) as its raw material. The oil yield, about
40%, is even higher for rapeseed (canola). In tropical areas, massive planta-
tions of palm trees are being planted to produce palm oil for biodiesel, since
the yield of oil per square kilometer greatly exceeds that from soybean or
rapeseed crops. Unfortunately, in the rush to produce more palm oil destined
to become biodiesel in Europe, huge areas of tropical rain forest in Malaysia,
Brazil, and Borneo and peatland in Indonesia have been burned and cleared
and thereby destroyed; the result is large amounts of greenhouse gas emis-
sions, totaling one-twelfth of all global CO2 in the case of Indonesia. The
advantage of biofuels in producing lower greenhouse gases than conventional
gasoline or diesel will be overcome by these emissions for many years.
Anther concern about biofuels is the effect they have on the price of
food. In 2007, the Food and Agriculture Organization of the United Nations
noted that the rapidly increasing demand for biofuels is transforming agricul-
ture worldwide and contributing to the increase in food prices. The inflation
in prices applies not only to the corn, sugar, and vegetable oil sources but also
indirectly to prices for the livestock that are usually fed these crops.
In the future, species of algae that contain as much as 50% oil may be
grown as raw material from which biodiesel fuel would be obtained, since the
yield per square kilometer could greatly exceed that of even tropical palm oil.
However, the practical mass production of single-species algae has not yet
been achieved.
Green Chemistry: Valuable Chemical Feedstocks

from Glycerin, a Waste By-Product in the Production
of Biodiesel
As mentioned above, biodiesel is produced from a transesterification reaction
of the triglycerides that make up animal fats and vegetable oils (Figure 8-11).
This reaction not only produces the methyl esters of the fatty acids, which
comprise biodiesel, but also yields glycerin as a by-product. For every 9 L of
biodiesel produced, about 1 L of glycerin is formed. The market for the glyc-
erin by-product has not kept pace with biodiesel production; consequently,
there is now a glut of glycerin on the market. Chemists and engineers have
been searching for new uses for glycerin and for processes to convert glycerin
to other valuable and useful chemicals.
Professor Galen Suppes and his group at the University of Missouri won
a 2006 Presidential Green Chemistry Challenge Award for their discovery of
a process to convert glycerin to propylene glycol and acetol (Figure 8-12).
Although other methods exist for the conversion of glycerin to propylene
glycol, they require high temperatures (200–400°C) and high pressures
(1450–4700 psi). As a result of the stringent reaction conditions, these other
CH29O R CH29OH
O
CH3OH, CH3O –
HC 99 O R' HC9OH
O
CH29O R" CH29OH

triglyceride glycerin
(oils and fats)
O O O
H3C H3C H 3C
+ O R + O R' + O R"
biodiesel FIGURE 8-11 Preparation
(fatty acid methyl ester) of biodiesel.
methods require specialized costly equipment that prohibits their commer-

cialization. These methods also suffered from poor yields and low selectivity.
In the Suppes synthesis (Figure 8-12), propylene glycol is formed by reac-
tion of glycerin with hydrogen in the presence of copper chromite catalyst. The
advantage of this synthesis is that it takes place at relatively low temperatures
and pressures, with high yields and high selectivity, making it commercially
feasible. Since the present commercial synthesis of propylene glycol is from
petroleum-based feedstocks, the Suppes synthesis offers a way to reduce our
dependence on fossil fuels by producing propylene glycol from biomass (waste
glycerin from biodiesel production). Propylene glycol has a relatively large
market, over a billion kilograms per year; finding a commercially viable use
for the glycerin by-product of biodiesel production will help lower the cost of
biodiesel and in turn encourage its production and use.
OH OH OH copper chromite
OH OH
H−H, 200°C, 200 psi
H2C99CH9CH2 H2C99CH9CH3
glycerin propylene FIGURE 8-12 Preparation
glycol of propylene glycol and
acetol from glycerin. In the
OH O absence of H2, acetol can
be isolated as the major
H2C99C9CH3 product by distillation as it
acetol is formed.
Propylene glycol has many desirable properties, including its low toxicity,
which allow it to be used in a number of different products. Propylene glycol
is the only glycol approved by the U.S. Food and Drug Administration for
use in products meant for human consumption. It can be found in alcoholic
beverages, confections and frostings, ice cream, nuts and nut products, and
seasoning and flavorings. This compound may also be present in cosmetics,
pharmaceuticals, pet food, tobacco, paints, detergents, fragrances, resins, and
antifreeze. Propylene glycol’s many functions include preservative, moistur-
izer, wetting agent, coolant, and solvent. Currently, the bulk of automobile
antifreeze is composed of ethylene glycol, which is acutely toxic. The eco-
nomical production of large quantities of propylene glycol from the glycerin
waste product of biodiesel production offers the potential to replace ethylene
glycol in antifreeze with a significantly less toxic substance.
The Suppes group also discovered that glycerin could be reacted with
copper chromite in the absence of hydrogen to produce acetol (Figure 8-12).
They believe that this discovery could be even more important than the for-
mation of propylene glycol, since acetol can act as precursor to many other
organic compounds. Thus these other organic compounds could ultimately
be formed from biomass rather than the petroleum-based precursors from
which they are presently made. This would not only decrease the dependence
on crude oil but would also lower the price of biodiesel by making the glyc-
erin by-product more valuable.
Hydrogen—Fuel of the Future?

Hydrogen gas can be used as a fuel in the same way as carbon-containing
compounds; some futurists believe that the world will eventually have a
hydrogen-based economy. Hydrogen gas combines with oxygen gas to pro-
duce water, and in the process it releases a substantial quantity of energy:
spark
H2(g) 1/2 O2(g) H2O(g) H 242 kJ/mol
The idea that hydrogen would be the ultimate fuel of the future goes back
at least as far as 1874, when it was mentioned by a character in the novel
Mysterious Island by Jules Verne. Indeed, hydrogen has already found use as
fuel in applications for which lightness is an important factor, namely, in
powering the Saturn rockets to the moon and the U.S. space shuttles.
Hydrogen is superior even to electricity in some ways, since its transmis-
sion by pipelines over long distances consumes less energy than the transmis-
sion through wires of the same amount of energy as electricity and since
batteries are not required for local storage of energy.
However, as we shall see in the material that follows, the substantial
technical problems in the production, storage, transportation, and usage of
hydrogen—the need to create a new infrastructure for it—mean that a hydro-
gen economy is probably still many decades away.
Combusting Hydrogen
Hydrogen gas can be combined with oxygen to produce heat by conventional
flame combustion or by low-temperature combustion in catalytic heaters. The
combustion efficiency, i.e., the fraction of energy converted to useful energy
rather than to waste heat, is approximately 25%, about the same as for gaso-
line. The main advantages to using hydrogen as a combustion fuel are its low
mass per unit of energy produced and the smaller (but not zero) quantity of
polluting gases its combustion produces, when compared to other fuels. BMW,
Ford, and Mazda may begin marketing hydrogen-fueled combustion-engine
cars by 2010.
Although it is sometimes stated that hydrogen combustion produces only
water vapor and no pollutants, this in fact is not true. Of course, no carbon-
containing pollutants, including carbon dioxide, are emitted. Since combustion
involves a flame, however, some of the nitrogen from the air that is used as the
source of oxygen reacts to form nitrogen oxides, NOX . Some hydrogen peroxide,
H2O2 , is released as well. Thus hydrogen-burning vehicles are not really zero-
emission systems. It is true that the lower flame temperature for the H2 O2
combustion, compared to that for fossil fuels with oxygen, inherently produces
less NOX , perhaps two-thirds less. The nitrogen oxide release can be eliminated
by using pure oxygen rather than air to burn the hydrogen; alternatively, it can
be reduced even further by passing the emission gases over a catalytic converter
or by lowering the flame temperature as much as possible, e.g., by reducing the
H2/O2 ratio to half the stoichiometric amount.
Generating Electricity by Powering

Fuel Cells with Hydrogen
Hydrogen and oxygen can be combined in fuel cells in order to produce
electricity (a hydrogen technology also used in space vehicles). Fuel cells are
similar in operation to batteries except that the reactants are supplied contin-
uously. In the hydrogen–oxygen fuel cell, the two gases are passed over sepa-
rate electrodes that are connected by an external electrical connection
through which electrons travel and also by an electrolyte through which ions
travel.
The components of a fuel cell, then, are the same as those of an elec-
trolysis operation in which water would be split into hydrogen and oxygen, but
the chemical reaction that occurs is exactly the opposite. Instead of electri-
city being used to drive the electrolysis reaction, it is produced. Fuel cells have
the advantage over combustion since a more useful form of energy is produced
(electricity rather than heat) and the process produces no polluting gases as
by-products. In principle, the only product of the reaction is water. At the
catalytic surface of the first electrode, the H2 gas produces H ions and
electrons, which travel around the external circuit to the second electrode,
across which O2 gas is bubbled (see Figure 8-13). Meanwhile, the H ions
travel through the electrolyte and recom-

Electrodes bine with the electrons and O2 to produce
water at the electrode. Although some of
the reaction energy is necessarily released
as heat—about 20%, due to requirements
(Electrolyte)
of the second law of thermodynamics—
H2O
vapor
most of it is converted to electrical energy
Recycle associated with the current that flows
unreacted out
H2 between the electrodes. Electric motors,
H+ whether in a fuel-cell or battery vehicle,
are 80 – 85% efficient in converting elec-
Proton exchange
trical to mechanical energy. Real fuel cells

overall are now about 50 – 55% efficient;
membrane
H2 O2 70% efficiency may be attained eventually.

fuel By contrast, internal combustion engines
– +
using gasoline are 15 – 25% efficient,
e– diesels 30 – 35%.
Many auto manufacturers are currently
Load pursuing the development of electric cars
H2 2 H+ 4 H+ + O2 + 4 e–
that use fuel cells. Prototype buses running
+2 e– 2 H2O in Vancouver and Chicago use innovative
fuel cells for their power source. The
electrolyte used in the fuel cells of these
FIGURE 8-13 Schematic vehicles is a hair-thin (about 100 ␮m)
diagram of a hydrogen – synthetic polymer that acts as a proton exchange membrane. The membrane,
oxygen fuel cell (PEMFC when moist, conducts protons well since it incorporates sulfonate groups.
version). It also keeps the hydrogen and oxygen gases from mixing. The electrodes
of such polymeric-electrolyte-membrane fuel cells, labeled PEMFC in
Figure 8-14, are graphite with a small amount of platinum dispersed as
nanoparticles in thin layers (about 50 ␮m thick) on its surface. Each cell,
which operates at about 80°C, generates about 0.8 V of electricity, so many
must be stacked together in order to provide sufficient power for the vehicle.
In the current versions of the buses, compressed hydrogen is stored in tanks
under the roof of the bus.
Some incentives to develop vehicles that use fuel cells powered by
hydrogen are
• to reduce urban smog, which is partially produced from emissions from
gasoline and diesel engines;
• to reduce energy consumption, since fuel cells are much more efficient in
producing motive power than are combustion engines; and
• to reduce carbon dioxide emissions, since fuel cells powered by hydrogen
are carbon-free.
Some analysts point out that the cost of

Anode Electrolyte Cathode
improving air quality and CO2 emissions
by switching the transportation system to
such vehicles over the next few decades is
much higher than alternative strategies, H2O SOFC (500–1,000˚C)
O2 (air)
such as scrapping old cars, improving vehi- CO2 O2–
Internal
cle fuel efficiency, reducing NOX emissions re-forming
from power plants, and capturing and H2, CO O2 (air)
H2O MCFC (650˚C)
sequestering CO2 emissions from power CO2 CO32–
plants. In addition, hydrogen leaked into CO2
the air acts indirectly as a greenhouse gas,
since it reacts with and decreases the con- External H2O
PAFC (200˚C)
re-forming O2 (air)
centration of OH; this result will slightly H2, CO2 H+
increase the atmospheric lifetime of
methane and hence its concentration, External
since the main sink for CH4 is its reaction PEMFC (80˚C) H2O
re-forming O2 (air)
H+
with OH, as discussed in Chapters 5 and 6. H2, CO2
(CO
removal)
H2O AFC (70˚C)
Obtaining Fuel-Cell Hydrogen H2
OH–
O2 (air)
from Liquid Fuels (CO2
removal)
Because of the limited practicality of
transporting hydrogen in individual cars
and trucks, there is active research in designing systems that allow it to be FIGURE 8-14 Operating
characteristics of various
extracted as needed from liquid fuels, which are much more convenient to fuel cells. [Source: B. C. H.
transport. For example, in the near future, the hydrogen may instead be Steele and A. Heinzel,
obtained as needed from liquid methanol by onboard decomposition of the “Materials for Fuel Cell Tech-
latter to hydrogen gas using the reverse of the methanol-formation reaction nologies,” Nature 414 (2001):
345.]
discussed earlier:
CH3OH 9: 2 H2 CO
In the General Motors version of this process, the re-former unit operates at
275°C and uses a copper oxide/zinc oxide catalyst to promote the reaction.
The water-gas shift reaction is subsequently used to react the CO in the
synthesis gas with steam and provide additional H2 gas, giving the overall
reaction
CH3OH H2O 9: 3 H2 CO2
Similar processes have been developed that convert gasoline, diesel fuel,
octane, or aqueous ethanol into carbon dioxide and hydrogen. Unfortunately,
the current PEMFC and alkaline fuel cells (see Problem 8-9), as well as one based
on phosphoric acid, all require relatively pure hydrogen, free especially of carbon
monoxide—a gas that is formed in the re-former process and is difficult to eliminate
completely. Carbon monoxide bonds to the sites of the catalyst (e.g., platinum)
intended to promote the fuel-cell reaction and blocks the catalytic activity there.
Concentrations of CO greater than 20 ppm in the hydrogen gas slow down most
fuel cells appreciably. Perhaps a CO-tolerant electrode catalyst, possibly one
incorporating a second metal or a metal oxide as well as platinum, will be devel-
oped in the future to overcome this problem by oxidizing the adsorbed CO to
carbon dioxide. Hydrogen that is virtually free of carbon monoxide could be pro-
duced from methanol by an oxidative steam re-forming process at 230°C:
4 CH3OH O2 2 H2O 9: 10 H2 4 CO2
Since oxygen is involved, however, not all the fuel value of methanol is
captured in the hydrogen product.
P R O B L E M 8-9
An alkaline electrolyte can be used in the H2 – O2 fuel cell to replace the acidic
environment mentioned previously (see Figure 8-13). Assuming that the reaction
of O2 with water and electrons produces hydroxide ions, OH, and that these ions
travel to the other electrode, where they react with hydrogen to give up electrons
and produce more water, deduce the two balanced half-reactions and the balanced
overall reaction for such a fuel cell. (The alkaline fuel cell, labeled AFC in Figure 8-14,
is used in space shuttles and Apollo spacecraft to provide electricity.)
Fuel cells may also be used in the near future in small electric power plants,
partly because pollutant emissions from them are so small compared to those from
fossil-fuel combustion (e.g., only about 1% of the NOX). Indeed, phosphoric
acid–based fuel cells (PAFC in Figure 8-14) have been operating since the early
1990s in some hospitals and hotels to generate power. The most promising fuel
cells for power plants involve a molten carbonate salt—e.g., potassium and
lithium carbonates, plus additives, at 650°C—as the electrolyte. (The molten-
carbonate fuel cell is labeled MCFC in Figure 8-14.) The hydrogen gas reacts with
carbonate ions, CO32, to produce carbon dioxide, water, and electrons at the
anode, while the carbon dioxide reacts with electrons and oxygen from air to
re-form the carbonate ions at the cathode. The carbon dioxide must be recycled
from the anode back to the cathode during the cell’s operation. The hydrogen is
produced on-site by reaction of methane with steam, so CH4 is the actual source
of the fuel energy here. By-product waste heat can be recovered and used in a
cogeneration mode, and the dc electricity produced by the fuel cell is converted
to ac for distribution. MCFC efficiency approaches 50%.
Like the molten-carbonate fuel cell, a cell based on solid oxides (see
SOFC, Figure 8-14) is much more tolerant of carbon monoxide impurities in
the fuel hydrogen gas than are the other fuel cells. The electrolyte in the
solid-oxide fuel cell is a ceramic mixture of oxides of zirconium and yttrium.
The oxide anion, O2, produced from oxygen gas carries the charge between
the electrodes, travels through the solid from cathode to anode as the fuel is
consumed, and forms water at the anode. The high operating temperature
(up to 1000°C) of the solid-oxide cell allows fuel to be re-formed internally
and to form hydrogen ions without the use of expensive catalysts, so methane
or other hydrocarbons can be used as the fuel instead of hydrogen. However,
carbon deposits tend to form at the anode and stick to it at the high operat-
ing temperatures that are involved with these units.
The solid-oxide fuel cell, like the molten-carbonate one, is practical for
central power plants, and its fuel efficiency is also high. Both types suffer from
practical problems with electrodes, such as carbon deposition. The latter
problem for solid-oxide fuel cells can be overcome by operating at a lower
temperature.
P R O B L E M 8-10
For the molten-carbonate fuel cell, obtain balanced half-reactions for the
processes at the two electrodes and add them together to determine the over-
all reaction.
Electric Cars Powered by Batteries

An alternative to vehicles that use fuel cells are those powered by batteries.
Some electric cars have already been produced, and most use a number of the
same sort of lead-acid batteries that gasoline-powered vehicles have tradi-
tionally employed singly to operate the starter motor. In the future, electric
cars will probably use nickel-cadmium, nickel-metal hydride, and lithium-
based batteries. The practical difficulties that discourage widespread adoption
of such vehicles are their high cost, the low driving range between battery
charges, the length of the battery recharge period, and the weight of the bat-
teries. Like fuel-cell systems, they have the attraction of zero emissions dur-
ing operation, little operating noise, and low maintenance costs. Of course,
pollution is emitted into the environment when the electricity required for
these cars is generated in the first place. Some researchers have predicted that
lead pollution stemming from the manufacture, handling, disposal, and recy-
cling of lead-acid batteries would raise lead emissions into the environment
by an amount that would exceed the levels that were associated with leaded
gasoline. Critics of this analysis have pointed out that the data used are
flawed and that not all the lead lost in the processing steps will be emitted
into the environment rather than disposed of properly.
Even electric vehicles are not really pollution-free if a fossil fuel is burned
to generate the electricity to charge the battery, since the fossil fuel’s combus-
tion in any power plant yields NOX that is released into the atmosphere.
The turn of the century saw the introduction of hybrid combustion/
electric powered vehicles, such as the Toyota Prius, into the market. Such
vehicles overcome the requirement of long and frequent recharging of

all-battery systems, since the battery is recharged continuously when the
(small) gasoline engine is in operation and is producing excess power.
During braking, recovered kinetic energy is channeled back to the battery.
Motive power for the vehicle is supplied by both the gasoline and electric
motors, the proportion depending on the driving situation. Hybrid vehicles
are highly fuel efficient, so they emit much less carbon dioxide and much less
nitrogen oxides, carbon monoxide, and VOCs than conventional vehicles.
The batteries involved are nickel-metal hydride, which are lighter and more
compact than lead batteries of equivalent potential.
Other Uses for Fuel Cells

The first wave of consumer products powered by fuel cells will likely be on the
market in the next year or two. Laptop computers will be powered by fuel cells
rather than rechargeable batteries. These fuel cells will use methanol rather than
hydrogen directly as fuel and will contain removable cartridges containing the
alcohol. The advantage for the user of fuel cells over battery power is a much
longer working time before the power runs out. Using methanol or natural gas
rather than H2 directly as the fuel in fuel cells does avoid the problem of the gen-
eration and storage of hydrogen. One problem with methanol is the generation
of by-product carbon monoxide, which poisons the catalyst, as discussed previ-
ously. Diluting the methanol with water lessens this problem but cuts the power
output of the cell. In addition, neither methanol nor any other liquid fuel that
could in principle be used directly instead of H2 in a fuel cell reacts fast enough
to produce the required electrical current in a vehicle, although recent research
on the use of dilute solutions of methanol indicates that these problems may be
overcome eventually.
Storing Hydrogen
In rocketry applications, hydrogen is stored as a liquid, as is oxygen. Since
hydrogen’s boiling point of only 20 K (253°C) at 1 atm pressure is so low, a
large amount of energy must be expended in keeping it very cold, in addition
to the energy used to liquefy it. This drawback effectively limits the applica-
tions of liquid hydrogen to a few specialized situations in which its lightness
(low density) is the most important factor.
Hydrogen could be stored as a compressed gas, in much the same way as
is done for methane in the form of natural gas. However, compared to CH4,
hydrogen has a drawback: A much greater amount of H2 gas needs to be
stored in order to release the same amount of energy. Compared with
methane, the combustion of one mole of hydrogen consumes only one-
quarter of the oxygen and consequently generates about one-quarter of the
energy, even though both occupy equal volumes under the same pressure
(ideal gas law). Thus the “bulky” nature of hydrogen gas limits its applica-
tions (see Problem 8-13).
It is instructive to compare the volumes of hydrogen under different con-
ditions required to fuel a hydrogen-fuel-cell car (assuming 50% efficiency) to
travel 400 km (240 miles), approximately the distance one can obtain in an
efficient gasoline-powered car with a tank capacity of 40 – 50 L. The amount
of hydrogen required is 4 kg, which occupies
• 45,000 L, or 45 m3—e.g., a balloon having a 5-m diameter or a cube
3.6 m on each side, if it exists as a gas at normal atmospheric pressure; or
• 225 L (about 60 gal, equal to about five normal-sized gasoline tanks) as a
gas compressed to about 200 atm (routinely achievable); or
• 56 L as a liquid (or solid) maintained at 252°C (at 1 atm pressure); or
• 35 – 75 L if stored as a metal hydride, if effective systems can be devel-
oped, as discussed below.
A practical and safe way to store hydrogen for use in small vehicles may
be in the form of a metal hydride. Many metals, including alloys, absorb large
amounts of hydrogen gas reversibly—as a sponge absorbs water. The molecu-
lar form of hydrogen becomes dissociated into atoms at the surface of the
metal as it is absorbed and forms metal hydrides by incorporating the small
atoms of hydrogen in “holes” in the crystalline structure of the metal. Thus
the hydrogen exists as atoms, not molecules, within the lattice, which
expands slightly to incorporate them. For example, titanium metal absorbs
hydrogen to form the hydride of formula TiH2, a compound in which the den-
sity of hydrogen is twice that of liquid H2! Heating the solid gradually releases
the hydrogen as a molecular gas, which then can be burned in air or oxygen
to power the vehicle.
Research continues to find a light metal alloy that can efficiently store
hydrogen without making the vehicle excessively heavy. Even existing metal
hydride systems are lighter than the pressurized tanks needed to store liquid
hydrogen. Most industrial research now centers on metal systems. Practical
considerations require that an alloy to store hydrogen
• be capable of quickly and reversibly absorbing hydrogen,
• not become brittle after many repeated cycles of absorption and desorption,
• operate in the pressure and temperature ranges of 1 – 10 atm and 0 – 100°C,
• not be so dense that it weighs down the vehicle excessively (a concentra-
tion of hydrogen of at least 6.5 mass % is the U.S. Department of Energy tar-
get), and
• not require a huge volume (at least 62 kg H/m3, equivalent to 4 kg in
65 L, is the target).
Lanthanum–nickel alloys derived from LaNi5 have all the above charac-
teristics except one: They are too heavy (mass % 2), a deficiency shared
by all known metal hydrides that operate near ambient temperature. Many
lighter hydrides and alloys, such as MgH2 and Mg2NiH4, are known, but they
do not operate reversibly under moderate conditions. Research on systems
formed by the lighter metals continues but has not yet been successful in pro-
ducing alloys that fulfil all five conditions listed.
One of the practical difficulties in using hydrogen as a fuel is its tendency
to react over time with the metal in pipelines or storage containers in which
it is used. This reaction embrittles the metal, eventually deteriorating it to
form a powder. Recent progress has been made in overcoming this difficulty
by using composite materials rather than simple metals as the structural mate-
rials for storage and transport facilities.
Some research in the past reported that tiny fibers made of graphite, a
light material, can store up to three times their weight in hydrogen
between the graphite layers and would be a safe, lightweight storage mech-
anism for hydrogen. However, research in the late 1990s involving exten-
sive hydrogen storage in carbon nanotubes has not proven to be
reproducible. One of the difficulties is the very tiny (milligram) samples of
carbon nanotubes that are available for experimentation. Some
researchers believe that, if the nanotubes are broken so that they have an
open end, hydrogen can enter the tube. Other experiments indicate that
only a single layer of H2 gas conventionally adsorbed to the outside of the
tubes is actually stored, a concentration too small (2% by mass) to be
useful.
Overall, the problem of devising a practical, economical, and safe way of
storing hydrogen has not yet been achieved, and in the eyes of some analysts,
“no breakthrough is yet in sight,” despite much interest and research activity.
It may be that the weight requirements associated with all practical methods
of storing hydrogen will limit its use to large vehicles such as buses and air-
planes.
As mentioned in the discussion of fuel cells, in some applications it may
be more feasible to transport and store hydrogen in the form of an energy-
dense liquid such as methanol and to use it as required for power generation.
Toluene, C7H8, has also been proposed as a long-distance hydrogen carrier; it
could then be dehydrogenated when the hydrogen is required.
Another way to temporarily store hydrogen is by means of the alkali salt
(lithium or sodium) of the borohydride ion, BH4. For their prototype mini-
van that runs on fuel cells, Chrysler uses a 20% solution of sodium borohy-
dride in water to store hydrogen, which is released when the solution is
pumped over a ruthenium catalyst, prompting the redox reaction of the H
in borohydride with the H in water to produce H2:
BH4 3 H2O 9: 4 H2 H2BO3

200
Diesel
Volumetric density (kg/m3)
100 Gasoline
80 DOE target
Low-temperature
60 metal hydrides Chemical
storage
40
(NaBH4)
Liquid hydrogen
20 High-temperature metal hydrides FIGURE 8-15 The

performance of various
hydrogen storage
10 Compressed hydrogen techniques. Note that both
8 horizontal and vertical
6 scales are logarithmic.
1.0 2 4 6 8 10 20
[Source: R. F. Service, “The
Gravimetric density (% weight H2) Hydrogen Backlash,” Science
305 (2004): 958–961.]
The density of hydrogen in the borohydride solution is comparable to

that in liquid hydrogen. The analogous alanate ion, AlH4, in the form of
its sodium salt is also a candidate for hydrogen storage in vehicular fuel
cells:
2 NaAlH4 9: 2 NaH 2 Al 3 H2
Several molecular boron compounds, including BH3NH3 and an

organoboron–phosphorus system, have recently been proposed as hydrogen
carriers.
The performance of metal systems for storing hydrogen is compared to
that of the compressed and liquefied element and that of gasoline and diesel
fuel in Figure 8-15. No practical system discovered to date has reached the
target of the U.S. Department of Energy (Figure 8-15) in terms of combining
high density with a high percentage of hydrogen in its mass (“gravimetric
density” of at least 6%).
The possibility of storing hydrogen in clathrates in water—much like
methane in water clathrates (Chapter 6)—may be feasible. Although hydro-
gen molecules are too small to be efficiently trapped at low pressures, it has
been discovered recently that two or four H2 molecules can be stored in each
ice clathrate at room temperature at enormous pressures, about 2000 atm.
Once formed, though, the clathrate can be stored at liquid nitrogen temper-
atures at reduced pressure.
P R O B L E M 8-11
Calculate the mass of titanium metal required to absorb each kilogram of
hydrogen and form TiH2 in a “tankful” of hydrogen. Repeat the calculation
for magnesium if the hydride has the formula MgH2. Which metal is superior
for storage of hydrogen from a weight standpoint?
P R O B L E M 8-12
Assuming that the energy released by combustion of H2 is proportional to the
amount of oxygen it consumes, estimate the ratio of heat released by one
mole of methane compared to one mole of hydrogen gas.
P R O B L E M 8-13
Using the thermochemical information in the H2 combustion equation, cal-
culate the enthalpy (heat) of combustion of hydrogen per gram, and by com-
paring it to that of methane (see Problem 7-4), decide which fuel is superior
on a weight basis. By comparing the actual energy released by combustion per
mole of gas—and hence per molar volume—decide which fuel is superior on
a volume basis.
Producing Hydrogen
It is important to realize that hydrogen is not an energy source, since it does
not occur as the free element in the Earth’s crust. Hydrogen gas is an energy
vector, or carrier, only; it must be produced, usually from water and/or
methane, with the consumption of large amounts of energy and/or other fuels.
The industrial infrastructure that would be required to produce enough hydro-
gen to fuel all the vehicles in the United States is enormous, since it would
require about as much energy as the current electric power capacity.
The most expensive commercial way to produce hydrogen is by electrolysis
of water, using electricity generated by some energy source:
electricity
2 H2O(l) 2 H2(g) O2(g)
Unfortunately, about half the electrical energy is inadvertently converted to
heat and therefore wasted in this process.
A hope for the future is that wind power or solar energy from photo-
voltaic collectors will become economically efficient in providing electricity
to generate hydrogen. Currently, there are prototype plants in Saudi Arabia
and Germany that use electricity from solar energy to produce hydrogen, a
process about 7% efficient. The stored energy is later recovered by reacting
the hydrogen with oxygen. Excess electricity from hydroelectric or nuclear
power or wind-power installations—i.e., power generated but not required

immediately for use—could be used to produce hydrogen by electrolysis
of water.
Even better than the use of solar electricity to electrolyze water would be
the direct decomposition of water into hydrogen and oxygen by absorbed
sunlight, but no practical, efficient method has yet been devised to effect this
transformation. One of the difficulties in using sunlight to decompose water
is that H2O does not absorb light in the visible or UV-A regions; thus some
substance must be found that can absorb sunlight, transfer the energy to the
decomposition process, and finally be regenerated. The substances proposed to
date for this purpose are very inefficient in converting sunlight into energy. In
addition, since the light-absorbing substances and others required are not 100%
recoverable at the end of the cycle, they must be continuously resupplied—thus
the hydrogen that is produced is not really a renewable fuel.
One catalyst that has been found to convert sunlight into hydrogen by
electrolyzing water is titanium dioxide, TiO2. A small potential is applied to
the electrode in the cell’s operation. Titanium dioxide is stable to sunlight
(unlike many other potential light-absorbing materials) and cheap, but pure
TiO2 absorbs only ultraviolet light. By blending carbon into TiO2 so that C
replaces some of the oxide ions, the efficiency in producing hydrogen gas is
increased eightfold, to more than 8% of the Sun’s energy, because the addi-
tion of carbon extends absorption into the visible region (to 535 nm).
P R O B L E M 8-14
Determine the longest wavelength of light that has photons capable of
decomposing liquid water into H2 and O2 gases, given that for this process
H 285.8 kJ/mol of water. In which region of the spectrum does this
wavelength lie? [Hint: Recall from Chapter 1 the relationship between reaction
enthalpy and light wavelength.]
In principle, the thermal conversion of sunlight into heat can produce

temperatures hot enough to decompose water into hydrogen and oxygen.
Research in Israel, using a solar tower of mirrors to concentrate sunlight by a
factor of 10,000 and thereby produce temperatures of about 2200°C in a
reactor, has succeeded in splitting about one-quarter of water vapor at low
pressures into H2 and O2.
Various thermochemical cycles by which water can indirectly be
decomposed by heat into hydrogen and oxygen have been proposed. Ideally,
such cycles should operate at moderate temperatures, be efficient in conver-
sion of heat into hydrogen, and not degrade the reactants so they can be
recycled. Perhaps the most practical is the sulfur–iodine cycle, in which
elemental iodine is first reduced by sulfur dioxide to hydrogen iodide and

sulfuric acid:
I2 SO2 2 H2O 9: 2 HI H2SO4 (at 120°C)
The hydrogen iodide is then thermally decomposed into hydrogen gas, recov-
ering the elemental iodine, and the sulfuric acid is thermally decomposed
into oxygen gas, recovering the sulfur dioxide:
2 HI heat (320°C) 9: H2 I2
H2SO4 heat (830°C) 9: SO2 H2O 1/2 O2
Since the reactants HI and SO2 are recovered in high yield, the cycle can be
repeated over and over. Heat produced by nuclear reactors could drive this
cycle, which has a conversion efficiency of about 50%.
Hydrogen gas can be produced by reacting a fossil fuel such as coal or
petroleum or natural gas with steam to form hydrogen and carbon dioxide.
The energy value of the fuel is transferred from carbon to the hydrogen
atoms of water; chemically speaking, the reduced status of the carbon is
transferred to the hydrogen. The net reactions, assuming coal to be mainly
graphite, are:
C 2 H2O 9: 2 H2 CO2
CH4 2 H2O 9: 4 H2 CO2
Notice that as much carbon dioxide is produced in this way as would be
obtained by combustion of the fossil fuels in oxygen. As discussed previously,
the actual conversions occur in two steps: First the fossil fuel reacts with steam
to yield carbon monoxide and some hydrogen (Figure 8-10). Then the CO/H2
synthesis gas mixture and additional steam are passed over a suitable catalyst to
obtain additional hydrogen and complete the oxidation of the carbon by the
water-gas shift reaction driven in the direction shown here:
catalyst
CO H2O CO2 H2
It is interesting to note that at the turn of the twentieth century and for
several decades thereafter, the synthesis gas produced when coal reacts with
steam was itself used as the fuel in many municipal street-lighting systems
around the world.
Hydrogen gas could be produced in a renewable way from biomass
grown for this purpose. Some research indicates that aqueous solutions of
both glucose and glycerol can be decomposed at moderate temperatures
(225 – 265°C) and pressures (27 – 54 atm) with a platinum-based catalyst to
produce hydrogen and carbon dioxide (Figure 8-10).
Associated with every conversion of one fuel to another are energy
losses, mainly to waste heat, some of which are dictated by the second law of
thermodynamics and therefore cannot be avoided. The energy of natural gas

can be transferred to hydrogen with an efficiency of about 72%; transfer from
coal is 55 – 60% efficient. Thus, if the resulting fuel is used only to generate
heat, significantly less CO2 is emitted if the original fossil fuel is burned rather
than being first converted to hydrogen.
Finally, it should be mentioned that hydrogen is considered to be a danger-
ous fuel due to its high flammability and explosiveness; it ignites more easily
than do most conventional fuels. On the positive side, however, spills of liquid
hydrogen rapidly evaporate and rise high into the air. (Some of the fears
surrounding hydrogen stem from the 1930s incident in which the airship
Hindenburg was destroyed in a catastrophic fire. However, it was the thin layer
of aluminum encasing the hydrogen gas that initially was ignited, not the
H2 itself.)
Review Questions
1. Define the term renewable energy, and list sev- maximum fraction of heat that can be transformed
eral forms of it. Which form is growing the fastest? into electricity?
2. Name four environmental/social problems asso- 11. Define the photovoltaic effect. What is the chief
ciated with the expansion of hydroelectric power. difficulty preventing the widespread use of solar cells?
3. What is the mathematical relationship between 12. List four advantages and four disadvantages of
the energy generated by a windmill and (a) the solar energy.
wind’s speed and (b) the length of the windmill 13. What are the advantages and disadvantages of
blades? using alcohol fuels in regard to air pollution? What
4. Explain the origin of coastal winds. is meant by E10 fuel?
5. List four pros and cons of wind power. 14. Describe the method used in producing
ethanol in high volume for use as a fuel. What are
6. Define energy payback, and state which form of the potential feedstocks for this process?
renewable energy has the lowest payback period
and the lowest cost at present. 15. What are the highly energy-intensive steps
involved in production of fuel ethanol? Why isn’t
7. What is meant by geothermal energy? Give some ethanol a fully “renewable” fuel? What is meant by
examples of how and where it is tapped. the term cellulostic ethanol?
8. Describe the difference between the two meth- 16. What is the water-gas shift reaction? Describe
ods of absorbing energy from sunlight. What is the the methods by which methanol can be produced
difference between active and passive systems? in volume for use as a fuel. What does M85 mean?
9. What is meant by solar thermal electricity, and 17. Chemically speaking, what is biodiesel and
how is it generated? What is meant by the term how is it produced?
cogeneration?
18. Describe the three ways in which hydrogen
10. State the second law of thermodynamics. can be stored in vehicles for use as a fuel, and dis-
According to this law, what formula gives the cuss briefly the disadvantages of each method.
19. Does the burning of hydrogen really produce 21. Describe how a hydrogen fuel cell works, and
no pollutants? Under what conditions do no pollu- write balanced half-reactions for its operation in
tants form? acidic media. What other types of fuel cells exist?
20. What is the difference between an energy 22. Describe the production of hydrogen gas by
source and an energy carrier (vector)? Into which electrolysis. Can solar energy be used for this pur-
category does H2 fall? pose? Why isn’t water decomposed directly by
absorption of sunlight?

See the discussion of focus areas and the princi- discussed in this chapter) can be obtained from bio-
ples of green chemistry in the Introduction mass while propene is a petrochemical. Another
before attempting these questions. aspect of these two preparations of propylene glycol
to consider when assessing their environmental
1. The first reaction below is the Suppes synthesis
impact is their atom economy. Calculate the atom
of propylene glycol from glycerin (which won a
economy of these syntheses. To aid you, for each
Presidential Green Chemistry Challenge Award);
synthesis, the atoms of the reactants that are incor-
the second reaction is the commercial synthesis of
porated into propylene glycol are given in green
propylene glycol from propene. Glycerin (as was
while those that are wasted are in black.
OH OH OH OH OH
copper chromite
H9H, 200°C, 200 psi
H2C99CH9CH2 H2C99CH9CH3
glycerin propylene glycol
H9O Cl OH OH
O
Cl2 NaOH H2O
H3C9 CH" CH2 H2O
H3C9CH9CH2 H3C9HC9CH2 H3C9HC9CH2
120 –190°C
high pressure
2. The development of the preparation of propy- version of fats and oils to biodiesel and glycerin as
lene glycol and acetol from glycerin by Suppes won shown in Figure 8-11.
a Presidential Green Chemistry Challenge Award.
4. Where does diesel fuel come from? How is it
(a) Into which of the three focus areas for these produced? What compounds make up diesel fuel?
5. Ethanol and methanol are being used as auto-
(b) List at least two of the twelve principles of
mobile fuels. What do you think about the use of
green chemistry that are addressed by the green
the alcohols propylene glycol and glycerin as auto-
chemistry developed by Suppes.
mobile fuels? [Hint: It many be useful to look up the
3. If you have had a course in organic chemistry, boiling points of ethanol, methanol, ethylene glycol,
try to deduce a reaction mechanism for the con- and glycerin.]
Additional Problems
1. Given that an average of 342 W of sunlight the total carbon dioxide resulting from the produc-
energy falls on each square meter of Earth, tion and combustion of methanol synthesized from
that the surface area of a sphere is 4r2, and that this synthesis gas that would be renewable, i.e.,
the Earth’s radius r is about 6400 km, calculate in recycled from the consumption of carbon dioxide
joules the total amount of sunlight received annu- in the process.
ally by the Earth. What percentage of this quantity
needs to be captured in order to provide our cur- 5. Contact several new car dealerships in your
rent commercial energy needs? area to discover which vehicles currently on sale
can use one or more of the alternative fuels CNG,
2. Consider the use of methanol, CH3OH, as an LPG (propane; see Chapter 7), M85, E100 or E85,
oxygenated liquid fuel for suitably modified cars. hydrogen, or electricity. For each fuel and vehicle,
(a) By writing the balanced chemical equation for inquire about the average kilometers or miles per
its combustion in air, determine whether it is more liter or gallon of fuel; from this information and
similar to coal, oil, or natural gas in terms of the using fuel prices obtained from local service
joules of energy released per mole of CO2 produced. stations, estimate the driving cost per kilometer
(b) Determine the balanced equation by which or mile for each vehicle and fuel combination.
methanol can be produced by reacting elemental Are any of the combinations competitive in cost
carbon (coal) with water vapor, given that CO2 is with gasoline?
the only other product in the reaction. (c) Does the 6. Contact a garage in your area that converts
combined scheme of parts (a) and (b) represent a existing gasoline-fueled vehicles into those that
way of using coal but producing less carbon dioxide accept CNG or LPG (propane; see Chapter 7).
per joule than by its direct combustion? Explain Determine the common conversion price and what
your answer. the likely kilometers-per-liter or miles-per-gallon
3. Deduce the fraction of the CO or H2 produced performance for the new fuel in a common vehicle
by the reaction of coal with steam that must be will be. From the cost of the fuels in your area,
converted to H2 or CO, respectively, by the water- estimate the distance that the vehicle must be
gas shift reaction in order to obtain the 2:1 ratio of driven before the cost of the conversion has been
hydrogen to carbon monoxide that is required to met by savings on the fuel.
synthesize methanol. Deduce also the net reactions
7. The Bay of Fundy, located between the
of conversion of coal to methanol.
Canadian provinces of Nova Scotia and New
4. Deduce the balanced reaction in which synthe- Brunswick, has the highest tides in the world. The
sis gas is formed by combining equal volumes of difference between high and low tides can be as
methane and carbon dioxide. From enthalpy of much as 16 m. A total of 14 billion tonnes of sea-
formation data given in Problems 7-4 and 8-7, water flow into and out of Minas Basin, a part of
deduce the enthalpy change for this reaction. By the Bay of Fundy, during each tide. The energy
applying Le Châtelier’s principle, deduce whether tapped as tidal power comes from the change in
the conversion of the gases to carbon monoxide potential energy of this water as it falls in the
and hydrogen will be favored by low or by high Earth’s gravitation field. Given that the potential
pressures, and by low or by high temperatures. energy of a mass m at height h in a gravitational
Combining these results with those obtained in field is given by m g h, where g is the gravita-
Additional Problem 3, determine the fraction of tional constant, 9.807 m/s2, calculate the amount
of energy that corresponds to a tidal drop of 16 m 9. The use of biomass fuels, including scavenged
in the Minas Basin. wood and wood-chip waste, has been proposed as
a way of reducing CO2 emissions, even though
8. One way of considering the direct environmen-
such fuels would produce a large amount of CO2
tal impact of the combustion of various fuels is to
per unit of heat produced. Explain the rationale
look at the amount of heat produced per unit of
behind this idea.
CO2 generated. Determine and compare the values
of kilojoules of heat per mole of CO2 produced in 10. Assuming that MTBE reacts in the atmo-
the case of the combustion of methanol, ethanol, sphere at the methyl group attached to the oxygen,
and n-octane. Use the following molar enthalpies use the principles of atmospheric reactivity devel-
of combustion (Hc, in kJ/mol): methanol, 726; oped in Chapter 5 to show that the first stable
ethanol, 1367; and n-octane, 5450. Comment product in its decomposition sequence in air is
on the values obtained. an ester.
Further Readings
1. S. Pacala and R. Socolow, “Stabilization 4. R. Gomez and J. L. Segura, “Plastic Solar
Wedges: Solving the Climate Problem for the Cells,” Journal of Chemical Education 84 (2007):
Next 50 Years with Current Technologies,” Science 253–258.
305 (2004): 968–972.
5. P. Hoffmann, Tomorrow’s Energy: Hydrogen,
2. M. Hoogwijk et al., “Assessment of the Global Fuel Cells, and the Prospects for a Cleaner Planet
and Regional Geographical, Technical, and (Cambridge, MA: MIT Press, 2001).
Economic Potential of Onshore Wind Energy,”
6. R. F. Service, “The Hydrogen Backlash,” Science
Energy Economics 26 (2004): 889–919.
305 (2004): 958–961 (the August 13, 2004, issue
3. N. Fell, “Deep Heat,” New Scientist (22 February of Science contains many articles on the hydrogen
2003): 40–42. economy).
C H A P T E R
9
RADIOACTIVITY, RADON,
AND NUCLEAR ENERGY

topics are used:
 Mass and atomic numbers; isotope symbolism;
elementary particles
 Half-lives; exponential decay and first-order processes

 Concepts of free radicals (Chapter 1) and synergism (Chapter 4)
 Half-life equation (Chapter 6)
 Second law of thermodynamics (Chapter 8)
Introduction
In all other chapters of this book, we
are concerned with chemicals and
chemical processes. In this chapter,
we consider nuclear processes and
how they affect the environment, our
health, and our energy supply. These
concerns all center on the effects of
radioactivity, and it is with this topic
that we begin. This allows us to discuss
radon, the most important radioac-
tive indoor air pollutant, and depleted
uranium. We then switch to nuclear
energy and explore the ways in which
electricity can be produced from it
and the environmental consequences The San Onofre nuclear power generating station at San Diego, California.
of the radioactive waste that these All current nuclear energy is generated by fission, though fusion plants
processes generate. may be viable in the future. (Corbis Images)
367
368 Chapter 9 Radioactivity, Radon, and Nuclear Energy
Radioactivity and Radon Gas

The Nature of Radioactivity
Although most atomic nuclei are stable indefinitely, some are not. The
unstable, or radioactive, nuclei spontaneously decompose by emitting a
small particle that is very fast moving and therefore carries with it a great
deal of energy. In some types of nuclear decomposition processes, atoms
are converted from those of one element to those of another as a conse-
quence of this emission. Very heavy elements are particularly prone
to this type of decomposition, which occurs by the emission of a small
particle. The nuclei produced by emission of the particle may or may not
themselves be radioactive; if they are, they will undergo another decom-
position at a later time.
Recall from introductory chemistry that the mass number is the number
of heavy particles—protons and neutrons—and not the actual mass of
the nucleus. An alpha (␣) particle is a radioactively emitted particle that
has a charge of 2 and a mass number of 4—it has two neutrons and two
protons—and it is identical to a common helium nucleus. Thus an a particle
is written as 42He, where 4 is its mass number and 2 refers to its nuclear charge
(i.e., number of protons). The nucleus that remains behind after an atom has
lost an a particle has a nuclear charge that is 2 units less than the original,
and it is 4 units lighter. For example, when a 226
88 Ra (radium-226) nucleus emits
an particle, the resulting nucleus has a mass number of 226 4 222 units
and a nuclear charge of 88 2 86; this is a wholly new element that is an
isotope of the element radon. The process can be written as a nuclear reaction:
226
88 Ra 9: 222
86 Rn + 2He
4
Notice that both the total mass number and the total nuclear charge individ-
ually balance in such equations.
A beta (B) particle is an electron. It is formed when a neutron splits
into a proton and an electron in the nucleus. Since the proton remains
behind in the nucleus when the electron leaves it, the nuclear charge (or
atomic number) increases by 1 unit (you may imagine this effect as “subtract-
ing a negative particle”). There is no change in mass number of the nucleus,
since the total number of neutrons plus protons remains the same. For exam-
ple, when an atom of the lead isotope 214
82Pb (lead-214) decays radioactively by
the emission of a b particle, the nuclear charge of the product is 82 1 83,
corresponding to the element bismuth; the mass number remains 214:
214
82 Pb 9: 214
83Bi +
0
-1e
Notice that the symbol -10e used here for the electron shows its mass number
(zero) and its charge; in the equation the total mass numbers and nuclear
charge numbers each balance.
Summary of Small Particles Produced

TABLE 9-1 by Radioactivity
Particle Symbol Chemical Effect on Nucleus of

and Name Symbol Comment Particle Emission
a (alpha) 4
2He Nucleus of a Atomic number reduced
helium atom by 2
0
b (beta) 1e Fast-moving Atomic number increased
electron by 1
g (gamma) None High-energy None
photon
One other important type of radioactivity is the emission of a gamma (G)

particle (also called a ray) by a nucleus. This is a huge amount of energy con-
centrated in one photon and possesses no particle mass. Neither the nuclear
mass number nor the nuclear charge changes when a g particle is emitted.
The emission of a g ray often accompanies the emission of an a or b particle
from a radioactive nucleus. The properties of all three types of nuclear radia-
tion are summarized in Table 9-1.
P R O B L E M 9-1
Deduce the nature of the species that belongs in the blank for each of the fol-
lowing nuclear reactions:
4
86 Rn 9: 2He _____
(a) 222
83Bi 9: b _____
(b) 214
(c) - Po 9: 214
214
- Pb _____
(d) _____ 9: 23490Th a
The Health Effects of Ionizing Radiation

The a and b particles that are produced in the radioactive decay of a nucleus
are not in themselves harmful chemicals, since they are simply the nucleus of a
helium atom and an electron. However, they are ejected from the nucleus with
an incredible amount of energy of motion. When this energy is absorbed by the
matter encountered by the particle, it often ionizes atoms or molecules; for that
reason, it is called ionizing radiation, or just radiation. This radiation is poten-
tially dangerous if we absorb it, since the molecular components of our bodies
can be ionized or otherwise damaged.
Although a and b particles are energetic, they cannot travel far within
the human body, since they lose more and more of their energy—and
consequently slow down—as they collide with more and more atoms.
Alpha particles can travel only a few thousandths of a centimeter within

the body, so they are not penetrating. This is true because they are relatively
massive, and when they interact with matter they slow down, capture electrons
from it, and are converted into harmless atoms of helium gas. If an a particle is
emitted outside the body, it will usually be absorbed in the air or by the layer of
dead skin, so it will do you no harm. However, inhaled or ingested radioactive
atoms can cause serious internal damage when they emit a particles. The damage
is particularly severe with a particles since their energy is concentrated in a
small area of absorption located within about 0.05 mm of the point of emission.
In their interaction with matter, a particles are highly damaging—the most
highly damaging of all particles—since they can knock atoms out of molecules
or ions out of crystal sites. If the molecules affected are DNA or its associated
enzymes, cell death can result. A more serious consequence for the individual
can be the creation of mutations that could lead to cancer.
Beta particles move much faster than a particles since they are much
lighter and can travel about 1 m in air or about 3 cm in water or biological
tissue before losing their excess energy. Like a particles, they can cause con-
siderable damage to cells if they are emitted from particles that have been
inhaled or ingested and the radioactive nucleus is consequently close to the
cell when it decays.
Gamma rays easily pass through concrete walls—and our skin. A few cen-
timeters of lead are required to shield us from g rays. Gamma particles are the
most penetrating and therefore the most damaging of the three, traveling a
few dozen centimeters into our bodies or even right through them. They are
generally the most dangerous type of radioactivity, since they can penetrate
matter efficiently and do not have to be inhaled or ingested. Although they
can pass through our bodies, g rays lose some of their energy in the process,
and cells can be damaged by this transferred energy, since it can ionize molecules.
Ionized DNA and protein molecules cannot carry out their normal functions,
potentially resulting in radiation sickness and cancer.
The ions produced by radiation when its energy is transferred to
molecules are free radicals; hence they are highly reactive (Chapters 1, 3,
and 5). For example, a water molecule can be ionized by an a, b, or g ray
or by an X-ray. The resulting H2O free-radical ion subsequently dissociates
into a hydrogen ion and the hydroxyl free radical, OH:
H2O radiation 9: e H2O
H2O 9: H OH
If the affected water molecule is contained in a cell, the hydroxyl radical can
engage in harmful reactions with biological molecules in the cell, such as
DNA and proteins. In some cases, radiation damage is sufficient to kill cells
of living organisms. This is the basis of food irradiation, where the death of
microorganisms helps prevent subsequent spoilage of the food.
If human beings are exposed to substantial, though sublethal, amounts

of ionizing radiation, they can develop radiation sickness. The earliest effects
of this malady to be observed occur in tissues containing cells that divide
rapidly, because damage to the cell’s DNA or protein can affect cell division.
Such rapidly dividing cells are found in bone marrow, where white blood
cells are produced, and in the lining of the stomach. It is not surprising,
then, to find that early symptoms of radiation sickness include nausea and a
drop in white blood cell count. Children are more susceptible to radiation
than adults because their tissues involve more cell division. On the other
hand, radiation can be effectively used to kill cancer cells since they are
dividing rapidly. Unfortunately, radiation therapy cannot be completely
selective in terms of the cells it affects, so it has side effects such as nausea.
Long-term effects from radiation may show up in genetic damage,
because chromosomes may have undergone damage or their DNA may have
mutated. Such damage may lead to cancer in the person exposed or to effects
in her or his offspring if the changes occurred in the ovaries or testes.
Quantifying the Amount of Radiation Energy Absorbed

The amount of radiation absorbed by the human body is measured in rad
(radiation absorbed dose) units, where 1 rad is the quantity of radiation that
deposits 0.01 joule of energy to 1 kilogram of body tissue. The rad is not a
particularly useful quantity, however, since the damage inflicted by 1 rad of
a particles is 10 to 20 times greater than that inflicted by 1 rad of b particles
or g rays. The scale of absorbed radiation that incorporates this biological
effectiveness factor is the rem (roentgen equivalent man). A more modern
unit than the rem is the sievert, Sv, which equals 100 rem.
On average, we each receive about 0.3 rem, i.e., 300 mrem or 3000 mSv,
of radiation annually. The origin on average is about
• 55% from radon in indoor and outdoor air;
• 8% from cosmic rays from outer space;
• 8% from rocks and soil;
• 11% from natural radioactive isotopes (e.g., 40 K, 14 C ) of elements that
are present in our own bodies; and
• 18% from anthropogenic sources, chiefly medical X-rays.
The average contribution from nuclear power production is negligible at
present.
An acute exposure of more than 25 rem results in a measurable decrease
in a person’s white blood cell count; over 100 rem produces nausea and hair
loss; and an exposure of over 500 rem results in a 50% chance of death within
a few weeks.
Radioactive Nucleus Decay

The radioactive decay of the atoms in an isotope sample does not occur all at
once. For example, in a sample of uranium-238, 238U, just large enough to be
visible, there are about 1020 atoms. Only about 107 of the 238U nuclei in the
sample decompose in a given second, so it requires billions of years for the
decomposition process to be complete for
the sample as a whole.
(a) Since all radioactive nuclei disin-
238 U tegrate by processes that are kinetically
236 first-order, it is convenient to express the
234 Th Pa U decomposition rate as the time period
232 required for half the nuclei in a sample to
230 Th disintegrate—its half-life, t1/2. (This is the
228 same property that was used in earlier chap-
226 Ra
ters to discuss the decomposition of sub-
Atomic mass
224
stances by chemical reactions.) For
222 Rn
example, the half-life of 238U is about 4.5
220
billion years. Thus about half of this isotope
218 Po
of uranium existing when the Earth was
216
formed (about 4.5 billion years ago) has
214 Pb Bi Po
212
now disintegrated; half the remaining 238U,
210 Pb Bi Po
amounting to one-quarter of the original,
208 will disintegrate over the next 4.5 billion
206 Pb (nonradioactive) years, leaving one-quarter of the original
204 still intact. After three half-lives have
passed, only one-eighth of the original will
81 82 83 84 85 86 87 88 89 90 91 92 93 remain, and only one-sixteenth will be
Atomic number there after four half-lives.
(b)
a a a
226 222 218 214
88 Ra 1600 y 86 Rn 3.8 d 84 Po 3m 82 Pb
b b a b
P R O B L E M 9-2
214 214 210 210
83Bi Po
84 1 s 82 Pb 83 Bi
27 m 20 m 22 y
Recall from introductory chemistry that for
first-order processes, the fraction F of reac-
tant left after time t of reaction has elapsed
FIGURE 9-1 (a) The 238U
radioactive decay series.
is given by F ekt, where k is the rate
(b) The radium–radon por- constant. Calculate the time required for 99% of a sample of 238U to disinte-
tion of the 238U radioactive grate. [Hint: The relationship between k and t1/2 is k 0.693/t1/2.]
decay series. The symbol
above the arrow signifies
the type of particle (a or b)
emitted during the transi- Radon from the Uranium-238 Decay Sequence
tion. The time period indi-
cated below an arrow is the Many rocks and granite soils contain uranium, so the radioactive decay
half-life of the unstable process takes place under our feet each day, with radon gas being one of its
isotope. unwelcome products. Each 23892 U nucleus eventually emits an a particle, and
an atom of the thorium isotope 234

90 Th is formed:
238
92 U 9: 234
90 Th + 2He
4
This is the first of 14 sequential radioactive decay processes that a 238U

nucleus undergoes, as illustrated in Figure 9-1a. The last of these reactions
produces 206
82 Pb, a nonradioactive (stable) isotope of lead; therefore, the
sequence stops. The concentration of each member of the series can be
determined using steady-state principles (see Box 9-1).
BOX 9-1 Steady-State Analysis of the Radioactive Decay Series
he various members, except the first and to the half-life decay period of the species that
T last, of the 14-step radioactive series of
Figure 9-1a in a body of undisturbed uranium
produces it. For example, the half-life of 222Rn
is 3.8 days and that of the 226Ra that produces it
ore are each in a steady state (Chapter 1) is 1600 years, or 1.5 105 times as long, so
with respect to their concentrations. Since all the steady-state ratio of radon to radium is
nuclear disintegration processes are kineti- 1/1.5 105 or 6.5 106. In qualitative
cally first-order, the rate of production of each terms, the radon concentration never comes
species, C, is proportional to the concentra- close to reaching that of the radium since it
tion of B, the species that precedes it in the decays so quickly after it is formed.
chain A : B : C : D : . The rate of
disintegration of C is proportional to its own
PROBLEM 1
concentration. Thus
Show that the ratio of the steady-state con-
d [C]兾dt kp [B] kd [C] 0 centration of C relative to the first member,
at steady state A, of the radioactive series A : B :
so C : D : is equal to the ratio of their
half-lives for disintegration, and thus that the
[C]ss 兾[B]ss kp兾kd steady-state concentration of each member of
the series is directly proportional to its disinte-
Since each first-order rate constant is inversely gration half-life.
proportional to the half-life period for the
process, it follows that
PROBLEM 2
[C]ss 兾[B]ss tC兾tB
Using the equations developed in Box 14-4,
where tC and tB correspond to the half-life deduce how long it will take for radon-222 to
periods for decay by disintegration of C and B. reach 80% of its steady-state concentration
Thus the steady-state concentration of any after a sample of radium-226 is purified of con-
species along the series relative to the one that tamination by any other substance. [Hint:
precedes it is directly proportional to its half- Recall that for first-order reactions, t0.5
life decay period and inversely proportional 0.693/k.]
Of particular interest is the portion of the 14-step sequence of 238U

radioactive decay that involves radon, since this element is the only one, other
than the helium produced from the a particles, that is gaseous and therefore is
mobile. Details concerning this portion of the radioactive decay series are shown
in Figure 9-1b. The immediate precursor of the radon is radium-226, which has
a half-life of 1600 years and decays by emission of an a particle:
226
88 Ra 9: 222
86 Rn + 2He
4
The 222Rn isotope has a half-life of 3.8 days, which can be long enough for
it to diffuse through the solid rock or soil in which it is initially formed. Most
radon escapes directly into outdoor air when the surface of the Earth where it
appears is not covered, e.g., by a building. The very small background concen-
tration of radon in air that this produces nevertheless yields about half of our
exposure to radioactivity, as listed above. Although the radon decays in a few
days, it is constantly replaced by the decay of more radium.
Some scientists have pointed out that radon gas accumulates to
unhealthy levels in caves, including some that are often used for recre-
ational purposes. However, it is in certain homes that radon becomes an
important indoor air pollutant. Most radon that seeps into homes comes
from the top meter of soil below and around the foundation; radon pro-
duced much deeper than this will probably decay to a nongaseous and
therefore immobile element before it reaches the surface. Loose, sandy soil
allows the maximum diffusion of radon gas, whereas frozen, compacted, or
clay soil inhibits its flow. Radon enters the basements of homes through
holes and cracks in their concrete foundations. The intake is increased sig-
nificantly if the air pressure in the basement is low. The material used to
construct the homes and water from artesian wells are other potential
sources of radon in homes. Groundwater systems serving up to a few hun-
dred people often have radon levels almost 10 times those of surface
waters. When well water is heated and exposed to air, as occurs when it
exits from a showerhead, radon is released to the air. However, radon from
water usually represents only a small fraction of that arising from soil,
although it represents a greater health hazard than that contributed from
water disinfection by-products and other dissolved chemicals.
Measuring the Rate of Disintegration and Health

Threat from Environmental Radiation
The rate of radioactive disintegrations in a sample of matter is usually mea-
sured in bequerels, Bq, where 1 Bq corresponds to the disintegration of one
atomic nucleus per second. The other unit used is the curie, Ci, which equals
3.7 1010 Bq and is the radioactivity produced by one gram of 226Ra. Envi-
ronmental regulations are usually expressed in the number of bequerels per
unit volume or, in the United States, in terms of the number of picocuries,
where 1 pCi 1012 Ci. For example, the U.S. EPA uses 4 pCi per liter of air
as the upper limit for a safe radon level in houses.
We can calculate the amount of energy from radiation that is absorbed by
a person’s lungs in a year if he or she breathes air containing radon at the
4 pCi/L level, since the energy of each a particle emitted by a radon atom is
known by measurement to be 9.0 1013 J. Since 4 pCi/L is equivalent to
4 1012 3.7 1010 0.15 disintegrations per liter per second, and since
there are 60 60 24 365 sec in a year, the total annual number of disin-
tegrations in 1 L of air is 4.7 106. Thus the total amount of energy liberated
annually in the process is 4.7 106 9.0 1013 J 4.2 106 J. If we
assume that all this energy is absorbed by a person’s lung tissues (rather than by
the air in the lungs), that the lung volume is about 1 L, and that the lung mass
is about 3 kg, then since 1 rad 0.01 J/kg, the energy absorbed is 1.4 104
rad or 0.14 mrad. Using a factor of 10 to convert rads to rems for a-particle
radiation, we find that the annual radiation dose is about 1.4 mrem, i.e., about
0.5% of background exposure.
The Daughters of Radon

Radon, the heaviest member of the noble gas group, is chemically inert under
ambient conditions and remains a monatomic gas. As such, it becomes part of
the air that we breathe when it enters our homes. Because of its inertness,
physical state, and low solubility in body fluids, radon itself does not pose much
of a danger; the chance that it will disintegrate during the short time it is pres-
ent in our lungs is small and, as discussed above, the range of a particles in air
before they lose most of their energy is less than 10 cm.
The danger arises instead from the radioactivity of the next three elements
in the disintegration sequence of radon—namely, polonium, lead, and bismuth
(see Figure 9-1b). These descendants are termed daughters of radon, which in
turn is called the parent element. In macroscopic amounts, these particular
daughter elements are solids, and when formed in the air from radon they all
quickly adhere to dust particles. Some dust particles adhere to lung surfaces
when inhaled, and it is under these conditions that the elements pose a
health threat. In particular, both the 218Po, which is formed directly from
222
Rn, and the 214Po, which is formed later in the sequence (Figure 9-1b), emit
energetic a particles that can cause radiation damage to the bronchial cells
near which the dust particles reside. This damage can eventually lead to lung
cancer. Indeed, as will be discussed, radon (or rather its daughters) is the
second leading cause of such cancers, although it follows smoking by a wide
margin.
Although some radon daughters in the sequence disintegrate by b-particle
emission, the deleterious health effects of these particles are considered negligible
because the a particles carry much more energy and, as discussed, it is the disrup-
tion of cell molecules by the burst of high energy that initiates cancer.
Notice that the sequence (see Figure 9-1b) of radon decay to 210Pb for-
mation takes less than a week on average. In contrast, disintegration of 210Pb
to 210Bi has a half-life of 22 years, and, in fact, most of the lead will have been
cleared from the body before this process occurs.
Measuring the Health Danger from Radon and Its Daughters

The greatest exposure to a particles from radon disintegration is experienced by
miners who work in poorly ventilated underground uranium mines. Their rate
of lung cancer is indeed higher than that of the general public, even after cor-
rections to the data have been made for the effects of smoking. From statistical
data relating their excess incidence of lung cancer to their cumulative level of
exposure to radiation, a mathematical relationship between cancer incidence
and radon exposure has been developed. Scientists have extrapolated this rela-
tionship to determine the risk to the general population from the generally
lower levels of radon to which the public is exposed.
Based on linear extrapolation from the miners’ data and other sources,
the U.S. EPA estimates that radon currently causes about 21,000 excess lung
cancer deaths annually; the estimate for the United Kingdom is 2000 cases per
year. Most of the excess deaths are associated with smokers, since radon and
cigarette smoke are synergistic (see Chapter 4) in causing lung cancer. In par-
ticular, the risk of lung cancer by age 75 is 4 in 1000 for a nonsmoker living in
a house with zero radon and is only increased to 7 in 1000 if he or she has con-
stant exposure by inhalation to 400 Bq/m3 of radioactivity from the gas, for a
net increase of 3 in 1000. However, a smoker’s chances of lung cancer rise from
100 to 160 in 1000, an increase of 60, by exposure to the same level of radioac-
tivity. It is estimated that radon causes about 10% of all lung cancers, which is
about half the mortality rate from automobile accidents, for example.
The level of radioactivity in air is stated in units of becquerels (Bq)
per cubic meter. The average indoor radon concentration globally is about
39 Bq/m3, compared to the usual outdoor level of about 10 Bq/m3. The radioac-
tivity “action level” for indoor air, beyond which mitigation measures should
be taken, is 150 Bq/m3 (4 pCi/L) in the United States; that in Great Britain,
Norway, and Sweden—and that proposed for Canada—is 200 Bq/m3. Because
radon dissolved in drinking water can escape into the air when it comes out of
the tap, a maximum contaminant level of 150 Bq/L has been established by
the U.S. EPA; the World Health Organization (WHO) guideline is 100 Bq/L.
Radon concentrations at these levels are associated with groundwater that has
passed through rock formations that contain natural uranium and radium.
Those skeptical of using uranium miners’ data point out that the calcu-
lated estimates of radon-caused lung cancer may be too high, since miners
work in much dustier conditions than are found in homes and their breathing
during hard labor is much deeper than normal. Consequently, there is a much
greater chance that radon daughters will find their way deep into the lungs of
miners in comparison with the general population. The miners’ exposure to
arsenic and diesel exhaust may also contribute to an increase in the lung
cancer rate that would have been counted as due to radon.
In order to establish whether or not radon gas buildup in homes causes lung
cancer, several epidemiological studies were undertaken in the 1990s. These
analyses, one from Sweden, one from Canada, and one from the United States,
reached contradictory conclusions about the risk of radon to householders. In
the Swedish report the rate of lung cancer in nonsmokers and especially in
smokers was found to increase with increasing levels of radon in their homes.
The Canadian study focused on residents of Winnipeg, Manitoba, which has
the highest average radon levels in Canada; no linkage between radon levels
and lung cancer incidence was found. The U.S. study, conducted among non-
smoking women in Missouri, found little evidence for a trend of increasing
lung cancer with increasing indoor radon concentration.
The environmental radon problem has received the greatest attention in
the United States, where there are currently programs to test the air in the
basements of a large number of homes for significantly elevated levels of the
gas. Once radon is identified, the owners can then alter the air circulation
patterns to reduce radon levels in living areas, thereby reducing the additional
risk of contracting lung cancer. Gaps and cracks in basement walls are sealed,
and venting pipes through basement floor slabs are installed. About 800,000
U.S. homes have undergone mitigation to reduce high radon levels, at an
average cost of $1200 per house, since the 1980s. It has been pointed out,
however, that the normally high mobility of the U.S. population means that,
on average, a given individual who happens to live in a house with a high
level of radon will be there for only a few years and likely spend most of his or
her life in a house with a lower level (since only about 7% of houses have
high levels). Consequently, the estimate of increased lung cancer death men-
tioned at the beginning of this section is likely much too high.
A minority of scientists do not believe that radioactivity at very low levels
causes harm to humans. They are skeptical about the linear-no-threshold
(LNT) assumption—that the observed effects of high doses of radioactivity
can be extrapolated linearly to very low doses and that there is no threshold
below which radioactivity causes no harmful effects such as cancer. Some
point to evidence of a threshold near about 1000 Bq/m3 for the effects of res-
idential radon in causing lung cancer, and others point to the lack of cancer
incidence in many areas having high natural radon levels. However, reviews
published in 2005 and 2006 of epidemiological data from North America and
Europe find no threshold for increase in lung cancer with residential radon.
Some scientists believe in a theory called hormesis, which states that
exposure to radioactivity (and some chemicals) at very low doses for short
periods of time can be positive to human health. Although there are some
animal and cell studies that support this idea, it is not widely accepted among
scientists. Indeed, the LNT theory is supported by recent evidence concerning
cancer incidence among Russian citizens who were exposed inadvertently to
very low doses of radioactivity from nuclear weapons production.
Depleted Uranium
Depleted uranium is what remains of natural uranium once most of the 235U
isotope, used in power reactors and for nuclear weapons, and the 234U have been
extracted from it. Indeed, about 200 kg of depleted uranium is produced for
every kilogram of the highly enriched element, since uranium is only 0.7% 238U.
Because uranium is so dense (70% denser than lead), it is useful for making
armor-piercing weapons, especially projectiles used against tanks. When the
shells hit hard targets, the uranium ignites and the combustion creates clouds of
dust containing uranium oxide. This dust settles and contaminates the soil in the
area, but before that, it can be inhaled by people in the vicinity. Since most of
the 235U has been extracted from the uranium (for use in bombs and power pro-
duction), and since 238U has such a very long half-life, depleted uranium is less
radioactive in terms of a-particle emissions (by almost half) than the naturally
occurring element. However, the b emission from daughters of 238U is still pres-
ent. Concerns have been expressed about the effect of the residual radioactivity
from depleted uranium on troops and civilians exposed to it during wartime.
Dirty Bombs
A dirty bomb is a conventional, chemical-based explosive mixed with
radioactive material that would be distributed over a wide area as a result of
the bomb’s explosion. Dirty bombs could be made by terrorists, using
radioactive material stolen from either hospitals or research institutes, or pur-
chased on the black market from supplies originating in the former Soviet
Union or other countries that have undergone disruption with a consequent
loss of security at their nuclear energy facilities. Although the actual danger to
human health from a dispersal of dirty bomb materials into the environment
may well be quite small, the fear it would generate in the public and the
expense of decontamination of wide areas would be substantial.
A similar terrorist threat would be the deliberate crashing of hijacked air-
craft into nuclear power plants or into containers of nuclear fuel. However,
most nuclear energy industry executives deny that the power plants or con-
tainers could be breached, and radioactivity released, by such an event.
Nuclear Energy
Although most of the energy we use originates as heat generated by the
combustion of carbon-containing fuels, heat in commercial quantities can
also be produced indirectly when certain processes involving atomic nuclei
occur; this power source is called nuclear energy, used mainly to produce
electricity. Since nuclear forces are much stronger than chemical bond
forces, the energy released per atom in nuclear reactions is immense com-
pared to that obtained in combustion reactions. One of the attractions of
nuclear power is that it does not generate carbon dioxide or other greenhouse
gases during its operation. Some policymakers have promoted expansion of
nuclear power as a way to combat global warming in the future.
Nuclear Energy 379
There are two processes by which energy is obtained from atomic nuclei:
fission and fusion.
• In fission, the collision of certain types of heavy nuclei (all of which
have many neutrons and protons) with a neutron results in the splitting
of the nucleus into two similarly sized fragments. Since the separated
fragments are more stable energetically than was the original heavy
nucleus, energy is released by the process.
• The combination of two very light nuclei to form one combined nucleus
is called fusion. It also results in the release of huge amounts of energy,
since the combined nucleus is more stable than the original, lighter ones.
Fission Reactors
Currently, there are 440 fission-based nuclear power plants in operation in
more than 30 countries in the world. Collectively, they generate 17% of
global electricity demand, including 23% of that in developed countries, 16%
of that in the former Soviet Union, but only 2% of that in developing coun-
tries. Global production more than tripled between 1980 and 2000. The
fraction of electricity produced by nuclear energy in various countries is
listed in Table 9-2.
TABLE 9-2 Nuclear Power Around the World (2005)
Number of Proportion of Electricity

Country Power Reactors Generated by Nuclear Power
United States 103 19%

France 59 79%
Japan 55 29%
Russia 31 16%
Great Britain 23 20%
South Korea 20 45%
Canada 18 15%
Germany 17 31%
India 16 3%
Ukraine 15 49%
Sweden 10 45%
China 10 2%
Others 65
The most economically useful example of fission, and the one mainly used
by power plants, is induced by the collision of a 235U nucleus with a neutron.
The combination of these two particles is unstable. When it decomposes, the
products vary but are typically a nucleus of barium, 142Ba, one of krypton, 91Kr,
and three neutrons:
1
0n 235
U
92
142
56 Ba 91
36 Kr 3 01n
n
n 235
92 U 142
56 Ba 91
36 Kr n
n
Not all the uranium nuclei that absorb a neutron form exactly the same prod-
ucts, but the process always produces two nuclei of about the sizes of Ba and
Kr, together with several neutrons.
The two new nuclei produced in fission reactions are very fast-moving, as
are the neutrons. It is heat energy from this excess kinetic energy that is used to
produce electrical power. Indeed, the generation of electricity by nuclear energy
and by the burning of fossil fuels both involve using the energy source to produce
steam, which is then used to turn large turbines that produce the electricity.
An average of about three neutrons are produced per 235U nucleus that
reacts; one of these neutrons can produce the fission of another 235U nucleus,
and so on, yielding a chain reaction. In atomic bombs, the extra neutrons are
used to induce a very rapid fission of all the uranium that is constrained to
stay in a small volume, so energy is released explosively. In contrast, the
energy is released gradually in a nuclear power reactor by ensuring that, on
average, only one neutron released from each 235U fission event initiates the
fission of another nucleus. The extra neutrons produced in fission are absorbed
by the control rods in a nuclear power reactor. These are bars made from
neutron-absorbing elements such as cadmium. The position of the rods in the
reactor can be varied to control the rate of fission.
The neutrons that leave 235U nuclei upon fission are too fast-moving to
be efficiently absorbed by other nuclei and cause further fission, so they must
be slowed down if they are to be useful. This is accomplished by the modera-
tor, which, depending upon the type of reactor, can be regular water, heavy
water (i.e., water enriched in deuterium), or graphite. The coolant material
that is used to carry off the heat energy produced by fission in most reactor
types is water, but gaseous carbon dioxide is used in some. Ultimately, high-
pressure, high-temperature steam is created—just as in a fossil-fuel power
generating plant—and used to turn turbines and create electricity. The oper-
ating efficiency of nuclear power reactors is significantly lower than that of
fossil-fuel ones since the core of the nuclear reactor, from which heat is
drawn, is only a little above 300°C, whereas that of fossil-fuel plants may be
as high as 550°C. The various steps in the production of electricity by a
fission-based nuclear power plant are illustrated in Figure 9-2.
Nuclear Energy 381
Fuel rod 5 Generator creates

Control rod electricity.
3 Steam turns 4 Turbine drives
a turbine. a generator.
Nuclear reactor
in containment
building Steam
turbine Generator
Steam Condenser
Cooling tower
6 Steam from turbine

is condensed by
cooling water.
2 Energy from fission

1 Fission reaction reaction is used to boil
generates energy. water and produce steam.
FIGURE 9-2 Step-by-step schematic diagram of the production of electrical power by a

nuclear fission reactor.
P R O B L E M 9-3
Calculate the maximum percentage efficiency in converting heat at 300°C
into electricity according to the second law of thermodynamics (see Chapter 8),
assuming the cooling water is at 17°C. Repeat the calculation for 550°C heat.
Do your calculated values lie above the average efficiencies of 30% and 40%
observed for nuclear and coal-fired power plants, respectively?
The uranium in reactors is contained in a series of enclosed bars called

fuel rods. When the uranium fuel in a rod is “spent,” i.e., when its 235U content
is too low for it to be useful as a fuel since too few neutrons are produced per
second, it is removed from the reactor.
The only naturally occurring uranium isotope that can undergo fission is
235
U, which constitutes only 0.7% of the native element. The remaining
uranium is 238U (99.3% natural abundance). A neutron produced by the
fission of a 235U nucleus can be absorbed on collision by a 238U nucleus.
The resulting 239U nucleus is radioactive and emits a b particle, as does the
heavy product (239Np) of this process; consequently, a nucleus of plutonium,

239
Pu, is produced:
b b
1
0n 238
U
92
239
92 U 239
93 Np 239
Pu
94
n 238
92U 239
U
92 b 239
Np
93 b 239
94 Pu
Thus, 239Pu is produced as a by-product of the operation of nuclear power

reactors.
Unfortunately, both the nuclei into which the 235U nucleus fissions and
239
the Pu by-product are highly radioactive substances. As a consequence,
the material in spent fuel rods is much more radioactive than was the original
uranium. The fission products each consist of about half the original uranium
nucleus (minus a few neutrons), with atomic numbers in the 30s to 50s rather
than 92. Since the optimum neutron/proton ratio of nuclei increases with
mass number, the fission products are neutron-rich. The excess neutrons split
into a proton and an electron, with the latter expelled from the nucleus
as an energetic b particle, thereby increasing the atomic number by 1 and
lowering the neutron/proton ratio. Successive neutron decay continues until
the product is no longer neutron-rich. For example, the krypton produced in
the prototypical fission reaction previously discussed has a neutron/proton
ratio of 1.53, typical of that of a nucleus the size of uranium. It has a half-life
of only 10 seconds before it emits a b particle and becomes rubidium, which
in turn (1-minute half-life) emits a b particle to become strontium, which in
turn (10-hour half-life) emits a b particle to become yttrium, which in turn
(59-day half-life) emits a b particle to become a stable, nonradioactive iso-
tope of zirconium with a normal neutron/proton ratio (1.28) for elements of
this size.
91
36Kr 9: 91
37Rb 9: 38Sr 9: 39Y 9: 40Zr
91 91 91
+b +b +b +b
The spent fuel rods, in which heat is produced by the energy associated with
the b-particle emissions, are immersed in ponds of water for a few months
until most of such decay processes have occurred and the rods have cooled
down.
A few of the 235U fission products have longer half-lives than those dis-
cussed above. After 10 years, most of the radioactivity from spent fuel rods is
due to strontium-90, 90Sr (half-life of 29 years), and to cesium-137, 137Cs
(half-life of 30 years), both of which are b-particle emitters. The dispersal of
radioactive strontium and cesium into the environment would constitute a
serious environmental problem. Ions of both metals can be readily incorpo-
rated into the body because strontium and cesium readily replace chemically
similar elements that are integral parts of animal bodies, including humans.
Nuclear Energy 383
Strontium, a Group II metal, concentrates in the bones and teeth, replacing

ions of calcium, also a Group II metal that forms 2 ions. Ions of cesium, a
Group I metal, can replace those of potassium, also from Group I and also 1
in charge, which is widespread in all body cells. Once these elements are in
place in the body, their radioactive disintegration produces b particles that
can damage the cells in which they are present or near. Radioactive waste
from the spent fuel rods of nuclear power plants must therefore be carefully
monitored and will eventually have to be deposited in a secure environment
from which it cannot escape.
Environmental Problems of Uranium Fuel

Several of the steps in the nuclear fuel cycle, illustrated in Figure 9-3, generate
environmental waste.
Uranium ore
Mining
is mined.
Uranium ore is converted into

reactor fuel, such as uranium oxide,
Conversion
or into uranium hexafluoride,
which can be enriched.
Enrichment
Using gas centrifuges or lasers, a uranium enrichment

plant increases the proportion of 235U. Uranium enriched
up to 5% is a fuel for nuclear reactors, but uranium
enriched to 50% or more is a nuclear explosive.
Natural or low-enriched
uranium is burned in nuclear Uranium
Reactor
reactors to generate electricity, bomb
leaving radioactive spent fuel.
The atomic bomb that
The spent fuel is destroyed Hiroshima in
reprocessed to separate August 1945 contained
Reprocessing around 60 kg of highly
plutonium from
radioactive waste. enriched uranium.
FIGURE 9-3 The
Waste remains The atomic bomb that nuclear fuel cycle.
Radioactive radioactive for Plutonium destroyed Nagasaki in [Source: R. Edwards,
waste hundreds of bomb August 1945 contained “A Struggle for Nuclear
thousands of years. around 6 kg of plutonium. Power,” New Scientist
(22 March 2003): 8.]
Major suppliers and processors of uranium ore are Canada, Australia,

Russia, Niger, Ukraine, and Kazakstan. During the mining of uranium,
contamination of the environment by radioactive substances commonly
occurs. Since naturally occurring uranium slowly decays into other substances
that are also radioactive, uranium ore contains a variety of radioactive ele-
ments. As a result, the very large volume of waste material that remains after
the uranium is chemically extracted from the ore is itself radioactive.
The radioactive material that was immobilized in the original rock ore is in
the form of liquid and powder tailings after mining. Gaseous emissions also
escape from the wastes. As in other mining operations, the liquid tailings are
normally held in special ponds until the solids separate. Pollution of the local
groundwater can occur if these ponds leak or overflow. In addition, when the
solid tailings are exposed to the weather and are partially dissolved by rainfall,
they can contaminate local water supplies.
The use of the solid tailings as landfill on which buildings are constructed
can also lead to problems, since the radon produced by the radioactive decay
of the radium in the tailings is quite mobile. As previously noted, radon is a
particular hazard for uranium ore miners, since the radioactive gas is always
present in the ore and is released into the air of the mine. Indeed, the inci-
dence of lung cancer among such miners was particularly high until mine ven-
tilation was improved to permit more frequent changes of air and thus a more
efficient clearing out of accumulated radon gas.
In most but not all nuclear power reactors (the Canadian CANDU system
being the main exception), the uranium fuel must be enriched in the fis-
sionable 235U isotope; its abundance is increased to 3.0% from the 0.7% in the
naturally occurring element. The extent of enrichment required for use in
bombs is much greater. Uranium sufficiently enriched for this purpose, called
weapons-grade material, is 90% or more 235U. Enrichment is a very expensive,
energy-intensive process since it requires physical rather than chemical means
of separation, given the fact that all isotopes of a given element behave iden-
tically chemically. For separation, the uranium is temporarily converted to the
gaseous compound uranium hexafluoride, UF6.
The CANDU reactor is able to use nonenriched uranium by employing
heavy water rather than normal water as a moderator, since doing so
decreases the probability that neutrons will be absorbed and therefore
unavailable to continue the chain reaction. Heavy water contains a much-
higher-than-normal fraction of deuterium, 2H, the naturally occurring
(0.02% natural abundance) nonradioactive isotope of hydrogen. Some of
the neutrons produced by fission are absorbed by deuterium nuclei, produc-
ing tritium, 3H.
2
H + 1n 9: 3H
Indeed, CANDU reactors produce about 30 times as much tritium as do
light-water reactors. Tritium levels in moderator and coolant water increase
Nuclear Energy 385
with time, as the product of this reaction accumulates. Small losses of coolant
from reactors result in the release of tritium into the aqueous environment.
Tritium is radioactive, a low-energy b-particle emitter with a half-life of
12.3 years. Less than 1% of the tritium in the present environment occurs
naturally; the remainder is due to fallout from nuclear weapons testing in
past decades and to releases from nuclear power reactors. The U.S. EPA
classifies tritium as a human carcinogen; there is evidence that it is muta-
genic and teratogenic (causes birth defects) as well. The EPA’s maximum
limit for tritium in drinking water is 740 Bq/L; Canada’s limit is almost
10 times as high. The waters of Lake Huron and Lake Ontario, along whose
shores several CANDU reactors are located, contain about 7 Bq/L of tri-
tium, compared to 2 Bq/L for Lake Superior, which has no nuclear reactors
nearby.
The Future of Fission-Based Nuclear Power

In North America and much of Europe, public opinion about fission-based
nuclear power shifted from positive to negative in recent decades, partly as a
consequence of the accidents at the Three Mile Island power plant in Harrisburg,
Pennsylvania, in 1979 and at the Chernobyl, Ukraine, power station in 1986.
No new reactors have been ordered in the United States since the Three Mile
Island incident, and several power plants in both the United States and Canada
have been shut down. The last new plant opened in Great Britain in 1995, and
there are no plans for new ones.
Because of the increased need for electricity in developing countries and
the desire to produce electricity with fewer greenhouse gas emissions, nuclear
power has made a comeback in the twenty-first century. About 168 new reac-
tors are expected to start up by 2020, the majority of them in China, India,
Russia and elsewhere in eastern Europe, South Korea, Taiwan, and South
Africa; some new ones are also expected to be built in the United States,
Japan, Europe, and Canada. In addition, a nuclear energy plant may be built
to generate the heat needed to extract oil from the tar sands in Alberta,
Canada. Many existing reactors in these countries are approaching the ends
of their useful lives, giving rise to some of the impetus for new units. The only
new plant actually under construction in Europe is in Finland. The main
advantages and disadvantages of nuclear power production are summarized in
Table 9-3.
The Catastrophe at Chernobyl

A more realistic fear than a nuclear power plant running out of control and
blowing up like an atomic bomb is that the highly radioactive fission products
contained in operating fuel rods could be spread into the surrounding
Inherent Advantages and Disadvantages

TABLE 9-3 of Nuclear Power Production from Fission
Advantages Disadvantages
Minimal air and water pollution Production of radioactive wastes that

require special handling
Efficient use of fuel resources Possibility of an accident producing
serious human health problems
Relatively low operating cost Long-term storage of waste and
decommissioning of plants will
likely involve high costs
Requirement of an international
security system to prevent diversion
of nuclear materials to weapons use
countryside if a nonnuclear explosion occurs in a power plant. This in fact did

occur at one of the nuclear power plants in Chernobyl, Ukraine, in 1985.
During a routine test, engineers at the plant lost control of the reactor by
overriding the plant’s safety mechanisms and withdrew most of the control
rods from the reactor core. As a consequence, the reactor overheated and a
fire broke out in the graphite moderator. This produced a huge explosion,
which blew off the heavy plate covering the building, and several hundred
million curies of radioactivity were released into the air and spread over a
wide area. Several dozen people, mainly plant operators and firefighters, died
immediately from high doses of radiation. The dispersed radioactivity was
mainly concentrated in the noble gas isotopes 131Xe and 85Kr, in 131I, and in
the cesium isotopes 134Cs and 137Cs, all of which are fission products.
The major chronic health consequence to the public of the explosion at
Chernobyl has been the great increase in thyroid cancer among children in
the area. The thyroid cancer was initiated presumably by b radiation from
radioactive iodine, 131I, which has a half-life of only 8 days. The human body
concentrates iodine in the thyroid gland. Thankfully, thyroid cancer has a
high cure rate. In the most contaminated areas of Ukraine, about 4 times as
many children as normal have been diagnosed with thyroid cancer, with very
young children the most susceptible to the radioactivity. The probability of a
Ukrainian child having thyroid cancer was found to increase in direct propor-
tion to the dose of radioactive iodine ingested after the accident. Most of the
iodine in the children’s systems resulted from drinking milk from cows that
had grazed on contaminated plants and from eating leafy vegetables, since
the radioactive iodine was deposited from the air onto plant surfaces. The soil
Nuclear Energy 387
in the affected areas is chronically deficient in iodine, so the substance

would readily have been taken up by the thyroid in children chronically
deficient in the element. Indeed, tablets of potassium iodide, KI, designed to
flood the body with iodine and thereby dilute the radioactive form, were
distributed to the inhabitants around Chernobyl—but not until a week after
the explosion.
Radiation experts predict that about 4000–9000 premature deaths among
people who were living in the heavily contaminated regions—Ukraine,
Belarus, and Russia—have or will eventually be associated with radioactivity
from the Chernobyl event, including not only 131I but also the longer-lived
cesium isotopes 134Cs and 137Cs (the latter having a half-life of 30 years). Can-
cers other than that of the thyroid have much longer development times.
There is some fear that females who were lactating or pubescent just after the
accident may be at higher risk of breast cancer. A much larger number of
Europeans—perhaps as many as 60,000—living outside the most affected areas
who ingested smaller doses may also be affected eventually if the dose–response
relationship for radiation does not have a threshold. However, according to
the World Health Organization, the largest public health problem for the
people who were living in the highly contaminated regions at the time of the
Chernobyl disaster is a long-term decrease in their mental health, stemming
from the traumas of perceived health risks and from relocation out of areas
declared uninhabitable, as was the case for a third of a million people.
The Accident at Three Mile Island

The other nuclear power plant accident was much less serious than the
one at Chernobyl. It occurred in 1979 at the Three Mile Island plant in
Pennsylvania. The problem originated with failures in the water-based cool-
ing systems in the reactor. Although control rods were inserted into the core
and the fission process stopped, the reactor kept heating. The source of the
heat was the radioactive decay by g-ray emission, not of uranium, but of
fission products that had naturally built up over time in the fuel rods. Because
of mechanical malfunction and operator error, the core became partially
uncovered; it was therefore heated even further ( 2200°C), and half of it
melted. Hydrogen and oxygen gases were produced from the decomposition
of the superheated water.
Fortunately, there was no large explosion at Three Mile Island: The con-
tainment facility was not breached. In contrast to the Chernobyl accident, the
liquid and solid radioactive materials that escaped from the reactor did not
escape from the containment building; the release of 131I was about a million
times less. Significant amounts of radioactive noble gas isotopes 131Xe and 85Kr
did escape into the air but, as at Chernobyl, they were quickly diluted in the
atmosphere.
Plutonium
The plutonium-239 isotope that is produced during uranium fission is an
a-particle emitter and has a long half-life of 24,000 years. After 1000 years,
the main sources of radioactivity from spent fuel rods will be plutonium and
other very heavy elements, since the medium-sized nuclei produced in fission,
having much shorter half-lives than 1000 years, will have largely decayed by
that time. Thus the long-term radioactivity of the spent fuel rods can be
greatly reduced by chemically removing the very heavy elements from it.
P R O B L E M 9-4
Given that the half-life of 239Pu is 24,000 years, how many years will it take
for the level of radioactivity from plutonium in a sample to decrease to 1/128
(i.e., about 1%) of its original value?
The 239Pu that forms in fuel rods is itself fissionable; once its concentration
in the rods becomes high enough, some of it also undergoes fission and con-
tributes to the power output of the reactor. However, many of the other fission
by-products are efficient neutron absorbers, and their concentration eventually
builds up to the point where the nuclear chain reaction cannot occur. The plu-
tonium that accumulated over time, and the remaining uranium, in such fuel
rods can be chemically removed from the rest of the spent fuel by reprocessing.
In this procedure, the rods are first dissolved in concentrated nitric acid,
HNO3. The actinide elements—uranium, plutonium, and minor amounts of
several others produced by fission and subsequent radioactive decay—are sepa-
rated from the non-actinide fission by-products such as barium. This is done by
selectively complexing the actinides with a ligand that makes them much more
soluble in an organic medium than in an aqueous one. In the PUREX (pluto-
nium and uranium recovery by extraction) process, 30% tri-n-butyl phosphate,
O“P(O9CH2CH2CH2CH3)3, in a hydrocarbon solvent such as kerosene is
mixed with the nitric acid solution. The actinides complex with the phosphate
and migrate into the kerosene component of the two-phase kerosene–nitric
acid system. Unfortunately, some of the fission by-products dissolve in the
organic phase, since the phosphate compound becomes decomposed to some
extent by the radioactivity present and forms a product that can complex the
fission metals. For this reason, several solvent extraction cycles are required to
completely separate actinides from fission by-products. The aqueous layer is a
highly radioactive form of high-level waste (HLW).
In some situations, it is desirable to separate the uranium from the pluto-
nium before or after it has been extracted from spent fuel. For example, the
uranium still contains about 0.3% 235U, which can be converted again into
reactor fuel. Alternatively, removing the uranium from the rods greatly
reduces the volume of material that must be stored. If the uranium is extracted
Nuclear Energy 389
from the dissolved fuel rods while the plutonium remains mixed with the
highly radioactive fission by-products, there is less reason to worry about the
latter being diverted into the making of bombs. In the UREX (uranium
recovery by extraction) process, plutonium in the dissolved rods is selectively
reduced from Pu4 to Pu3 by addition of a mild reducing agent such as
acetohydroxamic acid (AHA), CH39C(“O)9NHOH. Uranium as U4 (or
as U(VI) in UO22) is then isolated by solvent extraction with tributyl phos-
phate, producing a two-phase system, as in the PUREX process, but with the
plutonium remaining in the aqueous phase since Pu3 preferentially exists in
water rather than in an organic solvent.
Since reprocessing uses chemical procedures, it is much less energy-
intensive than the isotope separation processes. However, the liquid that
remains after the valuable heavy elements have been removed is still highly
radioactive due to the presence of fission products. No method of disposal
for this waste has yet been approved or implemented; it is still stored in
metal tanks. Unfortunately, many of the older tanks in which the liquid is
stored have begun to leak at installations such as Hanford, Washington,
where plutonium for nuclear weapons was manufactured by reprocessing.
Reprocessing is costly, in part because the radioactive waste it produces must
be stored.
Spent fuel rods from civilian power reactors in a number of countries have
been reprocessed in France, the United Kingdom, India, Russia, and Japan,
though not in the United States or Canada. This reprocessing has resulted in a
buildup of hundreds of tonnes of plutonium. Comparable quantities of the ele-
ment are also available from the dismantling of nuclear weapons by the United
States and Russia (see Box 9-2).
Aside from questions of health and safety, a major problem associated with
the handling of plutonium from both civilian and military sources involves the
security measures needed to prevent the material from slipping into the hands
of terrorists and rogue governments who wish to fashion their own bombs.
Only a few kilograms of weapons-grade plutonium, which consists of 93%
or more of 239Pu, is required to make an atomic bomb. A somewhat larger
quantity of reactor-grade plutonium, which contains more of the other isotopes
of plutonium and similar elements, is needed for a bomb. The world’s current
stockpile of plutonium exceeds 1000 metric tons and continues to grow.
Breeder reactors are nuclear power reactors that are designed specifically
to maximize the production of by-product plutonium; such reactors actually
produce more fissionable material than they consume. The special fast
breeder reactors start with a small amount of 238Pu (initially obtained from
conventional uranium-fueled reactors) and produce more of it from 238U
from the reaction previously discussed. The reactors are cooled by liquid
sodium, since water is not adequate for the purpose and would absorb neu-
trons. They use fast neutrons, rather than those moderated to produce fission,
since fast neutrons are more likely to be captured by 238U and produce its
BOX 9-2 Radioactive Contamination by Plutonium Production
lutonium has been deliberately produced will not be completed earlier than 2020. One
P for more than 50 years to provide the
readily fissionable material needed for nuclear
proposed—though expensive—technique for
immobilizing the radioactive wastes involves
weapons. In the United States, most plutonium passing a strong electrical current through the
production and processing were carried out at contaminated soil for a period of days; the
Hanford, Washington. Because huge quanti- electricity would fuse the soil and sand into a
ties of radioactive waste were produced, stored, glassy rock from which the contaminants
and disposed of at this facility, the surrounding could not escape.
environment is now so heavily polluted that it Plutonium was used as the actual explosive
has been called the “dirtiest place on Earth.” material in some atomic bombs and as a “trig-
About 190,000 m3 of highly radioactive solid ger” for hydrogen (fusion) bombs, forcing the
waste and 760 million liters of moderately reactants together and thereby initiating the
radioactive liquid waste and toxic chemicals thermonuclear explosion. Consequently, about
were deposited in the ground at this site. As 100 metric tons of plutonium must be removed
much as a metric ton of plutonium may be from nuclear weapons as tens of thousands of
contained within the masses of solid wastes them are dismantled by the United States and
buried there. The cleanup of the wastes Russia over the next few decades.
will cost between $50 and 200 billion and
daughters, which in turn quickly decay to plutonium. The plutonium must be

separated from the residual uranium by reprocessing before it can be used as a
fuel. Unfortunately, in an accident involving failure of the cooling system,
the reactor core could melt since plutonium’s melting point is only 640°C.
Another potential problem is the violent explosion that would occur if liquid
sodium were to come into contact with water or air.
Alternatively, the thermal breeder reactor converts 232Th by neutron
absorption and b decay into 233U, which can also be used as fuel in nuclear
reactors since it will undergo fission; India has experimented with this design
since it has substantial natural reserves of thorium.
Because there have been operational problems with the very technolog-
ically sophisticated fast breeder reactors, the programs were abandoned in the
United States, the United Kingdom, Germany, and France. Russia and Japan
still operate demonstrator breeder reactors, and both India and China are
building demonstration units. Overall, the future of breeder reactors is in
doubt.
The radiation from plutonium is weak and becomes a concern only if the
material is ingested or inhaled, since its radiation (a particles) cannot pass
through dead layers of skin or clothing or indeed through even a few
centimeters of air. Elemental, metallic plutonium cannot be easily absorbed by
Nuclear Energy 391
the body. However, when exposed to air, plutonium forms the oxide PuO2,
a powdery dust that disperses readily and can be inhaled. Even microscopic
amounts of plutonium oxide lodged in the lungs can induce lung cancer.
Two methods have been proposed to dispose of excess plutonium:
• Mix it with other highly radioactive liquid waste and then vitrify the
mixture into durable glass logs that would be buried far underground in
metal canisters, as will be discussed. Vitrification chemically bonds liquid
waste into a stable and durable borosilicate glass in which fission product
oxides make up about 20% of the mass.
• Convert it to plutonium dioxide, PuO2, and mix it with uranium oxide to
produce a mixed oxide fuel, MOX (containing a few percent plutonium),
that could be used in existing nuclear power plants. Indeed, some MOX is
now employed in reactors in France, Germany, and Switzerland and in the
future will probably be used in the United States, Canada, Belgium, and
Japan. However, producing MOX fuel is much more expensive at present
than is producing low-enriched uranium, so the incentive to use it is not
economic. The issue of using mixed oxide fuel is very controversial in
Great Britain, where one-third of the world’s nonmilitary plutonium is
presently stockpiled.
Nuclear Waste
Although nuclear energy has been used to generate electricity for many
decades, there is still no consensus among scientists and policymakers concerning
the best procedure for the long-term storage of the radioactive wastes generated by
these plants. Initially, spent fuel rods are simply stored above ground—often under
cooled water—for several years or decades until the level of radioactivity has been
reduced and the rods have therefore cooled somewhat. At this stage, the rods can
be transferred to dry storage, e.g., in concrete canisters. If the fuel rods are
reprocessed to remove the uranium and plutonium, the remaining highly
radioactive liquid waste is subsequently solidified by heating to dehydrate it
and decompose the nitrate salts. The resulting powder, composed mainly of
oxides of the fission product metals, is then incorporated into borosilicate glass
(at about the 20% level) for storage in metal cylinders.
Whether or not the plutonium is removed, most nuclear waste disposal
plans assume that the solid material would be encapsulated and immobilized
in a glass or ceramic form and then buried far below the Earth’s surface. The
container for this ultimate disposal would likely be made of a metal, such as
copper or titanium, that is highly resistant to corrosion. The canisters are
designed to last for at least several hundred years before leakage could occur;
by that time the level of radioactivity would have declined substantially,
though almost all of the plutonium would remain. In Sweden, canisters
are being designed to last for 100,000 years, at which time the level of
radioactivity inside would be no greater than that of uranium ore.
Canisters will ultimately be buried in vaults 300–1000 m below the surface.

The geological features of the burial sites should include high stability (from
disruption by earthquakes or volcanic activity) and low permeability to assure
minimal interactions with groundwater and the biosphere. Deep geological dis-
posal is the only method by which safety requirements can be met without bur-
dening future generations with monitoring and management responsibilities.
However, some governments do not accept the idea of permanent disposal of
such wastes. They want to be able to eventually recover the plutonium from
spent fuel rods if it is needed in the future for nuclear power.
Originally, the U.S. plan for the storage of high-level nuclear waste was
to use about 10,000 stainless-steel containers, each weighing several tonnes.
However, a nickel–chromium–molybdenum alloy of steel (C-22) is now pro-
posed for this role since it is more resistant to corrosion. The United States
plans to use a depository to be created 300 m below the surface at Yucca
Mountain, Nevada. In contrast to the plans of other countries, the deposi-
tory will be in the unsaturated zone (see Chapter 14), 300 m above the water
table, where air is still present in the soil. Conditions in the unsaturated
zone are oxidizing. The original idea was to have a dry repository, since water
would have been the main agent for release and transport of radioactive
nuclei. However, some evidence now exists that there is rapid transport of
water through the area even at this depth. Consequently, a so-called drip
shield of titanium would eventually be placed over each canister to keep
water away from it. Other countries, including Canada, plan to use deeper
sites, which will be in the saturated zone so that ambient conditions will be
reducing.
After the engineered barriers have eventually failed, the release of
radioactive nuclei will depend on the chemical durability of the fuel. Since
the uranium in the spent nuclear fuel occurs as U(IV) in the form of UO2,
even small amounts of moisture will result in its oxidation to U(VI), as
UO22 + , which is quite soluble and mobile, at a much faster rate than would
occur under reducing conditions. The presence of Fe2, resulting from the
rusting of the steel canister, would reverse the oxidation and precipitate the
uranium oxide of any U(VI) that came into contact with it.
As of the mid-2000s, no country had as yet implemented permanent
geological storage for nuclear waste, all such schemes having been delayed by
technical or political setbacks. As a consequence, about a quarter of a million
tonnes of spent fuel rods are currently stored in water pools. In some sites in
the United States—home to 70,000 tonnes of waste—the rods are so
crowded together that neutron-absorbing boron panels must be inserted
between them in order to prevent chain reactions from occurring.
Perhaps the most advanced research on nuclear waste disposal is under
way in Sweden, where large iron canisters coated with copper have been
buried in a chamber half a kilometer underground, covered with clay, and the
chamber sealed off with concrete. Electric heaters are used to mimic the
Nuclear Energy 393
effects of radioactive decay. Sensors are used to monitor the temperature and
water movement in the chamber walls.
Fusion Reactors
The optimum energetic stability per nuclear particle (protons and neutrons)
occurs for nuclei of intermediate size, such as iron. That is why the fission of a
heavy nucleus into two fragments of intermediate size releases energy. Simi-
larly, the fusion of two very light nuclei to produce a heavier one also releases
substantial quantities of energy. Indeed, fusion reactions are the source of the
energy in stars, including our own Sun, and in hydrogen bombs.
Unfortunately, fusion reactions all have extremely large activation energies
due to the huge electrostatic repulsion that exists between the positively charged
nuclei when they are brought very close together, which must happen before
fusion can occur. Consequently, it is difficult to initiate and sustain a controlled
fusion reaction that provides more energy than it consumes.
The fusion reactions that have the greatest potential as producers of useful
commercial energy involve the nuclei of the heavier isotopes of hydrogen,
namely deuterium, 2H, and tritium, 3H. Note that two different sets of products
can be produced from these sample reactions:
3
2 He 1
n
0
2
1H 2
1 H or
deuterium deuterium
3
1 H 1
H
1
The energy that is released when one of these reactions occurs is about
4 108 kJ/mol, which is about 1 million times the energy produced in a typ-
ical exothermic chemical reaction. An abundant supply of deuterium is avail-
able, since it is a nonradioactive, naturally occurring isotope (constituting
0.015% of hydrogen) and thus is a natural component of all water.
A somewhat lower activation energy is required for the reaction of
deuterium with tritium:
2
1 H 3
1 H 4
2He 1
n
0
deuterium tritium
However, because tritium is a radioactive element (a b emitter) with a short
half-life (12 years), it is not a significant component of naturally occurring
hydrogen and would have to be synthesized by the fission of the relatively
scarce element lithium.
The environmental consequences of generating electrical power from
fusion reactors should be less serious than those associated with fission
reactors. The only radioactive waste produced directly in quantity would be tri-
tium, although the neutrons emitted in the process could produce radioactive
substances when they are absorbed by other atoms. Although the b particle
that tritium emits is not sufficiently energetic to penetrate the outer layer of
human skin, tritium is nevertheless dangerous since biological systems incor-
porate it as readily as they do normal hydrogen (1H or 2H)—by inhalation,
absorption through the skin, or ingestion of water or food. Currently, tritium
in drinking water (some of which results from artificial sources) constitutes
the source of about 3% of our exposure to radioactivity.
About 80% of the energy emitted in the deuterium–tritium reaction is
associated with the neutrons. The energy, captured by using neutron-heated
coolants, would be used to create superheated steam to drive turbines.
Unfortunately, the intense neutron bombardment will cause severe degradation
of the structure used to confine the fusion reactants and will generate large
amounts of radioactive nuclei. These problems would be largely overcome if
so-called advanced fuels were to be used as reactants. Thus the fusion reaction
of deuterium with helium-3 (32He) releases only a few percent of its reaction
energy as neutrons (the products of the dominant process being protons and
4
He nuclei), and that of two 3He nuclei (to produce two protons and 4He) is
essentially neutron-free. These processes could operate with much higher
energy conversion efficiencies but require even higher initiation temperatures
and confinement conditions. The other serious problem is the lack of 3He on
Earth: The Moon is the best source for this material!
P R O B L E M 9-5
Write and balance the two fusion reactions involving 3He mentioned above.
In 2006, a consortium consisting of the European Union, the United

States, China, India, Russia, Japan, and South Korea agreed to finance the
ITER (International Thermonuclear Experimental Reactor) project, the
world’s first nuclear fusion reactor, to be built by about 2016 in Provence,
France, at a cost of $13 billion. The reactor will not produce usable energy,
but it is being constructed to demonstrate that it is possible to build a reactor
that will generate more power than it consumes. The reactor design is based
on the tokamak, a doughnut-shaped machine having a series of overlapping
magnetic fields that can hold the hot plasma within reactor walls. A demon-
stration power plant, which could use the excess heat to boil water and turn
turbines to generate electricity, is slated for about 2040; it will use the experi-
ence gained in the ITER project in dealing with the helium and tritium gen-
erated by the fusion reactions. Hopefully, the problem of radioactive reactor
materials generated by the neutrons emitted by the fusion reaction will also
have been overcome by that time.
The Energy Released in Nuclear Processes

The energy, E, released in fission and fusion processes comes from the conver-
sion of a tiny fraction, m, of the masses of the atoms and other particles
involved. According to Einstein’s famous equation, the energy released is

E mc2
where c is the speed of light.
For example, in the conversion of one mole of deuterium atoms (mass
2.0140 g) and one mole of tritium atoms (mass 3.01605 g) into one mole
of 4He atoms (mass 4.00260 g) and one mole of neutrons (mass 1.008665 g),
a total of 0.0188 g of matter is lost by conversion to energy. Since
m 0.0188 103 kg and c 2.99792 108 m/s, the energy released is
E mc2 (0.0188 103 kg) (2.99792 108 m/s)2
1.69 1012 kg m2/s2
1.69 1012 J
This energy, 1690 million kilojoules per mole, is about 7 million times the
energy released when the same quantity of hydrogen is burned in oxygen to
produce water.
P R O B L E M 9-6
Calculate the amount of energy released in the fission process described
earlier in the chapter in which uranium-235 and a neutron are fissioned to
barium-142, krypton-91, and 3 neutrons. Assume 1 mole of 235U reacts and
that the atomic masses of 235U, 142Ba, 91Kr, and a neutron are, respectively,
235.044, 141.926, 91.923, and 1.008665. Is the energy released much greater
than, much less than, or about the same per nucleus as that for the fusion
reaction between deuterium and tritium?
Review Questions
1. What is the particulate nature of the radioactive 8. Define fission and write the reaction in which
emissions a and b particles? What is a g ray? a 235U nucleus is fissioned into typical products.
2. Why are a particles dangerous to health only if 9. What are the functions in a fission power
ingested or inhaled? reactor of (a) the moderator and (b) the coolant?
3. What is meant by the terms rad and rem? 10. Explain why the spent fuel rods from fission
reactors are more radioactive than the initial
4. Explain the origin of radon gas in buildings.
fuel.
5. Explain what is meant by the term daughters of
11. Why would radioactive strontium and cesium
radon. Why they are more dangerous to health
be particularly harmful to human health?
than radon itself?
12. Write the nuclear reaction that produces
6. What is depleted uranium? Is it radioactive at all?
plutonium from 238U in a fission reactor.
7. Explain what is meant by a dirty bomb.
13. Describe why the mining of uranium ore often 16. Describe the two main methods that have
pollutes the local environment. been proposed to dispose of excess plutonium.
14. What is a breeder reactor? Why is it useful 17. Define fusion and give two examples of fusion
to breed fissionable fuel? What is meant by processes (i.e., reactions) that may be used in
reprocessing and why is it done? power reactors of the future.
15. Write the nuclear reaction that produces 18. Describe the nature of any radioactive
233
U from 232Th following the absorption of a by-products of the operation of fusion reactors.
neutron. What damage could the neutrons do?
Additional Problems
1. Another possible radioactive decay mechanism radioactive decay? Use the kinetics equation for
involves the emission of a positron, a particle with the first-order decay of a species A as a function
the same mass as an electron but the opposite (i.e., of time: [A] [A]o ekt, where k is the first-order
positive) charge. The net nuclear effect of positron rate constant for the decay. (The rate constant can
emission is the change of a proton into a neutron. be obtained from the value of the half-life given in
Explain how the result of positron emission differs the chapter: t1/2 0.693/k).
from b emission in terms of the periodic table.
3. One physical property that differs for 235UF6
Deduce the symbol for a positron to be used in
and 238UF6 is the rate of effusion of these gases
balanced nuclear equations, by analogy with the
through porous membranes. The lighter 235UF6
symbol 10 e used for a b particle (the symbol e for
will effuse faster, resulting in enrichment of this
an electron is also used here to represent a
desired isotope after passing through the mem-
positron). Predict the decay products and write the
brane. The effusion rate of gases can be described
balanced equation for the positron decay of the
by Graham’s law, which states that the effusion
radioactive isotopes 22 13
11Na and 7 N.
rate of a particle is inversely proportional to the
2. Tablets of KI were distributed to people living square of its mass. Use this law to determine relative
around Chernobyl a week after the nuclear reactor effusion rates of 235UF6 and 238UF6. Based on your
explosion occurred, to help flush the radioactive result, explain why it is necessary in practice to
131
I isotope out of their bodies. What percentage of perform this process through hundreds of membrane
the 131I released by the explosion would have barriers to achieve useful enrichment.
remained by that time? How long would it have
taken for 99% of the released 131I to undergo
Further Readings
1. J. H. Lubin et al., “Lung Cancer in Radon- 3. D. Butler, “Energy: Nuclear Power’s New
Exposed Miners and Estimation of Risk from Dawn,” Nature 429 (2004): 238; E. Marris,
Indoor Exposure,” Journal of the National Cancer “Nuclear Reincarnation,” Nature 441 (2006): 796.
Institute 87 (1995): 817.
4. K. Becker, “Residential Radon and the LNT
2. D. Williams, “Return to the Inferno: Chernobyl Hypothesis,” International Congress Series 1225
After 20 Years,” Science 312 (2006): 180. (2002): 259.
5. D. Krewski et al., “Residential Radon and the 8. K. D. Crowley and J. F. Ahearne, “Managing
Risk of Lung Cancer,” Epidemiology 16 (2005): 137. the Environmental Legacy of U.S. Nuclear-Weapons
Production,” American Scientist 90 (2002): 514.
6. N. Zevos, “Radioactivity, Radiation, and the
Chemistry of Nuclear Waste,” Journal of Chemical 9. G. Brumfiel, “Just Around the Corner” [fusion
Education 79 (2002): 692. power], Nature 436 (2005): 318.
7. R. C. Ewing, “Less Geology in the Geological
Disposal of Nuclear Waste,” Science 286 (1999): 415.
398 Environmental Instrumental Analysis II
Environmental Instrumental Determination

Instrumental
Analysis II
of Atmospheric Methane
In the preceding chapters, we have seen that each compound and, therefore, an individual
methane is an important gas, not only in chemical exit time or retention time.
reactions in the stratosphere and at ground level, High-resolution capillary GC columns,
but also in producing global warming. In this box, designed to separate literally hundreds of com-
the quantification of methane in environmental air pounds from a single mixture, have a very
samples is described. small inside diameter: less than 0.53 mm to as
small as 0.05 mm. Many different internal
he determination of methane concentra-
T tion in the atmosphere can be accom-
plished by return of atmospheric gas samples
chromatographic surfaces are available; each is
designed to separate different families of ana-
lytes. For the paraffin family, of which
to the laboratory for analysis or by measure-
methane is the first member, nonpolar chro-
ment using more rugged field instrumentation
matographic surfaces or phases are used. In a
for direct analysis where the sample is taken—
sample of air collected near a rain forest slash-
e.g., in a rain forest, on a research vessel at
and-burn site, many other hydrocarbons are
sea, or from an airplane. Both methods usually
routinely detected, e.g., isoprene (C5H8),
rely on gas chromatography (GC) as a means
ethane, propane, and ␤-pinene. The table
of separating the complex mixtures of atmos-
below details the concentration of these com-
pheric components and a very sensitive instru-
pounds 30 meters above the ground in the
ment called the flame ionization detector
biosphere near Manaus, Brazil, in July and
(FID) to actually measure each of those sepa-
August of 1985. Tethered balloons were raised
rated analytes.
and lowered to predetermined heights and a
The power of gas chromatography stems
radio-controlled valve system was used to
from its ability to separate individual compo-
collect samples of biospheric gases in Teflon
nents of a mixture injected into the chromato-
bags. These gas samples were transferred to
graphic column and to use the FID to identify
stainless steel canisters and then returned for
the analytes as they exit the column one by
GC/FID analysis to the National Center for
one. The GC separation process occurs as the
Atmospheric Research (Zimmerman et al.,
gaseous compounds, under the influence of
1988).
the column’s temperature and chromatographic
surface and a flowing gas called the carrier gas or
mobile phase, undergo a series of nondestruc- Concentration (ppb)
tive interactions with the chromatographic Compound at 30 m above ground
surface as they pass through the column. Since
each compound to be separated—methane and Methane 1657
other atmospheric components in this case— Ethane 1.17
interacts to a slightly different extent with the Isoprene 2.56
column’s chromatographic surface, the result is b-pinene 0.03
a different transit time through the column for
Instrumental Determination of Atmospheric Methane 399
Carbon dioxide sampled from the atmo- The FID response to hydrocarbons is
sphere can also be determined very sensitively based on the detection of carbon-containing
with this method if the carbon dioxide is ions created in the combustion processes of
reduced to methane before FID analysis. This the FID’s flame, which is created by burning a
is easily accomplished by flowing the sample hydrogen/air mixture. This extremely sensi-
across a hot metal catalyst such as nickel. tive system can detect CH4 in the picogram
The GC/FID system shown in the dia- (1012 g) range, which translates into parts
gram below contains three basic parts: the per billion by volume in atmospheric gas
injector, chromatographic column, and detec- samples.
tor. The chromatographic column is plumbed The result of all chromatographic meth-
into the GC’s injector, where the mixture is ods is, in one form or another, a graphical
initially introduced into the column. The col- representation of the data called a chro-
umn—whose temperature is controlled by a matogram. This is most often a plot of reten-
small oven—terminates in the base of the tion time versus detector signal. Careful
FID, where each exiting analyte is detected. analysis of the chromatogram yields the
FID
detector
(+)
Electrometer Computer
(–)
H2 & air
Injector flame
Signal
GC Chromatogram
Oven
Time
Column
400 Environmental Instrumental Analysis II
Environmental Instrumental Determination

Instrumental
Analysis II
of Atmospheric Methane (continued)
identity, based on known standards, and quan- progress” for each of the stages is presented in
tity of each of the components in the original the lower panels.
atmospheric mixture. The figure below shows Methane production and emission from
a schematic of five stages in the chromato- biospheric sources is an important field of
graphic process, with the injector—where the study because of the importance of methane in
sample is introduced—at the top of the col- the enhanced greenhouse effect. As the inset
umn and the detector at the bottom. In reality, in Figure 6-8 shows, atmospheric carbon diox-
the GC column is 10 m or longer and is curled ide concentration varies in a seasonal “breath-
up inside the GC oven. A chromatogram “in ing pattern,” with a decrease in atmospheric
Injector Injector Injector Injector Injector

Chromatographic column
Detector Detector Detector Detector Detector

Detector signal
Detector signal
Detector signal
Detector signal
Detector signal
Time Time Time Time Time

Instrumental Determination of Atmospheric Methane 401
CO2 in the spring as it is taken up by plants the atmosphere, taking into account methane
and a CO2 increase in the fall as it is released and negative and positive CO2 fluxes. Inter-
from decaying organic matter. Since CH4 is estingly, workers performing these same kinds
also produced and consumed in the biosphere, of studies with soils taken from the Arctic
scientists are interested in following its pro- tundra and examined in the lab found that
duction and consumption in various biomes normally moist soils in central Siberia are a
such as lakes or permafrost. Recent work in net atmospheric sink for methane year-round
Asia using this GC/FID method has shown (Rodionow et al., 2005).
that the methane flux from a subtropical lake
References: Chemistry-Based Animations, 2006:
in southeastern China varies greatly with the http://www.shsu.edu/~chm_tgc/sounds/sound.html.
season, as does that of CO2 (Xing et al., 2005).
A. Rodionow, H. Flessa, O. Kazansky, and G. Guggen-
But while CO2 flux is positive (to the atmo- berger, “Organic Matter Composition and Potential
sphere) in autumn and winter and negative in Trace Gas Production of Permafrost Soils in the Forest
spring and summer, methane flux is positive Tundra in Northern Siberia,” Geoderma (2006).
year-round in this setting. Using a small gas- Y. Xing, P. Xie, H. Yang, L. Ni, Y. Wang, and K. Rong,
collection chamber at the surface of this lake “Methane and Carbon Dioxide Fluxes from a Shallow
(lake area: 27.9 km2), researchers found an Hypereutrophic Subtropical Lake in China,” Atmos-
pheric Environment 39 (2005): 5532–5540.
average flux of 23 mg CH4 per m2 per day. This
works out to an emission of approximately P. R. Zimmerman, J. P. Greenberg, and C. E. Westberg,
“Measurements of Atmospheric Hydrocarbons and
2.4 H 105 kg CH4 per year from that lake. And Biogenic Emission Fluxes in the Amazon Boundary
overall, this investigation showed that annu- Layer,” Journal of Geophysical Research 93(D2) (1988):
ally the lake contributed 7.5 105 kg carbon to 1407–1416.
A PR AGM ATI C PRO GR A M
L
Humanity faces a choice between two futures: doing nothing
to curb emissions (which poses huge climate risks) and bringing
them under control (which has costs but also benefits).
A Plan toKeep
Carbon
Getting a grip on greenhouse gases is daunting but doable.
in
Check
The technologies already exist. But there is no time to lose
BY ROBERT H. SOCOLOW AND STEPHEN W. PACALA
Retreating glaciers, stronger hurricanes, tion of CO2 that was in the atmosphere
hotter summers, thinner polar bears: the in the 18th century, before the Industrial
OVERVIEW ominous harbingers of global warming are Revolution began. Every increase in con-
E Humanity can emit driving companies and governments to centration carries new risks, but avoiding
only so much carbon work toward an unprecedented change in that danger zone would reduce the likeli-
dioxide into the
atmosphere before the the historical pattern of fossil-fuel use. hood of triggering major, irreversible cli-
climate enters a state Faster and faster, year after year for two mate changes, such as the disappearance
unknown in recent centuries, human beings have been trans- of the Greenland ice cap. Two years ago
geologic history and
goes haywire. Climate ferring carbon to the atmosphere from the two of us provided a simple frame-
scientists typically see below the surface of the earth. Today the work to relate future CO2 emissions to
the risks growing world’s coal, oil and natural gas industries this goal.
rapidly as CO2 levels
approach a doubling dig up and pump out about seven billion We contrasted two 50-year futures. In
of their pre-18th- tons of carbon a year, and society burns one future, the emissions rate continues to
century value. nearly all of it, releasing carbon dioxide grow at the pace of the past 30 years for
E To make the prob-
lem manageable, the (CO2). Ever more people are convinced the next 50 years, reaching 14 billion tons
required reduction in that prudence dictates a reversal of the of carbon a year in 2056. (Higher or
emissions can be present course of rising CO2 emissions. lower rates are, of course, plausible.) At
broken down into
“wedges”—an The boundary separating the truly that point, a tripling of preindustrial car-
dangerous consequences of emissions from bon concentrations would be very diffi-
KENN BROWN
incremental reduction
of a size that matches the merely unwise is probably located near cult to avoid, even with concerted efforts
available technology.
(but below) a doubling of the concentra- to decarbonize the world’s energy systems
Robert H. Socolow and Stephen W. Parcala, “A Plan to Keep

Carbon in Check,” Scientific American, September 2006, 50–57.
MANAGING THE CLIMATE PROBLEM
At the present rate of growth, emissions of carbon dioxide will double (below right)—a level widely regarded as capable of triggering
by 2056 (below left). Even if the world then takes action to level severe climate changes. But if the world flattens out emissions
them off, the atmospheric concentration of the gas will be headed beginning now and later ramps them down, it should be able to keep
above 560 parts per million, double the preindustrial value concentration substantially below 560 ppm.
ANNUAL EMISSIONS CUMULATIVE AMOUNT

In between the two emissions paths is the “stabilization triangle.” It represents the total Each part per million of CO2 corresponds
emissions cut that climate-friendly technologies must achieve in the coming 50 years. to a total of 2.1 billion tons of
14 atmospheric carbon. Therefore, the
Historic 560-ppm level would mean about 1,200
Delay action until 2056 billion tons, up from the current 800
Carbon Emitted (billion tons a year)
Begin action now billion tons. The difference of 400 billion

Stabilization triangle tons actually allows for roughly 800
billion tons of emissions, because half
the CO2 emitted into the atmosphere
7 enters the planet’s oceans and forests.
The two concentration trajectories
shown here match the two emissions
paths at the left.
1,600
Carbon in Atmosphere (billion tons)

0 1,400
1956 2006 2056 2106 Doubling of
Year preindustrial level
1,200
THE WEDGE CONCEPT 1,000

The stabilization triangle can be divided into seven 1 billion tons a year
“wedges,” each a reduction of 25 billion tons of carbon 800
emissions over 50 years. The wedge has proved to be 25 billion
a useful unit because its size and time frame match tons total
600
what specific technologies can achieve. Many combi- 1956 2006 2056 2106
nations of technologies can fill the seven wedges. 50 years Year
over the following 100 years. In To hold global emissions con- in 2056 as today, the carbon inten-
the other future, emissions are stant while the world’s economy sity will need to fall not half as fast
frozen at the present value of continues to grow is a daunting but fully as fast as the global econ-
seven billion tons a year for the task. Over the past 30 years, as the omy grows.
next 50 years and then reduced by gross world product of goods and Two long-term trends are cer-
about half over the following 50 services grew at close to 3 percent tain to continue and will help. First,
years. In this way, a doubling of a year on average, carbon emis- as societies get richer, the services
CO2 levels can be avoided. The sions rose half as fast. Thus, the sector—education, health, leisure,
difference between these 50-year ratio of emissions to dollars of banking and so on—grows in im-
JEN CHRISTIANSEN
emission paths—one ramping up gross world product, known as the portance relative to energy-intensive
and one flattening out—we called carbon intensity of the global econ- activities, such as steel production.
the stabilization triangle [see box omy, fell about 1.5 percent a year. All by itself, this shift lowers the
on this page]. For global emissions to be the same carbon intensity of an economy.
A Plan to Keep Carbon in Check 405
Second, deeply ingrained in now (starting from zero today). 60 mpg in 2056 even in a world
the patterns of technology evolu- For example, a car driven 10,000 that pays no attention to carbon
tion is the substitution of clever- miles a year with a fuel efficiency cannot count this improvement as
ness for energy. Hundreds of of 30 miles per gallon (mpg) emits a wedge, because it is already
power plants are not needed close to one ton of carbon annual- implicit in the baseline projection.
today because the world has ly. Transport experts predict that Moreover, you are allowed to
invested in much more efficient two billion cars will be zipping count only strategies that involve
refrigerators, air conditioners and along the world’s roads in 2056, the scaling up of technologies
motors than were available two each driven an average of 10,000 already commercialized some-
decades ago. Hundreds of oil and miles a year. If their average fuel where in the world. You are not
gas fields have been developed efficiency were 30 mpg, their allowed to count pie in the sky.
more slowly because aircraft tailpipes would spew two billion Our goal in developing the wedge
engines consume less fuel and the framework was to be pragmatic
windows in gas-heated homes and realistic—to propose engineer-
leak less heat. ing our way out of the problem
The task of holding global Holding carbon and not waiting for the cavalry to
emissions constant would be out dioxide emissions come over the hill. We argued that
of reach, were it not for the fact even with these two counting rules,
that all the driving and flying in
constant for the world can fill all seven wedges,
2056 will be in vehicles not yet 50 years, without and in several different ways
designed, most of the buildings [see box on page 407]. Individual
that will be around then are not
choking off countries—operating within a
yet built, the locations of many of economic growth, framework of international coop-
the communities that will contain is within eration—will decide which wedges
these buildings and determine to pursue, depending on their insti-
their inhabitants’ commuting pat-
our grasp. tutional and economic capacities,
terns have not yet been chosen, natural resource endowments and
and utility owners are only now political predilections.
beginning to plan for the power tons of carbon that year. At 60 To be sure, achieving nearly
plants that will be needed to light mpg, they would give off a billion every one of the wedges requires
up those communities. Today’s tons. The latter scenario would new science and engineering to
notoriously inefficient energy sys- therefore yield one wedge. squeeze down costs and address
tem can be replaced if the world the problems that inevitably
gives unprecedented attention Wedges accompany widespread deploy-
to energy efficiency. Dramatic IN OUR FRAMEWORK , you are ment of new technologies. But
changes are plausible over the allowed to count as wedges only holding CO2 emissions in 2056 to
next 50 years because so much of those differences in two 2056 their present rate, without choking
the energy canvas is still blank. worlds that result from deliberate off economic growth, is a desirable
To make the task of reducing carbon policy. The current pace of outcome within our grasp.
emissions vivid, we sliced the sta- emissions growth already includes Ending the era of conventional
bilization triangle into seven equal some steady reduction in carbon coal-fired power plants is at the
pieces, or “wedges,” each repre- intensity. The goal is to reduce it very top of the decarbonization
senting one billion tons a year of even more. For instance, those agenda. Coal has become more
averted emissions 50 years from who believe that cars will average competitive as a source of power
406 A Plan to Keep Carbon in Check
and fuel because of energy security So cutting buildings’ electricity use in a carbon-constrained world,
concerns and because of an in half—by equipping them with coal mining and coal power can
increase in the cost of oil and gas. superefficient lighting and appli- stay in business, thanks to carbon
That is a problem because a coal ances—could lead to two wedges. capture and storage.
power plant burns twice as much Another wedge would be achieved The large natural gas power
carbon per unit of electricity as a if industry finds additional ways to plants operating in 2056 could cap-
natural gas plant. In the absence of use electricity more efficiently. ture and store their CO2, too, per-
a concern about carbon, the haps accounting for yet another
world’s coal utilities could build a wedge. Renewable and nuclear
few thousand large (1,000-
Decarbonizing the Supply energy can contribute as well.
megawatt) conventional coal plants EVEN AFTER energy-efficient tech- Renewable power can be produced
in the next 50 years. Seven hundred nology has penetrated deeply, the from sunlight directly, either to
such plants emit one wedge’s worth world will still need power plants. energize photovoltaic cells or, using
of carbon. Therefore, the world They can be coal plants but they focusing mirrors, to heat a fluid and
could take some big steps toward will need to be carbon-smart ones drive a turbine. Or the route can be
the target of freezing emissions by that capture the CO2 and pump it indirect, harnessing hydropower
not building those plants. The time into the ground [see “Can We Bury and wind power, both of which rely
to start is now. Facilities built in Global Warming?” by Robert H. on sun-driven weather patterns.
this decade could easily be around Socolow; SCIENTIFIC AMERICAN, The intermittency of renewable
in 2056. July 2005]. Today’s high oil prices power does not diminish its capac-
Efficiency in electricity use is are lowering the cost of the transi- ity to contribute wedges; even if
the most obvious substitute for tion to this technology, because coal and natural gas plants provide
coal. Of the 14 billion tons of car- captured CO2 can often be sold to the backup power, they run only
bon emissions projected for 2056, an oil company that injects it into part-time (in tandem with energy
perhaps six billion will come from oil fields to squeeze out more oil; storage) and use less carbon than if
producing power, mostly from thus, the higher the price of oil, the they ran all year. Not strictly
coal. Residential and commercial more valuable the captured CO2. renewable, but also usually includ-
buildings account for 60 percent of To achieve one wedge, utilities ed in the family, is geothermal
global electricity demand today need to equip 800 large coal plants energy, obtained by mining the
(70 percent in the U.S.) and will to capture and store nearly all the heat in the earth’s interior. Any of
consume most of the new power. CO2 otherwise emitted. Even these sources, scaled up from its
current contribution, could pro-
ROBERT H. SOCOLOW and STEPHEN W. PACALA lead the Carbon Mitigation duce a wedge. One must be careful
Initiative at Princeton University, where Socolow is a mechanical engi- not to double-count the possibili-
neering professor and Pacala an ecology professor. The initiative is fund- ties; the same coal plant can be left
THE AUTHORS
ed by BP and Ford. Socolow specializes in energy-efficient technology, unbuilt only once.

global carbon management and carbon sequestration. He was co-editor Nuclear power is probably the
(with John Harte) of Patient Earth, published in 1971 as one of the first most controversial of all the wedge
college-level presentations of environmental studies. He is the recipient strategies. If the fleet of nuclear
of the 2003 Leo Szilard Lectureship Award from the American Physical power plants were to expand by a
Society. Pacala investigates the interaction of the biosphere, atmosphere factor of five by 2056, displacing
and hydrosphere on global scales, with an emphasis on the carbon cycle. conventional coal plants, it would
He is director of the Princeton Environmental Institute. provide two wedges. If the current
15 WAYS TO MAKE A WEDGE
An overall carbon strategy for the next half a century produces seven wedges’ worth of emissions reductions. Here are 15 technologies
from which those seven can be chosen (taking care to avoid double-counting). Each of these measures, when phased in over 50 years,
prevents the release of 25 billion tons of carbon. Leaving one wedge blank symbolizes that this list is by no means exhaustive.
S ER V A T IO N
D CON AG
C Y A
N 1 R IC
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15
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A R C
Notes:
1 World fleet size in 2056 could well be two billion cars. Assume they average production. Assume half of carbon originally in the coal is captured.
10,000 miles a year. 7 Assume wind and solar produce, on average, 30 percent of peak power. Thus
2 “Large” is one-gigawatt (GW) capacity. Plants run 90 percent of the time. replace 2,100 GW of 90-percent-time coal power with 2,100 GW (peak) wind or
3 Here and below, assume coal plants run 90 percent of the time at 50 percent solar plus 1,400 GW of load-following coal power, for net displacement of 700 GW.
efficiency. Present coal power output is equivalent to 800 such plants. 8 Assume 60-mpg cars, 10,000 miles a year, biomass yield of 15 tons a hectare,
4 Assume 90 percent of CO is captured. and negligible fossil-fuel inputs. World cropland is 1,500 million hectares.
JANET CHAO
2
5 Assume a car (10,000 miles a year, 60 miles per gallon equivalent) requires 9 Carbon emissions from deforestation are currently about two billion tons
170 kilograms of hydrogen a year. a year. Assume that by 2056 the rate falls by half in the business-as-usual
6 Assume 30 million barrels of synfuels a day, about a third of today’s total oil projection and to zero in the flat path.
fleet were to be shut down and be a product of crop residues or powered car emits the same
replaced with modern coal plants dedicated crops, hydrogen made amount of CO2 as a gasoline-
without carbon capture and stor- from low-carbon electricity, or powered car, but synfuel fabrica-
age, the result would be minus low-carbon electricity itself, charg- tion from coal spews out far more
one-half wedge. Whether nuclear ing an onboard battery. Sources of carbon than does refining gasoline
power will be scaled up or down the low-carbon electricity could from crude oil—enough to double
will depend on whether govern- include wind, nuclear power, or the emissions per mile of driving.
ments can find political solutions coal with capture and storage. From the perspective of mitigating
to waste disposal and on whether Looming over this task is the climate change, it is fortunate that
plants can run without accidents. prospect that, in the interest of the emissions at a synfuels plant
(Nuclear plants are mutual can be captured and stored. If
hostages: the world’s least well- business-as-usual trends did lead
run plant can imperil the future of to the widespread adoption of
all the others.) Also critical will be
strict rules that prevent civilian
nuclear technology from becom-
39 percent synfuel, then capturing CO2 at
synfuels plants might well pro-
duce a wedge.
ing a stimulus for nuclear weapons
U.S. share of global Not all wedges involve new
development. These rules will have carbon emissions energy technology. If all the farm-
to be uniform across all countries, in 1952 ers in the world practiced no-till
so as to remove the sense of a dou- agriculture rather than conven-
ble standard that has long been a
spur to clandestine facilities.
23 percent tional plowing, they would con-
tribute a wedge. Eliminating
Oil accounted for 43 percent U.S. share in 2002 deforestation would result in two
of global carbon emissions from wedges, if the alternative were for
fossil fuels in 2002, while coal The U.S. share of deforestation to continue at cur-
accounted for 37 percent; natural rent rates. Curtailing emissions of
gas made up the remainder. More
global emissions methane, which today contribute
than half the oil was used for can be expected to about half as much to greenhouse
transport. So smartening up elec- continue to drop. warming as CO2, may provide
tricity production alone cannot fill more than one wedge: needed is a
the stabilization triangle; trans- deeper understanding of the
portation, too, must be decar- anaerobic biological emissions
bonized. As with coal-fired elec- energy security, the transport sys- from cattle, rice paddies and irri-
tricity, at least a wedge may be tem could become more carbon- gated land. Lower birth rates can
available from each of three com- intensive. That will happen if produce a wedge, too—for exam-
plementary options: reduced use, transport fuels are derived from ple, if they hold the global popu-
improved efficiency and decar- coal instead of petroleum. Coal- lation in 2056 near eight billion
bonized energy sources. People can based synthetic fuels, known as people when it otherwise would
take fewer unwanted trips (tele- synfuels, provide a way to reduce have grown to nine billion.
commuting instead of vehicle global demand for oil, lowering its
commuting) and pursue the travel cost and decreasing global depen- Action Plan
they cherish (adventure, family vis- dence on Middle East petroleum. WHAT SET OF POLICIES will yield
its) in fuel-efficient vehicles running But it is a decidedly climate- seven wedges? To be sure, the
on low-carbon fuel. The fuel can unfriendly strategy. A synfuel- dramatic changes we anticipate
RICH WORLD, POOR WORLD
To keep global emissions constant, both developed nations (defined here as members of the Organization for Economic
Cooperation and Development, or OECD) and developing nations will need to cut their emissions relative to what they would have
been (arrows in graphs below). The projections shown represent only one path the world could take; others are also plausible.
15%
12%
28% 14%
10%
Share of CO2
emissions in 2002 8%
4% 4% 6%
IN TRENDS: A COMPENDIUM OF DATA ON GLOBAL CHANGE. CARBON DIOXIDE INFORMATION ANALYSIS CENTER, OAK RIDGE NATIONAL LABORATORY, 2006
JEN CHRISTIANSEN; SOURCE: "GLOBAL, REGIONAL, AND NATIONAL FOSSIL FUEL CO2 EMISSIONS,” BY G. MARLAND, T. A. BODEN AND R. J. ANDRES,
To hold global emissions flat, the . . . to let non-OECD nations emit more
OECD must emit less than today ... as they develop economically OECD
Carbon Emissions (billion tons a year)
Current trend North America and Mexico

Constant global Europe
8 emissions 8
East Asia and Oceania
Cut
NON-OECD
South/Southeast Asia
4 4 Africa
Cut
East Asia
Former Soviet Bloc
West Asia
0 0 Central America and South America
2002 2052 2002 2052
Year Year
in the fossil-fuel system, includ- coal plants to capture and store also was the price of CO2 emis-
ing routine use of CO2 capture CO2 rather than vent it. The sions in the European Union’s
and storage, will require institu- price might fall as technologies emissions trading system for
tions that reliably communicate climb the learning curve. A car- nearly a year, spanning 2005
a price for present and future bon emissions price of $100 per and 2006. (One ton of carbon is
carbon emissions. We estimate ton is comparable to the current carried in 3.7 tons of carbon
that the price needed to jump- U.S. production credit for new dioxide, so this price is also $27
start this transition is in the ball- renewable and nuclear energy per ton of CO2.) Based on car-
park of $100 to $200 per ton of relative to coal, and it is about bon content, $100 per ton of
carbon—the range that would half the current U.S. subsidy of carbon is $12 per barrel of oil
make it cheaper for owners of ethanol relative to gasoline. It and $60 per ton of coal. It is
25 cents per gallon of gasoline industrial nations—the members opposed to five times as much
and two cents per kilowatt-hour of the Organization for Economic today. The U.S. could meet this
of electricity from coal. Cooperation and Development goal in many ways [see illustra-
But a price on CO2 emissions, (OECD)—account for almost tion on facing page]. These
on its own, may not be enough. exactly half the planet’s CO2 emis- strategies will be followed by
Governments may need to stimu- sions, and the developing countries most other countries as well. The
late the commercialization of low- plus the nations formerly part of resultant cross-pollination will
carbon technologies to increase the the Soviet Union account for the lower every country’s costs.
number of competitive options other half. In a world of constant Fortunately, the goal of decar-
available in the future. Examples total carbon emissions, keeping the bonization does not conflict with
include wind, photovoltaic power OECD’s share at 50 percent seems the goal of eliminating the world’s
and hybrid cars. Also appropriate impossible to justify in the face of most extreme poverty. The extra
are policies designed to prevent the the enormous pent-up demand for carbon emissions produced when
construction of long-lived capital energy in the non-OECD coun- the world’s nations accelerate the
facilities that are mismatched to tries, where more than 80 percent delivery of electricity and modern
future policy. Utilities, for instance, of the world’s people live. On the cooking fuel to the earth’s poorest
need to be encouraged to invest in other hand, the OECD member people can be compensated for by,
CO2 capture and storage for new states must emit some carbon in at most, one fifth of a wedge of
coal power plants, which would be 2056. Simple arithmetic indicates emissions reductions elsewhere.
very costly to retrofit later. Still that to hold global emissions rates
another set of policies can harness steady, non-OECD emissions can-
the capacity of energy producers to not even double.
Beyond 2056
promote efficiency—motivating One intermediate value results THE STABILIZATION triangle deals
power utilities to care about the if all OECD countries were to meet only with the first 50-year leg of
installation and maintenance of the emissions-reduction target for the future. One can imagine a relay
efficient appliances, natural gas the U.K. that was articulated in race made of 50-year segments, in
companies to care about the build- 2003 by Prime Minister Tony which the first runner passes a
ings where their gas is burned, and Blair—namely, a 60 percent reduc- baton to the second in 2056. Inter-
oil companies to care about the tion by 2050, relative to recent lev- generational equity requires that
engines that run on their fuel. els. The non-OECD countries the two runners have roughly
To freeze emissions at the cur- could then emit 60 percent more equally difficult tasks. It seems to
rent level, if one category of emis- CO2. On average, by midcentury us that the task we have given the
sions goes up, another must come they would have one half the per second runner (to cut the 2056
down. If emissions from natural capita emissions of the OECD emissions rate in half between
gas increase, the combined emis- countries. The CO2 output of 2056 and 2106) will not be harder
sions from oil and coal must every country, rich or poor today, than the task of the first runner (to
decrease. If emissions from air would be well below what it is gen- keep global emissions in 2056 at
travel climb, those from some erally projected to be in the present levels)—provided that
other economic sector must fall. absence of climate policy. In the between now and 2056 the world
And if today’s poor countries are case of the U.S., it would be about invests in research and develop-
to emit more, today’s richer coun- four times less. ment to get ready. A vigorous
tries must emit less. Blair’s goal would leave the effort can prepare the revolution-
How much less? It is easy to average American emitting twice ary technologies that will give the
bracket the answer. Currently the as much as the world average, as second half of the century a
A Plan to Keep Carbon in Check 411
running start. Those options could

include scrubbing CO2 directly ONE PLAN FOR THE U.S.
from the air, carbon storage in Savings from:
minerals, nuclear fusion, nuclear 3.0 Electricity end-use efficiency
thermal hydrogen, and artificial Other end-use efficiency
Passenger vehicle efficiency
photosynthesis. Conceivably, one 2.5
Carbon Emissions (billion tons a year)

Other transport efficiency
or more of these technologies may Renewables
arrive in time to help the first run- Carbon capture and storage
ner, although, as we have argued, 2.0
the world should not count on it.

As we look back from 2056, if 1.5
global emissions of CO2 are indeed
no larger than today’s, what will
have been accomplished? The 1.0
world will have confronted energy

production and energy efficiency at 0.5
the consumer level, in all economic
sectors and in economies at all lev-
els of development. Buildings and 0
1996 2016 2036 2056
lights and refrigerators, cars and Year
trucks and planes, will be trans-
formed. Transformed, also, will be L U.S. share of emissions reductions could, in this Natural Resources Defense
Council scenario, be achieved by efficiency gains, renewable energy and clean coal.
the ways we use them.
The world will have a fossil-
fuel energy system about as large
JEN CHRISTIANSEN; SOURCE: DANIEL A. LASHOF AND DAVID G. HAWKINS Natural Resources Defense Council
as today’s but one that is infused

have come into being to control treasure, innovation and energy
with modern controls and
the spread of nuclear technolo- to ward off rising sea level,
advanced materials and that is
gy from energy to weapons. heat, hurricanes and drought.
almost unrecognizably cleaner.
Economic growth will have Critically, a planetary con-
There will be integrated produc-
been maintained; the poor and sciousness will have grown.
tion of power, fuels and heat;
the rich will both be richer. Humanity will have learned to
greatly reduced air and water pol-
And our descendants will not address its collective destiny—
lution; and extensive carbon cap-
be forced to exhaust so much and to share the planet.
ture and storage. Alongside the
fossil energy system will be a non-
fossil energy system approximately MORE TO EXPLORE
as large. Extensive direct and indi-
Stabilization Wedges: Solving the Climate Problem for the Next 50 Years with Current
rect harvesting of renewable ener-
Technologies. S. Pacala and R. Socolow in Science, Vol. 305, pages 968–972; August
gy will have brought about the 13, 2004.
revitalization of rural areas and the
The calculations behind the individual wedges are available at
reclamation of degraded lands. If www.princeton.edu/cmi
nuclear power is playing a large Energy statistics are available at www.eia.doe.gov, www.iea.org and www.bp.com;
role, strong international carbon emissions data can also be found at cdiac.esd.ornl.gov
enforcement mechanisms will
PART III
TOXIC ORGANIC
COMPOUNDS
Contents of Part III
Chapter 10 Pesticides
Chapter 11 Dioxins, Furans, and PCBs
Chapter 12 Other Toxic Organic Compounds
of Environmental Concern
Environmental Instrumental Analysis III

 Electron Capture Detection of Pesticides
Environmental Instrumental Analysis IV

 Gas Chromatography/Mass Spectrometry (GC/MS)

 Tackling Malaria
C H A P T E R
10
PESTICIDES
topics are used:
 Elementary organic chemistry (as in the Appendix in this
book)
 Concepts of vapor pressure; solubility; half-life; chemical
versus physical change; enzymes; acids and bases
 Molarity

 Photochemical reactions (Chapters 1, 3, 5)
 Adsorption (Chapter 4)
Introduction
The term synthetic chemical is used to describe substances that generally do
not occur in nature but have been synthesized by chemists from simpler sub-
stances. The great majority of commercial synthetic chemicals are organic
compounds, and most use petroleum or natural gas as the original source of
their carbon.
In Chapters 10, 11, and 12, the environmental consequences of the wide-
spread use of synthetic organic chemicals are discussed. Our emphasis will be
on those substances whose toxicity has led to concerns regarding human
health, as well as the well-being of lower organisms.
In this chapter, we discuss pesticides, considering the environmental
problems associated with their use and some general principles of toxicology
that apply to their effects on human health. In Chapters 11 and 12, nonpes-
ticidal organic compounds of environmental concern are described.
Types of Pesticides
Pesticides are substances that kill or otherwise control an unwanted organ-
ism. The most common categories of pesticides are listed in Table 10-1. All
415
416 Chapter 10 Pesticides
Pesticides and Their

TABLE 10-1 Targets
Pesticide Type Target Organism
Acaricide Mites
Algicide Algae
Avicide Birds
Bactericide Bacteria
Disinfectant Microorganisms
Fungicide Fungi
Herbicide Plants
Insecticide Insects
Larvicide Insect larvae
Molluscicide Snails, slugs
Nematicide Nematodes
Piscicide Fish
Rodenticide Rodents
Termiticides Termites
chemical pesticides share the common property of blocking a vital metabolic

process of the organism to which they are toxic. In this chapter, we discuss first
insecticides—substances that kill insects—and then herbicides—compounds
that kill plants. Also mentioned in passing are some fungicides, substances
that are used to control the growth of various types of fungus, especially to
protect stored seeds before planting. Collectively, these three categories repre-
sent the great bulk of the 1 billion kilograms of pesticides that are used annu-
ally in North America.
About half of the usage of pesticides in North America involves agricul-
ture; worldwide the figure rises to 85%. Almost all commercial food crops are
now produced with the use of synthetic insecticides, herbicides, and fungi-
cides, except of course in organic farming, where natural pesticides are used.
Indeed, the current ability to produce and harvest large amounts of food on
relatively small amounts of land with a relatively small input of human labor
has been made possible by the use of pesticides. Currently, the greatest U.S.
use of insecticides occurs in the growing of cotton, whereas the majority of
herbicides are used in the growing of corn and soybeans. Recently the appli-
cation of insecticides to cotton has been significantly reduced by the intro-
duction of cotton that has been genetically modified to incorporate resistance
Introduction 417
to insects, in particular the bollworm. Depending upon the main crops they
produce, countries vary in what types of pesticides they consume in large
amounts. For example, herbicides account for three-quarters of pesticide use
in Malaysia, whereas insecticides are the most widely used pesticides in India
and the Philippines, as are fungicides in Colombia.
Some 80–90% of American domestic households contain at least one
synthetic pesticide; typical examples are weed killers for the lawn and garden,
algae controls for the swimming pool, flea powders for use on pets, and sprays
to kill insects such as cockroaches.
Almost since their introduction, synthetic pesticides have been a con-
cern because of the potential impact on human health of eating food contam-
inated with these chemicals. Half the foods eaten in the United States
contain measurable levels of at least one pesticide. For that reason, many
have been banned or restricted in their use. Nevertheless, the U.S. National
Academy of Science has pointed out that pesticide regulation to date has not
paid enough attention to the protection of human health, especially that of
infants and children, whose growth and development are at stake. Children,
kilogram for kilogram, eat more food than adults and tend to eat more foods
(such as apples, grapes, and carrots) with higher pesticide levels than do adults,
and their internal organs—including the brain—are still developing and
maturing, thereby making them more vulnerable to any negative effects these
chemicals may have. In addition, small children play on floors and lawns and
put many objects in their mouths, increasing their exposure to pesticides used
in homes and yards.
Some scientists dismiss these concerns by emphasizing that living plants
themselves manufacture insecticides in order to discourage insects and fungi
from consuming them, and consequently we are exposed in our food supply to
much higher concentrations of these natural pesticides than to synthetic
ones. Natural pesticides are not necessarily less toxic than are synthetic ones,
as we shall see.
Traditional Insecticides
Insecticides of one type or another have been used by society for thousands of
years. One principal motivation for using insecticides is to control disease:
Human deaths due to insect-borne diseases through the ages have greatly
exceeded those attributable to warfare. The use of insecticides has greatly
reduced the incidence of diseases transmitted by insects and the rodents
which bear them: malaria, yellow fever, bubonic plague, sleeping sickness,
and, recently, illness from the West Nile virus scarcely exhaust the list of these
scourges. The other principal motivation for insecticide usage is to prevent
insects from attacking food crops; nevertheless, even with extensive use of
pesticides, about one-third of the world’s total crop yield is destroyed by pests
or weeds during growth, harvesting, and storage. People also try to control
insects such as the mosquito and the common fly simply because their pres-
ence is annoying.
The earliest recorded usage of pesticides was the burning of sulfur to
fumigate Greek homes around 1000 B.C. Fumigants are pesticides that
enter the insect as an inhaled gas. The use of sulfur dioxide, SO2, from the
burning of solid sulfur, sometimes by incorporating the element in candles,
continued at least into the nineteenth century. Sulfur itself, in the form of
dusts and sprays, was also used as an insecticide and as a fungicide; it is
still employed as a fumigant against powdery mildew on plants. Inorganic
fluorides, such as sodium fluoride, NaF, were used domestically to control ant
populations. Both sodium fluoride and boric acid were used to kill cockroaches
in infested buildings. Various oils, whether derived from petroleum or from
living sources such as fish and whales, have been utilized for hundreds of years
as insecticides and as dormant sprays to kill insect eggs.
The use of arsenic and its compounds to control insects dates back to
Roman times. It was employed by the Chinese in the sixteenth century and
became quite widespread from the late nineteenth century until World War II.
Arsenic-containing salts have also been used as stomach poisons, and they
kill insects that ingest them. Arsenic compounds, which continued to be
heavily used as insecticides into the early 1950s, are discussed in more detail
in Chapter 15.
Unfortunately, most inorganic and metal-containing organic pesticides
are quite toxic to humans and other mammals, especially at the dosage levels
that are required to make them effective as pesticides. Mass poisonings have
occurred as a result of the use of some mercury-based fungicides, as will be dis-
cussed in Chapter 15. In addition, toxic metals and semimetals, such as the
arsenic commonly used in pesticides, are not biodegradable: Once released
into the environment, they will remain indefinitely in the water, wildlife, soil,
or sediments and may enter the food supply if liberated from these sites.
Organochlorine Insecticides
Organic insecticides developed during and after World War II have largely
displaced these inorganic and metal-organic substances. Usually only small
amounts of the organic compounds are required to be effective against the
target pests, so smaller amounts of chemicals enter the environment. Given a
dose of any of these compounds large enough to act as a pesticide, the organic
substances are generally much less toxic to humans than are the inorganic and
metal-organic pesticides. Pesticide formulations containing only organic
compounds were initially thought to be biodegradable, though as we shall see,
this has certainly not been found to be true in many cases.
In the 1940s and the 1950s, the chemical industries in North America
and western Europe produced large quantities of many new pesticides, espe-
cially insecticides. The active ingredients in most of these pesticides were
Introduction 419
organochlorines, which are organic compounds that contain chlorine. Many

organochlorines share several notable properties:
• stability against decomposition or degradation in the environment;
• very low solubility in water, unless oxygen or nitrogen is also present in
the molecules;
• high solubility in hydrocarbon-like environments, such as the fatty
material in living matter;
• relatively high toxicity to insects, but low toxicity to humans.
As an example of an organochlorine pesticide, consider hexachloroben-
zene (HCB), C6Cl6. The compound is stable, easy to prepare from chlorine
and benzene, and for several decades after World War II it found use as an
agricultural fungicide for cereal crops. Since it is extremely persistent and is
still emitted as a by-product in the chemical industry and in combustion
processes, it remains a widespread environmental contaminant. It is of con-
cern because it causes liver cancer in laboratory rodents and therefore per-
haps also in humans. Our current daily exposure to HCB is not sufficient
to pose a significant health hazard, even though it is estimated that 99% of
Americans have detectable levels of the chemical in their body fat.
Cl
Cl Cl
Cl Cl
Cl
hexachlorobenzene (HCB)
Hexachlorobenzene is one of the 12 chemicals, the “dirty dozen,” listed by

the United Nations Environmental Programme as persistent organic pollu-
tants, or POPs, which are being banned or phased out by international
agreement (see Table 10-2). Each country signing the Stockholm Treaty that
bans these POPs must develop its own implementation plan. Other com-
pounds with the same negative characteristics as the dirty dozen may be added
later to the list.
Another chlorinated benzene, namely the 1,4 isomer of dichloroben-
zene, is used as an insecticidal fumigant. It is used in one type of domestic
mothball and as a deodorizer in restroom urinals, garbage pails, and so on.
Although it is a crystalline solid, it has an appreciable vapor pressure. Conse-
quently, enough of it will vaporize to act as an effective insecticide in the
immediate area around the solid. The same compound has also been used as
a soil fumigant. However, it is an animal carcinogen and accumulates to some
extent in the environment. It may well be the chemical responsible for the
U.N.’s Persistent Organic Pollutants (POP) “Dirty Dozen”

TABLE 10-2 and Their Status in Several Countries
POP U.S. Canada U.K. Mexico China India Use
DDT X X X R R R Mosquitoes
Aldrin X X X X OK OK Termites
Dieldrin X X X X OK R Crops
Endrin X X X X OK X Rodents
Chlordane R X X OK R OK Termites
Heptachlor R X X X OK OK Soil insects
Hexachloro- X X X Fungicide
benzene
Mirex X X R R Ants, termites
Toxaphene X X X X OK X Ticks, mites
PCBs* X R R OK Many uses
Dioxins* BP BP BP BP BP BP
Furans* BP BP BP BP BP BP
Codes: *not pesticides; X banned or no registered uses; R severely restricted uses only; OK not restricted; BP by-product,
not produced deliberately.
greatest carcinogenic risk of all indoor VOCs (volatile organic compounds;

see Chapter 3). Recent research indicates that it is present in the blood of
most U.S. residents; its presence at high levels is associated with reduced pul-
monary function.
Pesticides in Water
The solubilities of trace substances such as HCB in liquids and solids are often
expressed on a “parts per” scale, rather than on a mass or moles per unit volume
basis. However, the “parts per” scales for condensed (nongaseous) media express
the ratio of the mass of the solute to the mass of the solution, not the ratio of
moles or molecules that is used for gases. Since the mass of 1 liter of a natural
water sample is very close to 1 kilogram, the HCB solubility of 0.0062 milli-
grams solute per liter corresponds to 0.0062 mg solute per 1000 grams of solu-
tion. Multiplying both numerator and denominator by 1000, we conclude that
0.0062 mg/L is equivalent to 0.0062 grams of solute per 1 million grams of solu-
tion, i.e., to 0.0062 parts per million. In general, the value for the ppm solubility of
any trace substance in water is the same as its value in units of milligrams per liter or
micrograms per gram. Similarly, the ppb scale in aqueous solutions is equivalent
to micrograms per liter, or nanograms per gram.
DDT 421
Another commonly used set of units for trace contaminants—

particularly for substances dissolved in a medium such as soil or a biological
specimen—is micrograms (of the contaminant) per gram (of the medium),
␮g/g. For example, the concentration of a pesticide in human fat could be
listed as 2.0 ␮g/g. However, this scale is equivalent to that of parts per mil-
lion, which can be seen by multiplying the numerator and denominator
of ␮g/g by 1 million, giving grams per million grams. Similarly, the
nanograms per gram (ng/g) scale is equivalent to parts per billion.
P R O B L E M 10-1
For aqueous solutions, (a) convert 0.04 ␮g/L to the ppm and ppb scales,
(b) convert 3 ppb to the ␮g/L scale, and (c) convert 0.30 ␮g/g to the ppb scale.
The pollution of aquatic environments is not merely a question of the con-

centration of pollutant actually dissolved in solution, and the small values for
the water solubilities of organochlorines may be deceptive on this score. Most
organochlorine compounds are much more soluble in organic media than in
water. In bodies of water such as rivers and lakes, organochlorines are much
more likely to be adsorbed on the surfaces of organic particulate matter sus-
pended in the water and on the muddy sediments at the bottom than to be
dissolved in the water itself. From these surfaces, they enter living organisms
such as fish. For reasons discussed in detail later, their concentration in fish is
often thousands or millions of times greater than in polluted drinking water. It is
due to this phenomenon that concentrations of organochlorines have often
reached dangerous levels in many species. Many organochlorine insecticides
have been removed from use as a consequence. For humans, the amount of
organochlorines ingested by eating a single lake fish is generally greater than the
total organochlorine acquired in a lifetime of drinking water from the same lake!
DDT
DDT, or para-dichlorodiphenyltrichloroethane, has had a tumultuous his-
tory as an insecticide, as discussed in detail in the online Case Study To Ban
or Not to Ban DDT? Its History and Future.
Unfortunately, following its introduction during World War II, DDT was
widely overused in the 1950s and 1960s, particularly in agriculture, which
consumed 70–80% of its production in the United States, and in forestry. As
a result, its environmental concentration rose rapidly and it began to affect
the reproductive abilities of birds that indirectly incorporated it into their
bodies. By 1962, DDT was being called an “elixir of death” by the writer
Rachel Carson in her influential book Silent Spring because of its role in
decreasing the populations of birds such as the bald eagle, whose dietary
intake of the chemical was very high.
DDT’s Structure
Structurally, a DDT molecule is a substituted ethane. At one carbon, all three
hydrogens are replaced by chlorine atoms, while at the other, two of the three
hydrogens are replaced by a benzene ring. Each ring contains a chlorine atom
at the para position, i.e., directly opposite the ring carbon that is joined to the
(shaded) ethane unit:
Cl
Cl 9 C 9 Cl
Cl C Cl
H
(DDT): para-dichlorodiphenyltrichloroethane
Many animal species metabolize (convert by biochemical reactions into

other substances) DDT by the elimination of HCl; a hydrogen atom is removed
from one ethane carbon and a chlorine atom from the other, thereby creating a
derivative of ethene called DDE, dichlorodiphenyldichloroethene:
Cl Cl
C
Cl C Cl
DDE
Substances that are produced by the metabolism of a chemical are called

metabolites; thus DDE is a metabolite of DDT. The chemical DDE is also
produced slowly in the environment by the degradation of DDT under alka-
line conditions and by DDT-resistant insects that detoxify DDT by this
transformation. Unfortunately, in some birds DDE interferes with the enzyme
that regulates the distribution of calcium, so contaminated birds produce eggs
that have shells (calcium carbonate) too thin to withstand the weight of the
parents who sit on them to hatch them.
P R O B L E M 10-2
The structures shown for DDT and DDE have both the ring chlorines in the
para position, and are sometimes labeled p,p
-DDT and p,p
-DDE, where the
p and p
prefixes refer to the para chlorine positions in the first and second
rings, respectively. Deduce the structures and the appropriate labels for all the
other unique isomers of both DDT and DDE in which there is one chlorine
atom on each ring. Note that the two rings are equivalent, so that, e.g.,
o,m
-DDT is the same compound as is m,o
-DDT.
DDT 423
DDE in Body Fat

DDT’s persistence made it an ideal insecticide: one spraying gave protection
from insects for weeks to years, depending upon the method of application.
Its persistence is due to
• its low vapor pressure and its consequent slow rate of evaporation;
• its low reactivity with respect to light and to chemicals and
microorganisms in the environment; and
• its very low solubility in water.
Its rate of evaporation from the upper layer of soil in southern Canada, for
example, is so slow that its volatilization half-life is about 200 years. Like
other organochlorine insecticides, DDT is soluble in organic solvents and
therefore in the fat of animal tissue. DDT and/or its degradation products
have been found in all birds and fish that have been analyzed, even those liv-
ing in deserts or ocean depths.
We all have some “DDT” (to the extent of about 3 ppm for North
American adults) stored in our body fat. In humans, most ingested DDT is
slowly but eventually eliminated. Most of the “DDT” stored in human fat is
actually the DDE that was present in the food we have eaten, having previ-
ously been converted from DDT that was originally in the environment.
Unfortunately DDE is almost nondegradable biologically and is very fat-
soluble, so it remains in our bodies for a long time.
DDT Levels in Modern Times

For environmental reasons, DDT is now banned from use in most Western
industrialized countries. Its use had been declining anyway as resistant insect
populations evolved that metabolized DDT to the noninsecticidal DDE and
thus rendered it inactive. The United Nations includes DDT on its list of
twelve persistent organic pollutants (Table 10-2). Of the dozen, only DDT
will not be totally banned. One permitted use is in the production of dicofol,
a miticide whose molecular structure is identical except that DDT’s remain-
ing hydrogen atom on the ethane unit is replaced by a hydroxyl group, 9OH.
A controversial exception to the ban on DDT is for its use in control-
ling mosquitoes involved in the transmission of malaria. The issues in this
debate are explored in the online Case Study To Ban or Not to Ban DDT? Its
History and Future.
DDT and DDE still enter the environment everywhere as a result of
long-range air transport—a topic discussed at length in Chapter 12—from
developing countries where DDT is still in use to control malaria and typhus
and for some agricultural purposes. DDT also continues to be degassed from
soils in developed countries where it was used for agricultural purposes
decades ago.
Thanks to restrictions and bans, the environmental concentrations of

DDT and DDE in developed countries dropped substantially in the early and
middle years of the 1970s and have now become stabilized at low levels, that
of DDT itself being very small. The concentration of DDT itself declined more
rapidly than that of its metabolites such as DDE. Nevertheless, as a result of
the substantial decline in DDE levels that has occurred, bald eagles have made
a comeback around Lake Erie and elsewhere. In fact, in the summer of 2007
bald eagles were removed from the list of endangered species in the United
States. Similarly, the population of Arctic peregrine falcons, a bird that was
driven to near-extinction due to the effects of DDE, has now recovered to such
an extent that it has also been removed from the endangered species list.
The concentration of DDT in humans has also declined drastically; for
example, its 1997 level in human breast milk of Swedish women was only
1% of what it was in 1967. As illustrated in Figure 10-1a, the DDT levels
(a)
1600
DDT concentration (ppb of lipids)
1400 DDT
1200
1000
800
600
400
200
0
1967 1971 1975 1979 1983 1987 1991 1995
Year
(b)
2500
DDE
DDE concentration (ppb of lipids)
2000
1500
FIGURE 10-1 Trends in 1000

(a) DDT and (b) DDE con-
centrations in breast milk
of Swedish women. [Source: 500
K. Noren and D. Meironyte,
“Certain Organochlorine and
Organobromine Contaminants 0
1972 1976 1980 1984 1988 1992 1996
in Swedish Human Milk in
Perspective of Past 20–30 Years,” Year
Chemosphere 40 (2000): 1111.]
in these women also began to decline exponentially beginning in the late

1960s, since DDT has a half-life of about 4 years. Data for women in North
America show similar declines over this period. The concentration of DDE
in breast milk did not drop as quickly as did that of DDT, its half-life being
somewhat longer, about 6 years (Figure 10-1b). However, DDE levels remain
high in regions such as Central and South America, Mexico, and Africa
where DDT has been used more recently.
The Accumulation of Organochlorines

in Biological Systems
Many organochlorine compounds are found in the tissues of fish in concen-
trations that are orders of magnitude higher than are those in the waters in
which they swim. Hydrophobic (water-hating) substances like DDT are partic-
ularly liable to exhibit this phenomenon. There are several reasons for this
bioaccumulation of chemicals in biological systems.
Bioconcentration
In the first place, many organochlorines are inherently much more soluble
in hydrocarbon-like media, such as the fatty tissue in fish, than they are in
water. Thus, when water passes through a fish’s gills, the compounds selec-
tively diffuse from the water into the fish’s fatty flesh and become more con-
centrated there: This process (which also affects other organisms besides
fish) is called bioconcentration. The bioconcentration factor, BCF, repre-
sents the equilibrium ratio of the concentration of a specific chemical in a
fish relative to that in the surrounding water, provided that the diffusion
mechanism represents the only source of the substance to the fish. BCF
values occur over a very wide range and vary not only from chemical to
chemical but also, to a certain extent, from one type of fish to another, par-
ticularly because of variations in the abilities of different fish to metabolize a
given substance.
The BCF of a chemical can be predicted, to within about a factor of 10,
for a typical fish from a simple laboratory experiment: The chemical is allowed
to equilibrate between the liquid layers in a two-phase system made up of
water and 1-octanol, CH3(CH2)6CH2OH, an alcohol that has been found
experimentally to be a suitable surrogate for the fatty portions of fish. The
partition coefficient, Kow, for a substance S is defined as
Kow [S]octanol兾[S]water
where the square brackets denote concentrations in molarity units. (Since

water and fat have approximately the same densities, the ratio of molarities
Selected Data for Some

TABLE 10-3 Pesticides
Pesticide Solubility in H2O (ppm) log Kow
HCB 0.0062 5.5 – 6.2

DDT 0.0034 6.2
Toxaphene 3 5.3
Dieldrin 0.1 6.2
Mirex 0.20 6.9 – 7.5
Malathion 145 2.9
Parathion 24 3.8
Atrazine 35 – 70 2.2 – 2.7
Data from K. Verschueren, Handbook of Environmental Data on Organic
Chemicals (New York: Van Nostrand Reinhold, 1996).
in the two phases is identical to the ratio of their masses; consequently, Kow
can also be taken as the ratio of ppm or ppb concentrations.) Largely as a
matter of convenience, the value of Kow is often reported as its base 10 loga-
rithm, since its magnitude sometimes is quite large. For example, for DDT
(see Table 10-3), Kow is about 1,000,000, i.e., 106, and so log Kow 6. Exper-
imentally, the bioconcentration factor for DDT lies in the range of about
20,000 to 400,000, depending upon the type of fish. The Kow value of a com-
pound is a fairly reliable approximation to the BCF values found for fish. The
approximation that Kow S typically breaks down when the molecules are
too large to diffuse into the fish.
In general, the higher its octanol–water partition coefficient Kow, the
more likely a chemical is to be adsorbed on organic matter in soils and sedi-
ment and ultimately to migrate to fat tissues of living organisms. However,
log Kow values of 7 or 8 or higher are indicative of chemicals with such strong
adsorption to sediments that they are actually unlikely to be mobile enough
to enter living tissue. Thus, it is chemicals with log Kow values in the 4–7
range that bioconcentrate to the greatest degree.
P R O B L E M 10-3
For HCB, log Kow 5.7. What would be the predicted concentration of HCB
due to bioconcentration in the fat of fish that swim in waters containing
0.000010 ppm of the chemical?
Biomagnification
5
Fish also accumulate organic chemicals
from the food they eat and from their
intake of particulates in water and sedi- 4
ments onto which the chemicals have been
Concentration (ppm)
adsorbed. In many such cases, the chemi-
3
cals are not metabolized by the fish: The
substance simply accumulates in the fatty
tissue of the fish, where its concentration 2
there increases with time. For example, the
concentration of DDT in trout from Lake
Ontario increases almost linearly as the fish 1
ages, as illustrated in Figure 10-2. The aver-
age concentration of many chemicals also 0
increases dramatically as one proceeds up a 1 2 3 4 5 6 7 8 9
Age (years)
food chain, which is a sequence of species,
each one of which feeds mainly upon the
one preceding it in the chain. The food
FIGURE 10-2 Variation
web, incorporating interlocking food chains, for the Great Lakes is illustrated with age of DDT concen-
in Figure 10-3. Over a lifetime, a fish eats many times its weight in food from tration in Lake Ontario
the lower levels of the food chain but retains rather than eliminates or meta- trout caught in the same
bolizes most organochlorine chemicals from these meals. year. [Source: “Toxic Chemi-
cals in the Great Lakes and
A chemical whose concentration increases along a food chain is said to
Associated Effects” (Ottawa:
be biomagnified. In essence, the biomagnification results from a sequence of Government of Canada, 1991).]
bioaccumulation steps that occur along the chain. The difference between
bioconcentration from water and biomagnification along a food chain is illus-
trated symbolically in Figure 10-4. The biomagnification of DDT along some
of the Great Lakes food chains is shown in Figure 10-3. Notice, for example,
the herring gull’s higher level of DDT compared with the fish below it in the
chains. Fish at the top of the aquatic part of the chain bioaccumulate DDT
rather effectively, so that even higher concentrations are found in the birds of
prey that feed on them.
As an example of biomagnification, consider that the DDT/DDE con-
centration in seawater in Long Island Sound and the protected waters of its
southern shore at one time was as high as 0.000003 ppm, but it reached
0.04 ppm in the plankton, 0.5 ppm in the fat of minnows, 2 ppm in the
needlefish that swim in these waters, and 25 ppm in the fat of the cormorants
and osprey that feed on the fish, for a total biomagnification factor of about
10 million. It is by such mechanisms that DDE levels in some birds of prey
became so great that their ability to reproduce successfully was impaired. The
bioaccumulation of organochlorines in fish and other animals is the reason
that most of the human daily intake of such chemicals enters via our food
supply rather than from the water we drink.
Bald eagle
Humans
6 ppm
Cormorant Herring gull

Salmon/Lake trout
1 ppm
Forage fish
Sculpin Smelt
0.4 ppm Chub Alewife
Snapping
turtle
0.01
ppm
Invertebrates Plankton
Waterfowl
FIGURE 10-3 Simplified
food web for the Great Mineral nutrients
Lakes with typical DDT
concentrations for some Dead animals
and plants Vegetation
species. [Source: “Toxic Chem-
Bacteria and fungi
icals in the Great Lakes and
Associated Effects” (Ottawa:
Government of Canada, 1991).]
FIGURE 10-4 Schematic

representation of the two Bioconcentration
modes of bioaccumulation
that operate in biological Biomagnification
matter present in a body
of water.
Less Persistent Analogs of DDT

A number of compounds having the same general molecular structure as DDT
are found to display similar insecticidal properties. This similarity arises from
the mechanism of DDT action, which is due more to its molecular shape than
to its chemical interactions. The shape of a DDT molecule is determined by the
two tetrahedral carbons in the ethane unit and by the two flat benzene rings. In
insects, DDT and other molecules with the same general size and 3-D shape
become wedged in the nerve channel that leads out from the nerve cell. Nor-
mally, this channel transmits impulses only as needed via sodium ions. But a
continuous series of Na+-initiated nerve impulses is produced when the DDT
molecule holds open the channel. As a consequence, the muscles of the insect
twitch constantly, eventually exhausting it with convulsions that lead to death.
The same process does not occur in humans and other warm-blooded animals
since DDT molecules do not exhibit such binding action in nerve channels.
Examples of other molecules with DDT-like action include DDD (some-
times called TDE), para-dichlorodiphenyldichloroethane, which is an envi-
ronmental degradation product of DDT: It differs only in that one chlorine
from the 9CCl3 group is replaced by a hydrogen. Since the overall shapes and
sizes of DDT and DDD are similar, their toxicity to insects is as well. In the past,
DDD was itself sold as an insecticide, but it has also been discontinued because
it bioaccumulates. Notice that DDE, unlike DDT and DDD, is based upon a
planar C“C unit rather than a C9C linkage which has tetrahedral groups
at each end. Thus, whereas DDD is a DDT-like insecticide, DDE is not, since
its three-dimensional shape is very different: DDE is flat rather than propeller-
shaped, so it does not become wedged in the insect’s nerve channels.
Scientists have devised analogs to DDT that have its same general size and
shape; consequently, they possess the same insecticidal properties but are more
biodegradeable and thus do not present the bioaccumulation problem associ-
ated with DDT. The most important of these analogs is methoxychlor:
CCl3
CH3O C OCH3
H
methoxychlor
The para-chlorines of DDT are replaced in methoxychlor by methoxy groups,

9OCH3, which are approximately the same size as chlorine but which react
much more readily. In particular, under reducing conditions, the O9CH3 bonds
in methoxychlor are subject to attack by hydrogen ions in water, converting the
O9CH3 units to O9H bonds and free methane molecules, CH4. The hydroxy-
lated products are water-soluble products that not only degrade in the environ-
ment but are excreted rather than accumulated by organisms. Methoxychlor is
still used both domestically and agriculturally to control flies and mosquitoes.
P R O B L E M 10-4
Draw the molecular structure of DDD.
P R O B L E M 10-5
Methyl groups are approximately the same size as chlorine atoms, but hydro-
gen atoms are significantly smaller. Would you expect insecticidal properties
for DDT molecules in which (a) the 9CCl3 group is replaced by 9(CH3)3,
and (b) the para-chlorines are replaced by hydrogens?
Other Organochlorine Insecticides

Toxaphene
During the 1970s, after DDT had been banned, the insecticide that replaced
it in many agricultural applications, such as the growing of cotton and soy-
beans, was toxaphene. It is a mixture of hundreds of similar substances, all of
which are produced when the hydrocarbon camphene, produced from chemi-
cals extracted from pine trees, is partially chlorinated.
CH2
camphene
Toxaphene became the most heavily used insecticide (1966–1976) in the

United States before restrictions were placed on its use in 1982 and a total
ban imposed in 1990. More than 85% of toxaphene use in the United States
occurred in the southeastern cotton-growing states, though some was used as
a herbicide in the growing of peanuts and soybeans.
Toxaphene is extremely toxic to fish. Indeed, it was first used in the 1950s in
North America to rid lakes of undesirable fish. However, it was found to be so
persistent that the lakes could not be successfully restocked for years thereafter!
Toxaphene bioaccumulates in fatty tissues and causes cancer in test
rodents; consequently it is one of the dirty dozen persistent organic pollutants
(Table 10-2) and is now banned in developed countries as well as some
developing ones. It still is being deposited in bodies of water remote from its
point of usage because of long-range transport by air (see Chapter 12) from
countries that still make restricted use of it.
Hexachlorinated Cyclohexane
During World War II, the derivative of cyclohexane having one of the two
hydrogens on each carbon replaced by chlorine, namely, 1,2,3,4,5,6-
hexachlorocyclohexane, was discovered to be an effective insecticide against
a wide variety of insects. In fact, there exist eight isomers having this formula;
they differ only in the relative orientations of the chlorine atoms bonded to
different carbons. (The diagrammatic formula below is not intended to illus-
trate the chlorines’ orientations—only their points of attachment.)
H Cl
H Cl
Cl H
H Cl
Cl H
H Cl
1, 2, 3, 4, 5, 6-hexachlorocyclohexane
(This compound is also known as benzene hexachloride or BHC, not to be con-

fused with hexachlorobenzene)
A commercial mixture of most of the hexachlorocyclohexane isomers was
used to control mosquitoes and in agricultural applications after World War II.
Its use has been restricted since the 1970s due to its toxicity and tendency to
bioaccumulate. Only one of the eight isomers, the gamma isomer, actually kills
insects; now sold separately under the name Lindane, it was the active ingredi-
ent in several commercial medical preparations used to rid children of lice and
scabies and agriculturally to treat seeds and seedlings.
Chlorinated Cyclopentadiene Insecticides

Cyclopentadiene, shown at left below, is an abundant by-product of petro-
leum refining. As its name implies, there are two double bonds in each mole-
cule. When fully chlorinated (diagram at right), it can be combined with one
of several other organic molecules (Diels–Alder reaction) to produce a series
of insecticidal compounds with properties, including environmental persist-
ence, that at first made them superficially attractive.
Cl
Cl
6 Cl2 Cl
6 HCl
Cl
Cl
Cl
cyclopentadiene perchlorocyclopentadiene
All the cyclodiene pesticides contain the hexachlorinated five-membered

ring bonded to at least two other carbon atoms and containing a residue of
one double bond.
Most cyclodiene insecticides that were commercially important have
now been branded as persistent organic pollutants by the United Nations
Environmental Programme and are listed in Table 10-2. They were used to
control soil insects, fire ants, cockroaches, termites, grasshoppers, locusts, and
other insect pests. In many such applications, their persistence was an advan-
tage since they did not have to be reapplied frequently.
The cyclodiene pesticides, starting with aldrin and dieldrin—which are
structurally identical except that the latter corresponds to the former with one
of its C“C bonds epoxidized (see Figure 12-2)—arrived on the market in
about 1950. Given their persistence, their potential toxicity, their tendency to
accumulate in fatty tissues, and the suspicion that dieldrin was causing excess
mortality of adult bald eagles, the use of almost all of these compounds has
now either been banned or severely restricted in North America and most
western European countries. Nonetheless, dieldrin and DDT were the most
common POPs still detectable in food in 2002. Some of the compounds are
still in use elsewhere (see Table 10-2).
Agricultural uses of dieldrin, mainly to combat soil insects, and its use in
buildings to control termites, were largely prohibited in North America by the
mid-1980s but continue in many developing countries. Dieldrin was used
extensively in tropical countries to control the tsetse fly and is still used in some
countries to kill termites. It continues to enter water systems even in developed
countries by percolating from waste disposal sites. Danish studies have found
a correlation between blood dieldrin levels in women and their increasing risk
of developing, and dying from, breast cancer. Dieldrin and another cyclodiene
insecticide containing a three-membered epoxide ring, heptachlor epoxide, have
been associated with increased risk of non-Hodgkin’s lymphoma.
If two perchlorocyclopentadiene molecules are chemically combined, the
resultant molecule, known commercially as as mirex, also acts as an insecti-
cide and is particularly effective against the fire ant found in the southeastern
United States.
Cl12
mirex
(All 10 carbon atoms are bonded to chlorine, but for clarity the individual
chlorine atoms are not shown; only the total is displayed in the formula.)
Mirex was also sold as a flame retardant additive for synthetic and natural
materials. Most mirex use occurred in the 1960s, although it is still produced
and used in China and is used to fight giant termites in parts of Australia.
Mirex is classified as a persistent organic pollutant by the U.N. and has been
banned in many countries since the mid-1970s.
For the most part, the chlorinated cyclodiene pesticides are chemical
products of the past. Their use has been phased out or at least severely
restricted because of environmental and human health considerations. The
only cyclodiene insecticide still in widespread use is endosulfan, which is dis-
cussed in detail in Box 10-1.
BOX 10-1 The Controversial Insecticide Endosulfan
E ndosulfan does not appear on the U.N.

list of POPs; indeed, it is one of the
few cyclopentadiene pesticides still widely
absorbed by the stomach and lungs and
through the skin. Although acutely toxic,
endosulfan does not persist in mammals
available on the market. Structurally, endo- because it is degraded into water-soluble com-
sulfan molecules consist of a perchlorinated pounds and eliminated from the body within a
five-membered ring attached by methylene few days or weeks. Because of its short lifetime,
groups to an O“S(O9)2 unit. the risk from consuming it in drinking water
or in food is usually not a concern. Conse-
Cl quently, most of the health concerns about
Cl endosulfan relate to its ability to act as an
O Cl acute poison to workers who handle and apply
O"S it in agricultural settings. It is also of environ-
O Cl mental concern due to its toxicity to nontar-
Cl get fish, birds, and other animals. Indeed,
Cl there have been massive fish kills in the
endosulfan
United States (Alabama) and in other coun-
tries in waters that were inadvertently con-
It is used as an insecticide and an acaricide in taminated with the insecticide.
agricultural applications, its domestic applica- Owing to its toxicity, endosulfan has been
tions having been phased out—at least in the banned in many countries and its use restricted
United States. Both its environmental persist- in others. The bans followed the accidental
ence and its tendency to bioconcentrate are deaths of farmworkers and nearby residents as
much lower than those of the other cyclodi- well as its use in committing suicide. For exam-
enes because it is much more reactive, owing ple, it was introduced into Sri Lanka to replace
to the presence of the sulfur–oxygen group. In category I insecticides that previously had been
the environment, some of it is converted to used in suicides, but it soon became employed
the sulfate, which has an additional oxygen for the same purpose. Since it was banned there
doubly bonded to the sulfur, thereby produc- in 1998, other category II insecticides that
ing S(VI) from S(IV) in the original pesticide. replaced it have been employed instead by
Unfortunately, endosulfan sulfate is just as would-be suicides.
toxic as endosulfan and is more persistent. In addition to its use on some food and
The remaining fraction of endosulfan in the grain crops as well as on tea and coffee planta-
environment is converted to the sulfur-free tions, endosulfan is also used in the growing of
diol in which the 9CH29 groups are each cotton in both developed countries, such as
bonded to 9OH, and which itself undergoes the United States and Australia, and develop-
further degradation reactions. ing countries. For example, endosulfan was
Although endosulfan is classified as mod- introduced late in the twentieth century into
erately toxic by the WHO, it is considered to be French-speaking countries in West Africa when
highly hazardous by the U.S. EPA. It is readily bollworm caterpillars (boll weevils)—which
BOX 10-1 The Controversial Insecticide Endosulfan (continued)
enter cotton flower buds and bolls and destroy be used when handling and spraying endo-
them—became resistant to the lower-toxicity sulfan. In addition, the cotton farmers some-
insecticides (pyrethroids) that previously had times use leftover endosulfan inappropriately
been employed. Unfortunately, most farmers as an insecticide on their vegetable crops.
in certain countries in this region, including Since endosulfan is almost insoluble in water,
Benin, cannot afford the protective clothing— washing food sprayed with it is largely
goggles, gloves, and respirators—that should ineffective.
Principles of Toxicology
Toxicology is the study of the harmful effects on living organisms of substances
that are foreign to them. The substances of interest include both synthetic
chemicals and those that exist naturally in the environment. In toxicology,
the effects are normally determined by injecting or feeding animals with the
substance of interest and observing how the health of the animal is affected.
By contrast, in epidemiology, scientists do not run experiments in a lab but
instead determine the health history of a selected group of human beings and
attempt to relate differences in disease rates and so on to differences in sub-
stances to which they have been accidentally exposed.
Toxicological data concerning the harmfulness of a substance to an
organism, such as an organochlorine pesticide or a heavy metal, are gathered
most easily by determining its acute toxicity, which is the rapid onset of
symptoms—including death at the extreme limit—immediately following
the intake of a dose of the substance. For example, experiments show that it
takes only a few tenths of 1 microgram of the most acutely toxic synthetic
compound—the “dioxin” to be discussed in Chapter 11—to kill most rodents
within a few hours after it is administered orally to them.
Although the acute toxicity of a substance is of interest when we are
exposed accidentally to pure chemicals, in environmental toxicology we are
usually more concerned about chronic (continuous, long-term) exposures at
relatively low individual doses of a toxic chemical that is present in the air
that we breathe, the water we drink, or the food we eat. Generally speaking,
any effects of such continuing exposures are also long-lasting and therefore
also classified as chronic.
The same chemical may give rise to both acute and chronic effects in
the same organism, although usually by different physiological mechanisms.
For example, a symptom of acute toxicity in humans of exposure to many
organochlorines is a skin irritation that leads to chloracne, a persistent, disfig-
uring, and painful analog to common acne, and there is the fear that persistent
exposure to much lower individual doses than those which produce the skin
disease could eventually lead to cancer.
The three types of substances that produce detrimental effects on human
health that are of most concern are
• mutagens, substances that cause mutations in DNA, most of which are
harmful and can produce inheritable traits if they occur in DNA of cells
present in sperm or eggs;
• carcinogens, substances that cause cancer; and
• teratogens, substances in the mother that cause birth defects in the fetus.
Some carcinogens operate in an initiation step, in which the substance—
sometimes after itself having been transformed in the body—reacts directly
with a strand of DNA. This alteration in DNA can lead to the growth of can-
cer cells. Others, called promoters, act only after cancer has been initiated, but
they speed up the process of tumor formation.
Dose–Response Relationships
Most of the quantitative information concerning the toxicity of substances is
obtained from experiments performed by administering doses of the sub-
stances to small animals, although recently tests on certain bacteria have
been used to determine whether a substance is likely to be a carcinogen or
not. Owing to practical considerations including cost and time, most experi-
ments involve acute rather than chronic toxicity, even though it is the latter
that usually is of primary interest in environmental science. To determine
directly the effects of continuous, low-level exposures over long periods
would require a very large number of test animals and a long project time.
The practical alternative is to evaluate the effects using high doses—at which
point the effects are substantial and clear-cut—and then extrapolate the
results down to environmental exposures. Unfortunately, there is no assur-
ance that such extrapolations are always reliable, since the cellular mecha-
nisms that produce the effects at high and low doses could differ.
The dose of the substance administered in toxicity tests is usually
expressed as the mass of the chemical, usually in milligrams, per unit of the
test animal’s body weight, usually expressed in kilograms, thus giving units
of milligrams per kilogram, mg/kg. The division by body weight is necessary
because the toxicity of a given amount of a substance usually decreases as the
size of the individual increases. (Recall that the maximum recommended
doses for medicines such as headache remedies are smaller for children than
for adults, primarily because of the difference in body masses.) It is also
assumed that toxicity values obtained from experiments on small test animals
are approximately transferable to humans provided the differences in body
weight are taken into account. Normally the toxicity of a substance increases
with increasing dose, although exceptions are known.
P R O B L E M 10-6
If a dose of a few tenths of a microgram of a certain substance is sufficient to
kill a mouse, approximately what mass of the substance would be fatal to you?
What average level of the substance would have to be present in the water
you drink if you were to receive a fatal dose from this source in a week? Note
that your weight in kilograms is that in pounds divided by 2.2.
Individuals differ significantly in their susceptibility to a given chemical:

Some respond to it even at very low doses, whereas others require a much
higher dose before they respond. It is for this reason that scientists created
dose–response relationships for toxic substances, including environmental
agents. A typical dose–response curve for acute toxicity is illustrated in Fig-
ure 10-5a. The dose is plotted on the (horizontal) x-axis, and the cumulative
100
(a) Linear dose scale
Percent of population affected
50
0
0 2 4 6 8 10 12 14 16 18 20
LD50 Dose (linear scale in mg/kg)
100
(b) Logarithmic dose scale
Percent of population affected
50
Threshold
FIGURE 10-5 Dose–
response curves for (a) linear 0
dose scale; (b) logarithmic Dose (logarithmic scale)
dose scale.
percentage of test animals that display the measured effect (e.g., death) when
administered a particular dose is shown on the (vertical) y-axis. For example,
in Figure 10-5a, about 60% of the test animals were affected by a dose of
about 4 mg/kg.
Because the range of doses on such graphs often exceeds an order of mag-
nitude, and because the effects at the low end of the concentration scale are
often important in environmental decision making and cannot be seen
clearly using linear scales, the dose–response plot is often recast by using
a logarithmic scale for doses. Usually an S-shaped or sigmoidal-shaped curve
results from this transformation—see Figure 10-5b.
Most often, the response effect on test animals that is used to construct
dose–response curves is death. The dose that proves to be lethal to 50% of the pop-
ulation of test animals is called the LD50 value of the substance; its determination
from a dose–response curve is illustrated by the dashed lines in Figure 10-5a.
The smaller the value of LD50, the more potent (i.e., more toxic) is the chemi-
cal, since less of it is required to affect the animal. A chemical much less toxic
than that illustrated in Figure 10-5b would have a sigmoidal curve shifted to
the right of the one shown.
Many sources quote values for the LOD50, the lethal oral dose, when the
chemical has been administered orally to the test animals, as opposed to der-
mal or some other means of delivery. For example, the LOD50 value for DDT
for rats is about 110 mg/kg. As mentioned previously, the presumption is
usually made that LD50 and LOD50 values are approximately transferable
between species. In the case of DDT, for example, humans are known to have
survived doses of about 10 mg/kg, so presumably the LOD50 value for humans
is greater than 10 mg/kg. However, we have no direct evidence that the
110 mg/kg value for rats is also valid for humans.
Of much more concern than the acute toxicity of DDT is its ability to
cause chronic effects in humans, such as cancer. Although DDT is not tradi-
tionally considered to be a human carcinogen, some small-scale epidemiolog-
ical studies found that the higher the concentration of DDE in a woman’s
blood, the more likely she was to have contracted breast cancer. However,
later full-scale studies in the United States have failed to confirm this associ-
ation between breast cancer and DDE. Thus it does not seem that lifetime
exposure to DDT is an important cause of breast cancer, but these studies do
not address the issue raised recently of whether exposure during the teenage
years, when breasts are developing rapidly, might be a factor in developing
breast cancer decades later.
The range of LD50 and LOD50 values for acute toxicity of various chemical
and biological substances is enormous, and spans about ten powers of 10.
Indeed, all substances are toxic at sufficiently high doses; as the Renaissance-
era German philosopher Paracelsus observed, all things are poison, and it is the
dose that differentiates a poison from a remedy. The World Health Organization
(WHO) has devised descriptors for four broad levels of toxicity for substances,
especially pesticides; the range and descriptor for each class is shown in
TABLE 10-4 WHO and U.S. EPA Pesticide Hazard Categorization
WHO Examples
Category U.S. EPA WHO LOD50† Synthetic “Natural”
Number Category* Description (mg/kg) Pesticide Pesticide
Ia I Extremely 5 aldicarb; parathion;

hazardous methyl parathion;
turbufos
Ib I Highly 5–50 azinphos-methyl; nicotine
hazardous carbofuran;
dichlorvos
II II Moderately 50–500 carbaryl; chlorpyrifos; permethrin;
hazardous diazinon; dimethoate; pyrethrins;
endosulfan; fenitrothion; rotenone
lindane; paraquat;
propoxur
III III Slightly 500–5000 alachlor; malathion; allethrin
hazardous metolachlor; 2,4-D
family
III IV 5000
* The United States EPA does not distinguish between WHO classes Ia and Ib but uses a single category I. The EPA also defines a
fourth category, IV, for substances with LOD50 values greater than 5000 mg/kg.
†The LOD50 values quoted are for the solid form and are based upon experiments with rats; LD50 ranges are a factor of 2 higher.
Lethal dose ranges for liquids are a factor of 4 larger than their respective LD50 and LOD50 ranges.
Table 10-4, along with some examples of pesticides that fall in each. All the
pesticides in the extremely toxic category Ia are synthetic, but nicotine—which
as a solution of its sulfate salt has been used as an organic insecticide in gardens
for many decades—falls in category Ib, highly hazardous. The U.S. EPA classifies
pesticides in a similar fashion to WHO but does not distinguish between
the two sublevels of WHO’s category I. Category II substances, moderately
hazardous, include many pesticides—both synthetic and organic—still on the
market. WHO’s category III, slightly hazardous, is subdivided into III and IV by
the U.S. EPA.
In the dose–response curves for some substances, there exists a dose
below which none of the animals are affected; this is called the threshold,
and it is illustrated in Figure 10-5b. The highest dose at which no effects are
seen lies slightly below it and is called the no observable effects level
(NOEL), although sometimes the two terms are used interchangeably. It is
difficult to determine the threshold or NOEL level: It may be that if more
animals were involved in a particular study, effects at low doses might be
uncovered that are not apparent with only a small number of test animals.
Most toxicologists believe that for toxic effects other than carcinogenesis
there is probably a nonzero threshold for each chemical. A few scientists hold
the controversial view that for some substances the curve in Figure 10-5b
actually falls below the zero or NOEL value for very low concentrations before
returning to zero at zero dose, indicating that tiny amounts of these substances
could have a positive rather than a negative effect on health.
Experiments involving test animals are also used to determine how car-
cinogenic a compound is. However, the simple Ames test, which uses bacteria,
can be used fairly reliably to distinguish compounds likely to be human car-
cinogens from those that are not.
A parameter that is useful in judging whether a specific chemical is pres-
ent in an environmental sample in dangerous amounts or not is the lethal
concentration, LC, of the substance. Usually this is listed as its LC50, the
concentration of the substance that is lethal to 50% of a specified organism
within a fixed exposure period. LC50 values may refer to the concentration of
a substance in air or in aqueous solution to which the organism is exposed and
usually have units of milligrams per liter. For example, the LC50 for rainbow
trout for a four-day exposure to endosulfan in water is only 0.001 mg/L;
indeed, this insecticide is “supertoxic” to many fish species. The LC50 for a
shorter exposure would be a value greater than 0.001.
Risk Assessment
Once toxicological and/or epidemiological information concerning a chemi-
cal is available, a risk assessment analysis can be performed. This analysis
tries to answer quantitatively the questions “What are the likely types of tox-
icity expected for the human population exposed to a chemical?” and “What
is the probability of each effect occurring in the population?” Where neces-
sary, risk assessment also tries to determine permissible exposures to the sub-
stance in question.
In order to perform a risk assessment on a chemical, it is necessary to
know
• hazard evaluation information; i.e., the types of toxicity (acute? cancer?
birth defects?) that are expected from it;
• quantitative dose–response information concerning the various possible
modes of exposure (oral, dermal, inhalation) for it; and
• an estimation of the potential human exposure to the chemical.
For chronic exposures, threshold or NOEL dose information is normally
expressed as milligrams of the chemical per kilogram of body weight per day.
In determining the threshold level for the most sensitive members of the
human population, it is common to divide the NOEL from animal studies by
a safety factor, typically 100. The resulting value is called the maximum
acceptable daily intake, ADI, or maximum daily dose; the U.S. EPA instead
refers to it as the toxicity reference dose, RfD. Note that the ADI or RfD
value does not represent a sharp dividing line separating absolutely safe from
absolutely unsafe exposures, since the transferability of toxicity information
from animals to humans is not exact, and in most cases the safety factor pre-
sumably is quite generous. Some scientists have suggested dividing the NOEL
by a further factor of 10 in order to protect very susceptible groups such as
children. Indeed, the Food Quality Protection Act in the United States
requires that the EPA set limits for residues of pesticides on foods 10 times
lower than what is considered to be safe for an adult.
P R O B L E M 10-7
The NOEL for a chemical is found to be 0.010 mg/kg/day. What would its
ADI or RfD value for adults be set at? What mass of the compound is the
maximum that a 55-kg woman should ingest daily?
As mentioned, in a risk assessment, an attempt is made to estimate the

exposure of the affected population. For example, for chemicals whose mode
of exposure is primarily through drinking water, regulatory agencies such as
the U.S. EPA consider a hypothetical average person who drinks about 2 L of
water daily and whose body weight averages 70 kg (154 lb) through life. If the
ADI (or RfD) of a substance is 0.0020 mg/kg/day, then for the 70-kg person,
the mass of it that can be consumed per day is 0.0020 70 0.14 mg/day.
Thus the maximum allowable concentration of the chemical in water would
be 0.14 mg兾2 L 0.07 mg/L 0.07 ppm. Of course, if there are other signif-
icant sources of the substance, they must be taken into account in deter-
mining the drinking-water standard. Also, exposure to several chemicals of
the same type (e.g., several organochlorines) could produce additive effects,
so the standard for each one should presumably be lowered to take this into
consideration.
The EPA regulates exposure to carcinogens by assuming that the
dose–response relationship has no threshold and can be linearly extrapolated
from zero dose to the area for which experimental results are available. The
maximum daily doses are then determined by assuming that each person
receives the dose every day over his or her lifetime and that this exposure
should not increase the likelihood of cancer to more than one person in every
million.
In determining regulations to control risk, usually no consideration is
given to the economic costs involved. Many economists believe that because
regulations cost money to implement, and because society may decide that
it has only limited resources that it is willing to spend overall on regulation,
a cost–benefit analysis should be used to help decide which substances to reg-

ulate. Associated with this line of thinking is the idea that regulations should
show a positive payback: The benefits from regulation should exceed the
costs. Of course, it is difficult to place a specific monetary value on environ-
mental benefits in many cases. For example, is the $200,000 average cost for
saving a life by regulating the chloroform content in water (see Chapter 14)
a reasonable amount to pay? If so, would it still be reasonable if the cost
instead was 10 or 100 or 1000 times this amount?
Organophosphate and Carbamate Insecticides

Organochlorine insecticides have now largely been replaced by those that are
less persistent and less subject to bioaccumulation. The most important classes
of these newer insecticides are organophosphates and carbamates, both of
which are discussed below.
Organophosphate Insecticides
Structurally, all organophosphate (OP) pesticide molecules can be consid-
ered as derivatives of phosphoric acid, O“P(OH)3, and consist of a central,
pentavalent phosphorus atom to which are connected
• an oxygen or sulfur atom doubly bonded to the P atom,
• two methoxy (9OCH3) or ethoxy (9OCH2CH3) groups singly bonded
to the P atom, and
• a longer, more complicated, characteristic R group singly bonded to
phosphorus, usually through an oxygen or sulfur atom, that differentiates
one organophosphate insecticide from another.
The organophosphates are toxic to insects because they inhibit enzymes
in the nervous system; thus they function as nerve poisons. In particular,
organophosphates disrupt the communication that is carried between cells
by the acetylcholine molecule. This cell-to-cell transmission cannot operate
properly unless the bound acetylcholine molecule is destroyed after it has
executed its function. Organophosphates block the action of the enzymes
whose job it is to destroy the acetylcholine, by selectively bonding to them.
(At the atomic level, it is the phosphorus atom of the organophosphate
molecule that attaches to the enzyme and stays bound to it for many hours.)
The presence of the insecticide molecule has the effect of suppressing the
dissociation of the bound acetylcholine. Consequently, continuous stimula-
tion of the receptor cell and its target muscle occurs. Normally the enzyme
occurs in large excess and therefore some exposure to OPs occurs without
immediate effects, but symptoms begin to appear if a majority of them
are inactivated. Since the affected nerves

include those controlling gastrointesti-
Field corn nal activities and bronchial secretions, mas-
sive gastric and respiratory secretions occur
Cotton
along with involuntary motions. Death
Other field crops * ensues if 80–90% or more of the enzyme
sites are inactivated.
Fruits and nuts The largest use of organophosphate
insecticides is in agriculture (see Fig-
Vegetables ure 10-6), but they also find many uses
Residential and domestically. Organophosphates generally
commercial uses are nonpersistent; in this respect, they rep-
Livestock resent an environmental advance over
and pets organochlorines since they do not bioac-
Forestry and cumulate in the food chain and present a
rangeland
chronic exposure and health problem to us
Grain storage later. However, they are generally much
Turf and more acutely toxic to humans and other
ornamental plants mammals than are organochlorines. Many
0 10 20
organophosphates represent an acute dan-
Millions of lb applied per year ger to the health of those who apply them
*Examples are canola and alfalfa.
and to others who may come into contact
with them. Exposure to these chemicals
by inhalation, swallowing, or absorption
FIGURE 10-6 Consump- through the skin can lead to immediate
tion of organophosphate health problems. However, organophosphates metabolize relatively quickly
pesticides by various and are excreted in the urine.
crops in the United States.
After application, most organophosphates decompose within days or
[Source: B. Hileman,
“Reexamining Pesticide Risk,” weeks and thus are seldom found to bioconcentrate appreciably in food
Chemical and Engineering chains. However, because they have a wide range of uses in homes, on
News (17 July 2000): 34]. lawns, in commercial buildings, and in agriculture, almost everyone is reg-
ularly exposed to them. There is some evidence that OPs cause chronic as
well as acute health problems. Children in the United States generally have
their greatest exposure to organophosphates through the food they eat,
with exposure from drinking water only 1–10% of that from food. A study
reported in 2003 concerning a group of preschool children in Seattle,
Washington, who consumed mainly organic fruits, vegetables, and juices
found that they had much lower exposure to organophosphates, as mea-
sured by metabolites in their urine, than children with conventional
diets. A number of recent studies, none of them large enough to be statisti-
cally definitive, have found links between indoor use of insecticides—
organophosphates especially—and childhood leukemia and brain cancer.
The U.S. EPA has placed OPs in its highest priority group in its current
re-examination of pesticides.
General Specific
structure example
O O
Type A:
R 9 O 9 P 9 O 9 CH3 CCl2 " CH 9 O 9 P 9 O 9 CH3
O 9 CH3 O 9 CH3
dichlorvos
S S
Type B:
R 9 O 9 P 9 O 9 CH3 O2N O 9 P 9 OCH2CH3
O 9 CH3 OCH2CH3
parathion
S S
Type C:
R 9 S 9 P 9 O 9 CH3 R 9 S 9 P 9 O 9 CH3
O 9 CH3 O 9 CH3
冉冊
where R
O
9 CH CH2C
OCH2CH3 2
malathion
FIGURE 10-7 General structures and examples of organophosphate insecticides. In some

molecules (e.g., parathion) the methoxy groups are replaced by ethoxy groups.
The three main subclasses of the organophosphate insecticides (for con-

venience called Types A, B, and C) are illustrated in Figure 10-7. Those con-
taining a P“S unit are converted within the insect into the corresponding
molecules with a P“O unit, producing a more toxic substance. The P“S
form is used initially because it penetrates the insect more readily and is more
stable than is the corresponding P“O compound. Such organophosphates
decompose fairly rapidly in the environment because oxygen in air alters
P“S bonds to P“O.
Most organophosphate insecticides decompose in the environment by
hydrolysis reactions, i.e., reaction with H2O. Water molecules split P9S and
P9O bonds in organophosphates—by adding H to the sulfur or oxygen
atom and OH to the phosphorus—and also add to the C9O bonds in the
phosphoric acid esters formed as intermediates, ultimately yielding nontoxic

substances such as phosphoric acid and alcohols and thiols: e.g.,
O O
‘ ‘
R
9S9P(OR)2 H9OH ¡ R
9S9H HO9P(OR)2
¡ ¡ R
SH 2 ROH O“P(OH)3
Dichlorvos is an example of a Type A organophosphate and so contains
no sulfur. It is a relatively volatile insecticide and is used as a domestic fumi-
gant released from impregnated fly strips hung from ceilings and light fixtures.
The chemical slowly evaporates, and its vapor kills flies in the room. Plastic
is impregnated with dichlorvos for use in flea collars. It is also used to treat
worm infections in animals and as an agricultural insecticide. It is classed as
highly hazardous (Table 10-4) to mammals; its LOD50 is 25 mg/kg in rats.
(Note the -os ending of the name of this insecticide. The commercial names
of organophosphate insecticides often have this or an -fos ending, signaling
their nature.)
Parathion (Figure 10-7) is an example of a Type B organophosphate, i.e.,
one in which the doubly bonded oxygen (only) has been replaced by sulfur.
It is described as extremely hazardous (LOD50 3 mg/kg) and has probably
been responsible for more deaths of agricultural field workers than any other
pesticide. Since it is nonspecific to insects, its use can inadvertently kill birds
and other nontarget organisms. Bees, too, which are often economically valu-
able, are indiscriminately destroyed by parathion. It is now banned in some
Western industrialized countries but is still widely used in developing coun-
tries. The background levels of parathion in homes in the agricultural com-
munity in the United States have dropped by an order of magnitude since it
was banned in 1991. The structure of fenitrothion is very similar to parathion,
but it is much less toxic (LOD50 250 mg/kg) because it is less effective
in deactivating bound acetylcholine in mammals as compared to insects.
Fenitrothion has been used extensively as a spray against spruce budworm in
evergreen forests in eastern Canada, though not without controversy.
Diazinon, another Type B O3P“S organophosphate, was widely used
for insect control in homes (against ants and roaches), gardens and lawns
(including grub control), shrubs, and on pets, since it was thought to be rela-
tively safe (moderately hazardous; LOD50 300 mg/kg), although its usage
did have some restrictions since it is toxic to birds. However, there now is
evidence that children treated for diazinon poisoning suffer persistent neuro-
behavioral problems. Consequently, the residential uses of diazinon in North
America have been phased out, though it is still used in agriculture.
Chlorpyrifos (moderately hazardous; LOD50 135 mg/kg), another
Type B insecticide, was commonly used in households to control cock-
roaches, ants, termites, and other insects. Indeed, it was the insecticide most
commonly sprayed by exterminators to kill cockroaches. However, it has

been withdrawn in the United States for home and garden use and banned
for certain crops due to potential health concerns, especially involving fetal
and childhood exposure, following experiments using rats, and due to unin-
tentional poisonings. It was detected in 93% of the 1300 Americans whose
blood was analyzed in a recent survey of common body contaminants. Its use
had been restricted as of the late 1990s by the EPA, as had that of methyl
parathion (which is identical to parathion except that it has methyl rather
than ethyl groups), which is heavily used in the growing of cotton.
Most indoor uses of organophosphates have been eliminated by regula-
tory action in recent years. A recent survey linked the use of indoor insecti-
cides, but not herbicides or outdoor insecticides, especially during pregnancy,
to an increase in leukemia among the children born following fetal exposures.
Malathion (slightly hazardous) is the most important example of Type C
organophosphates, which are those in which two oxygens have been replaced
by sulfur, resulting in a P“S and one P¬S unit. Upon exposure to oxygen,
malathion is converted to malaoxon, which has the doubly bonded sulfur
atom replaced by oxygen and is more toxic than malathion. Introduced in
1950, malathion is not particularly toxic to mammals (LOD50 885 mg/kg)
since they metabolize it faster than their livers convert the P“S form to the
activated P“O form, but insects do not have the requisite enzyme to deacti-
vate it and hence it is fatal to them. However, if improperly stored, malathion
can be converted to an isomer that is almost 100 times as toxic; it was respon-
sible for the death of five spray workers and the sickness of thousands more
during a malaria eradication program in Pakistan in 1976.
Malathion is still used in domestic fly sprays and to protect agricultural
crops. It and chlorpyrifos were the organophosphorus insecticides commonly
detected in the urine of the 23 schoolchildren from Seattle, Washington,
who participated in the experiment in 2003. When they switched to an all-
organic-food diet for a week, the insecticides in their urine samples fell imme-
diately to nondetectable levels. The insecticides were again detected once
the children in the survey switched back to conventional diets.
In combination with a protein bait, low concentrations of malathion
have been sprayed from helicopters over several areas in the United States
(California, Florida, Texas) to combat infestations of the Mediterranean
fruit fly, a dangerously destructive pest. As in California, aerial spraying of
malathion in Chile to combat the fruit fly has also proven to be controversial.
It has also been sprayed on parts of New York City (1999) and Florida (1990)
to protect against St. Louis encephalitis, carried by mosquitoes. For decades,
the entire city of Winnipeg, Manitoba, has been sprayed with malathion sev-
eral times each summer to keep down the mosquito population and now also
to protect against the West Nile virus. A recent analysis concluded that the
health risks from West Nile virus exceed those from the malathion used to
control the mosquitoes that carry it.
Dimethoate (moderately hazardous; LOD50 250 mg/kg) belongs to the

same O2SP“S structural Type C as malathion; it is widely used for insect
control on food crops, including those grown in backyards. Like malathion, it
is converted into its oxygen analog, which is the metabolite responsible for its
toxic action. Some of its uses in the United States have been terminated.
Yet another Type C member, azinphos-methyl, is classed as a highly
hazardous insecticide (LOD 5 mg/kg) but has been widely used by profes-
sionals on fruits and vegetables. However, all its uses in the United States
and Canada are slowly being phased out, since it can pose acute risks to agri-
cultural workers. According to a survey in the mid-1990s, azinphos-methyl
and another Type C organophosphate, phosalone, together with the fungicide
diphenylamine, were the most common pesticides present in residues in and on
apples grown commercially in Canada.
Carbamate Insecticides
The mode of action of carbamate insecticides is similar to that of the
organophosphates; they differ in that in carbamates, it is a carbon atom rather
than a phosphorus that attacks the acetylcholine-destroying enzyme. They
are more attractive for some applications since their dermal toxicity is rather
low. The carbamates, introduced as insecticides in 1951, are derivatives of
carbamic acid, H2NCOOH. One of the hydrogens attached to the nitrogen
is replaced by an alkyl group, usually methyl, and the hydrogen attached to
the oxygen is replaced by a longer, more complicated organic group symbol-
ized below simply as R:
O H O
H2N 9 C 9 OH CH3 9 N 9 C 9 O 9 R
carbamic acid the general formula of a carbamate
Like the organophosphates, the carbamates are short-lived in the environment

since they undergo hydrolysis reactions and decompose to simple, nontoxic
products. The reaction with water involves the addition of H¬OH to the
N¬C bond; the species HO¬C¬OR decomposes to release CO2 and the
alcohol R—OH.
O O
‘ ‘
CH3¬NH¬C¬O¬R H¬OH ¡ CH3¬NH2 [HO¬C¬O¬R]
¡ HO¬R CO2
Important examples of the carbamate pesticides are carbofuran (LOD50

8 mg/kg), carbaryl (LOD50 307), and aldicarb (LOD50 0.9). Although
carbaryl, a widely used lawn and garden insecticide, has a low toxicity to
mammals, it is particularly toxic to honeybees. Aldicarb is not only highly
toxic to mammals—including humans—it is also somewhat water-soluble
( 1 ppm) and persistent, so although it does not bioaccumulate, it can build
up in groundwater supplies—and in crops irrigated with the water.
Health Problems of Organophosphates and Carbamates

The organophosphates and carbamates solved the problem of environmen-
tal persistence and accumulation associated with organochlorine insecti-
cides, but sometimes at the expense of dramatically increased acute toxicity
to the humans and animals who encounter them while the chemicals are
still in the active form. These less persistent insecticides—together with
the pyrethroids mentioned below—largely replaced organochlorines in res-
idential uses. Organophosphates and carbamates are a particular problem in
developing countries, where widespread ignorance about their hazards and
failure to use protective clothing—due to lack of information or to the
heat—has led to many deaths among agricultural workers. The types of pes-
ticides used in developing countries are also more likely to be highly toxic,
even banned elsewhere for that reason. Estimates by the United Nations
and the World Health Organization put the number of persons who suffer
acute illnesses from short-term exposure to pesticides in the millions annu-
ally; 10,000–40,000 die each year from the poisoning, about three-quarters
of these in developing countries. Although most of the deaths from pesti-
cide poisonings occur in developing countries, about 20,000 people receive
emergency medical care in the United States annually for actual or sus-
pected poisoning from pesticides, and about 30 Americans annually die
from it.
Natural and Green Insecticides,

and Integrated Pest Management
Pesticides from Natural Sources
As pointed out earlier, many plants themselves manufacture certain mole-
cules for their own self-protection that either kill or disable insects. Chemists
have isolated some of these compounds so that they can be used to control
insects in other contexts. Examples are nicotine, rotenone, the pheromones,
and juvenile hormones.
One group of natural pesticides that has been used by humans for cen-
turies is the pyrethrins. The original compounds, the general structure for
which is illustrated on the next page, were obtained from the flowers of a
species of chrysanthemum.
O O
O9C
R1
R2
general pyrethrin structure

In the form of dried, ground-up flower heads, pyrethrins were used in
Napoleonic times to control body lice; they are still used in flea sprays for ani-
mals. They are generally considered to be safe to use. Like organophosphates,
they paralyze insects, though they usually do not kill them. Unfortunately,
these compounds are unstable in sunlight. For that reason, several synthetic
pyrethrin-like insecticides that are stable outdoors—and therefore can be
used in agricultural and garden applications—have been developed by
chemists. Semisynthetic pyrethrin derivatives, called pyrethroids, are usually
given names ending in -thrin to denote their nature (e.g., permethrin).
Pyrethroids are now also a common ingredient in domestic insecticides, as
any visit to a garden center will testify. They have also been used in Mexico
to spray houses in which malaria control is still necessary and to spray neigh-
borhoods in New York City to reduce mosquito populations carrying the
West Nile virus. In order to make them more effective as insecticides,
pyrethroid formulations are usually mixed with piperonyl butoxide, a semi-
synthetic derivative of the natural product safrole, which can be extracted
from sassafras plants. The piperonyl butoxide interferes with the enzyme that
insects use to detoxify the pyrethroids, thus making them more potent in
destroying the insects.
Pyrethroids are now so widely used that their metabolites were detected in
the urine of most of the elementary schoolchildren in the Seattle study group
mentioned previously. Interestingly, the pyrethroid levels did not decrease
when the children adopted an organic diet. However, the most important con-
tribution to high pyrethroid levels was not dietary but correlated with the use
of pyrethrin insecticides by their parents.
Rotenone, a complex natural product derived from the roots of certain
tropical bean plants, has been used as a crop insecticide for over 150 years and
for centuries to paralyze and/or kill fish. The compound enters fish via their
gills and disrupts their respiratory system. It is also highly efficient against
insects but is decomposed by sunlight. Rotenone is widely use in hundreds of
commercial products, including flea-and-tick powders and sprays for tomato
plants. Notice in Table 10-4 that the “natural” insecticides pyrethrins and
rotenone are classified as moderately hazardous, since they have about the
same acute toxicity as some synthetic ones such as malathion, even though
they are often marketed as safer, natural pesticides. There is epidemiological
and toxicological evidence that chronic exposure to rotenone can contribute
to the onset of Parkinson’s disease. Indeed, there is some evidence that expo-
sure to pesticides in general contributes to its incidence.
Integrated Pest Management

In recent years, integrated pest management (IPM) strategies have been
developed. They combine the best features of various feasible methods of pest
control—not just the use of chemicals—into a long-range, ecologically sound
plan to control pests so that they do not cause economic injury. Generally
speaking, a unique plan is developed for each area and crop, with chemicals
used only as a last resort and when the monetary cost of their use will be more
than recovered by increased crop yield. The six pest control methods that can
be combined are
• chemical control—the use of chemical pesticides, both synthetic and
natural;
• biological control—reducing pest populations by the introduction of
predators, parasites, or pathogens;
• cultural control—introducing farm practices that prevent pests from
flourishing;
• host-plant resistance—using plants that are resistant to attack, including
plants adapted by genetic engineering to have greater resistance;
• physical control—using nonchemical methods to reduce pest
population; and
• regulatory control—preventing the invasion of an area by new species.
Green Chemistry: Insecticides That Target

Only Certain Insects
Insecticides such as the organophosphates and carbamates interrupt the func-
tion of specific enzymes that are common to most insects (and to humans).
They are thus toxic to a wide array of insect species and are known as broad-
spectrum insecticides. Although it may be an advantage to kill more than
one species with a single pesticide, this often leads to the demise of beneficial
insects such as pollinators (bees) and natural enemies (lady bugs and praying
mantises) of insects that are pests.
An approach to limiting the environmental effect of an insecticide is to
develop insecticides that are toxic to only certain species, i.e., the target organ-
ism. One way to accomplish this is to find a biological function that is unique
to the target organism and develop an insecticide that interrupts only that
function. The Rohm and Haas Company of Philadelphia, Pennsylvania, won a
Presidential Green Chemistry Challenge Award in 1998 for the development
of Confirm, Mach 2, and Intrepid. The active ingredients in these insecticides
are members of the diacylhydrazine family of compounds (Figure 10-8a) and
are effective in controlling caterpillars.
Caterpillars are the larval stage of insects such as moths and butterflies, and
during the larval stage they must shed their cuticle to grow. The concentration
(a) C(CH3)3 of 20-hydroxyecdysone (Figure 10-8b), which

O is produced by the caterpillar and is a
R member of the steroid family of compounds,
N
NH increases during the molting process. As a
result of its presence, the caterpillar ceases
O
to feed and sheds its cuticle. The concen-
R tration of this natural compound then
decreases and the caterpillar resumes feed-
(b) ing. The diacylhydrazines present in the
HO OH commercial products Confirm, Mach 2, and
O
CH3 CH3 Intrepid mimic 20-hydroxyecdysone; how-
CH3 ever, their concentrations do not decline,
HO and consequently the insect never resumes
CH3 H3C feeding. The insect thus dies of starvation
OH or dehydration. These insecticides target
HO
only insects that go through molting stages
OH during their growth; most other insects will
FIGURE 10-8 (a) Diacyl- be unaffected.
hydrazine pesticides; Confirm and Intrepid are classified as reduced-risk pesticides by the
(b) 20-hydroxyecdysone. U.S. EPA. This classification program was started in 1993. To be placed in this
category, a pesticide must meet one or more of the following requirements:
1. it reduces pesticide risks to human health;
2. it reduces pesticide risks to nontarget organisms;
3. it reduces the potential for contamination of valued environmental
resources; or
4. it broadens the adoption of IPM (integrated pest management, discussed
in the preceding section) or makes it more effective.
The diacylhydrazene insecticides certainly meet the first two of these
requirements. In order to encourage the development of lower-risk pesti-
cides, the EPA rewards the developers of pesticides that contain active
ingredients that meet the EPA reduced-risk criteria with expedited review.
(http://www.epa.gov/opppmsd1/PR_Notices/pr97-3.html)
Green Chemistry: A New Method

for Controlling Termites
Termites invade over 1.5 million homes in the United States annually and
cause about $1.5 billion in damage. Traditional treatments for termites
involve treating the soil around the affected structure with 100–200 gal of
pesticide solution to create an impenetrable barrier. This process may result
in groundwater contamination, accidental worker exposure, and detrimental
effects to beneficial insects.
(a) (b)
2 F Cl
1 O
NH O
NH CF2 9 CHF2
3 F O Cl
FIGURE 10-9 (a) Sentricon monitoring/baiting station; (b) hexaflumuron structure.

[Source: Photo by Michael Cann.]
Dow AgroSciences in Indianapolis won a Presidential Green Chemistry

Challenge Award in 2000 for its development of Sentricon. In contrast to the
traditional control of termites, Sentricon employs monitoring stations to first
detect the presence of termites prior to the use of any insecticide. The monitor-
ing stations (Figure 10-9a) consist of pieces of wood (1) contained in perforated
plastic tubes (2), which are placed in the ground around the structure. If termites
are detected in any of the monitoring stations, the wood pieces are then replaced
by a perforated plastic tube (3) containing the bait. Bait stations may also be
placed in the structure. The bait consists of a mixture of cellulose and the pesticide
hexaflumuron (Figure 10-9b). Hexaflumuron interrupts the molting process of
termites and thus is not harmful to most beneficial insects. Termites that have
ingested the bait return to their nests and share the bait by trophallaxis, thus
spreading the insecticide throughout the colony. Once the colony has been dec-
imated, the bait is replaced with wood and monitoring resumes.
Hexaflumuron was the first pesticide to be classified as a reduced-risk pesti-
cide by the U.S. EPA. Hexaflumuron is significantly less toxic and is used in
quantities 100 to 1000 times smaller than traditional pesticides (see Table 10-5)
employed for termite control.
TABLE 10-5 Toxicities of Traditional Termiticides vs. Hexaflumuron*
Acute Oral LD50 Acute Dermal LD50

Pesticide (Compound Type) (mg/kg) (mg/kg)
Chlorpyrifos (organophosphate) 135 – 163 2000

Permethrin (pyrethroid) 430 – 4000 4000
Imidacloprid (chloronicotinyl) 424 – 475 5000
Fipronil (pyrazole) 100 2000
Hexaflumuron 5000 2000
* Typical quantity applied: traditional pesticides, 750 – 7000 g; hexaflumuron, 2– 5 g.
Herbicides
Herbicides are chemicals that destroy plants. They are usually employed to
kill weeds without causing injury to desirable vegetation; e.g., to eliminate
broad-leaf weeds from lawns without killing the grass. The agricultural use
of herbicides has replaced human and mechanical weeding in developed
countries and has thereby sharply reduced the number of people employed
in agriculture. Herbicides also are used to eliminate undesirable plants from
roadsides, railway and powerline rights-of-way, etc., and sometimes to defoli-
ate entire regions. Ever since the late 1960s, herbicides have been the most
widely used type of pesticide in North America. As of the early 1990s, about
half the U.S. herbicides used were applied to corn, soybean, and cotton crops.
In ancient times, armies sometimes used salt or a mixture of brine and
ashes to sterilize land that they had conquered, intending to make it unin-
habitable by future generations of the enemy. In the first half of the twentieth
century, several inorganic compounds were used as weed killers—principally
sodium arsenite, Na3AsO3; sodium chlorate, NaClO3; and copper sulfate, CuSO4.
The latter two belong to a large group of salts formerly used as herbicidal
sprays that kill plants by the rather primitive action of extracting the water
from them, while at the same time leaving the land treated in this way still
capable of supporting agriculture.
Organic derivatives of arsenic gradually replaced inorganic compounds as
agricultural herbicides since they are less toxic to mammals (see Chapter 15).
However, both inorganic and metal-organic herbicides have been largely
phased out because of their persistence in soil. Completely organic herbicides
now dominate the market; their utility is based partially on the fact that they
are much more toxic to certain types of plants than to others, so they can be
used to eradicate the former while leaving the latter unharmed.
Atrazine and Other Triazines

One modern class of herbicides is the triazines, which are based upon the
symmetric, aromatic structure shown below, which has alternating carbon
and nitrogen atoms in a six-membered benzene-like ring:
R1 N R2
N N
R3
the general formula of the triazines
In triazines that are useful as herbicides, R1 Cl and R2 and R3 amino groups,

which are nitrogen atoms singly bonded to hydrogens and/or carbon chains.
Herbicides 453
The best-known member of this group is atrazine, which was introduced

in 1958 and has been used since that time in huge quantities to destroy weeds
in corn fields. Indeed, atrazine is the most heavily used herbicide in the
United States (accounting for 40% of all weedkillers applied in the country,
including use on 75% of corn crops) and probably the world. In atrazine,
R2 is ¬NH¬CH2CH3 and R3 is ¬NH¬CH(CH3)2.
H
Cl N
N9CH2CH3
N N
H
H 9 N 9 C 9 CH3
CH3
atrazine
It is usually applied to cultivated soils, at the rate of a few kilograms per

hectare or one kilogram per acre, in order to kill grassy weeds, mainly in sup-
port of corn and soybean cultivation.
Biochemically, atrazine acts as a herbicide by blocking photosynthesis in
the plant in the photochemical stage that initiates the reduction of atmos-
pheric carbon dioxide to carbohydrate. Higher plants, including corn, toler-
ate triazines better than do weeds since they rapidly degrade them to
nontoxic metabolites. However, if the triazine concentration builds up in a
soil—e.g., because of lack of moisture to degrade it—a stage can be reached
where no plants will grow. In high concentrations, atrazine has been used to
eliminate all plant life, e.g., to create parking lots.
Some weeds are becoming atrazine-tolerant. The main ecological risk
from its widespread use is the death of sensitive plants in water systems close
to agricultural fields. Canada has set 2 ppb as the maximum concentration in
water for protection of aquatic life. Some controversial recent research
regarding the effects of low levels of atrazine on wildlife is discussed in
Chapter 12.
While in soil, atrazine is degraded by microbes. One such biochemical
reaction results in the replacement of chlorine by a hydroxyl group, ¬OH,
yielding a metabolite that is not toxic to plants. The other microbial path-
ways involve the loss of either the ethyl group or the isopropyl group from
an amino unit, with its replacement by hydrogen; these metabolites are toxic
to plants.
Although it only persists in most soils for a few months, once it or its
metabolites enter waterways, atrazine’s half-life is several years. For example,
in the Great Lakes, its half-life is about 2–5 years, whereas it is less than half
a year in Chesapeake Bay, presumably because the water is warmer so metab-

olism is faster there.
Atrazine is moderately soluble (30 ppm) in water. During rainstorms, it
is readily desorbed from soil particles and dissolved in the water moving
through the soil. In waterways that drain agricultural land on which atrazine
is used, its concentration typically is found to be a few parts per billion. Usu-
ally atrazine is detectable in well water in such regions. The possible risks of
atrazine to amphibians are discussed in Chapter 12.
Unfortunately, atrazine is not removed by typical treatments of drinking
water unless carbon filtration is used. However, less than 0.25% of the popu-
lation in the U.S. cornbelt states consume atrazine at greater than 3 ppb, its
maximum contaminant level, MCL. The MCL values for substances are the
maximum permissible concentrations of substances dissolved in the water of
any public system in the United States and are based on average annual con-
centrations. Currently the U.S. EPA is re-evaluating the potential risk of
atrazine to humans and the environment. Several European countries have
banned atrazine as they would any pesticide that exceeds a level of 0.1 ppb in
drinking water, regardless of whether or not it has been proven to be a human
health risk.
Since atrazine’s measured BCF is less than 10, bioaccumulation does not
represent a significant problem. Atrazine is not a very acutely toxic compound
(its LOD50 is about 2000 mg/kg). However, some surveys on the health of
farmers and other individuals exposed to it in high concentrations show
disturbing links to higher cancer rates and a higher incidence of birth defects.
No definitive studies linking atrazine use to human health problems have as
yet been reported. Nevertheless, the U.S. EPA has listed it as a possible human
carcinogen and has directed states to devise plans to protect groundwater from
herbicide contamination.
In certain American agricultural regions, atrazine usage has been banned
outright. For a few years, the triazine called cyanazine—which has the same
chemical formula as atrazine except that one hydrogen in the isopropyl group
is replaced by a cyanide group—became quite popular as an agricultural her-
bicide, but its manufacturer now has voluntarily phased it out of production
because of questions about its effect on human health. Other triazines with
similar uses are simazine and metribuzin.
Chloroacetamides and the Occurrence of Pesticides

in Groundwater
In some regions where soybeans and corn are grown intensively, atrazine has
yielded its status as the herbicide of choice to one of the chloroacetamides,
which are derivatives of chloroacetic acid, ClCH2COOH, in which the
¬OH group is replaced by an amino group ¬NR1R2. The most prominent
Herbicides 455
herbicides of this type are alachlor, metolachlor, and acetochlor. These three
compounds differ only in minor variations in the complicated organic groups
R1 and R2 attached to the amino nitrogen. Alachlor is a carcinogen in ani-
mals, and metolachlor is suspected of being one as well. The EPA has
proposed that the use of alachlor, metolachlor, atrazine, and simazine be care-
fully managed in areas where they are used intensively since they represent a
significant risk to groundwater.
O O
HO 9 C R1R2N 9 C
CH2Cl CH2Cl
chloroacetic acid general structure of chloroacetamide herbicides
Generally, the concentrations of these herbicides in waterways that drain

agricultural land peak in May and are nondetectable by the end of summer;
however, all are somewhat toxic to fish. Alachlor and its degradation products
have been detected in groundwater that lies under corn fields. Metolachlor is
known to degrade in the environment by the action of sunlight and of water.
The chloroacetamides degrade by reaction with water since their amide unit
undergoes hydrolysis, producing an amine and chloracetic acid:
O O
ƒƒ ƒƒ
R1R2N—C—CH2Cl H—OH ¡ R1R2N—H HO—C—CH2Cl
Atrazine and its metabolite and metolachlor were the agricultural herbicides
most often detected in streams and shallow groundwater in both urban and
agricultural areas according to an investigation by the U.S. Geologic Survey
in the 1990s. Domestic herbicides found most often were the triazines
simazine and prometon. Insecticides found in highest concentrations—
principally carbaryl and the organophosphates diazinon, malathion, and
chlorpyrifos—were higher in urban than rural regions, presumably because of
domestic usage. More than 95% of the streams, and 50% of the groundwater
samples, were found to contain at least one pesticide at detectable levels.
Research in Switzerland has found levels of atrazine, alachlor, and other
agricultural pesticides in rainwater that exceed drinking water standards.
Presumably the pesticides evaporated from farm fields.
Glyphosate
Glyphosate is an example of a phosphonate, a class of compounds that are
structurally similar to organophosphates except that one oxygen of the four
that surround phosphorus is missing and is replaced by an organic group, in

this case a methylene group, ¬CH2—, attached to the simple amino acid
glycine.
O H H H O
H9O9P9C9N9C9C9O9H
H9O H H
glyphosate
Glyphosate is widely used as a herbicide, e.g., as the commercial product

Roundup. It is rather nontoxic: its LD50 values are high for both oral and der-
mal routes of exposure, although acute ingestion of or exposure to large
quantities of it is fatal. Dermal and oral absorption of it is small, and it is
eliminated essentially unmetabolized. Glyphosate is nonresidual, and there
is no evidence that it bioaccumulates in animal tissue or is carcinogenic or
teratogenic. The same is true of its initial breakdown product, the substance
corresponding to cleavage of the rightmost NH—CH2 bond in the structure
above.
Glyphosate operates by inhibiting the synthesis of amino acids con-
taining the aromatic benzene ring, which in turn prevents protein synthe-
sis from occurring. Although it kills almost all plants, some strains of
soybeans have been genetically altered using biotechnology so that they are
resistant to glyphosate; consequently, it can be used as a weed killer in the
growth of the crop (see Box 10-2). Its advantages in growing soybeans are
that it replaces several different herbicides and that only one application is
required, though the total volume of herbicide used is not reduced substan-
tially. Its greater tendency to stay adsorbed on soil means that it has a lesser
tendency to occur in runoff and subsequently in water supplies than do the
herbicides atrazine and alachlor, which it replaces. The evidence gathered
so far indicates that glyphosate is a relatively benign herbicide.
Phenoxy Herbicides
Phenoxy weedkillers were introduced at the end of World War II. Environ-
mentally, the by-products contained in commercial products of such herbi-
cides are often of greater concern than the herbicides themselves, as we shall
see in Chapter 11. For that reason, we begin by discussing the chemistry of
phenol, the fundamental component of these compounds.
Phenols are mildly acidic; in the presence of concentrated solutions of a
strong base like NaOH, the hydrogen of the OH group is lost as H (as occurs
Herbicides 457
BOX 10-2 Genetically Engineered Plants
n 1940 the world population was 2.3 billion drought, pests, salinity, and frost, as well as
I people; by 1985 it had more than doubled,
and it now exceeds 6.5 billion. Fortunately,
improved taste and nutritional value. The
best-known examples of herbicide-resistant
beginning in the 1940s, a “green revolution” in plants that have been developed are known
agriculture took place that allowed the world as Roundup Ready. Roundup, as was previously
to feed this burgeoning population. Extensive mentioned, is a commonly used broad-
development and use of pesticides (many of spectrum herbicide. Monsanto, its manufac-
which have been mentioned in this chapter) turer, has developed and patented genetically
and fertilizers, along with irrigation and plant altered seeds for soy, corn, alfalfa, sorghum,
breeding programs, led to dramatic increases canola, and cotton which grow into plants that
in the yield per acre of crops. Total worldwide are resistant to destruction by Roundup. Fields
grain production increased from 600 million planted with these crops can be sprayed indis-
metric tons in 1950 to more than 1600 million criminately to destroy weeds, with little con-
metric tons by 1985. Since 1995, production cern for destruction of the crop.
has leveled off at 1800–2000 metric tons. How- The use of transgenic plants has been
ever, the human population continues to grow widely adopted in the United States. In 2005,
and is expected to reach 9 billion by 2050. 87% of all soybean acreage in the United
Since the 1980s, talk of a second green States was planted with transgenic crops, fol-
revolution has centered about genetically lowed by cotton at 79% and corn at 52%. The
engineered plants. Traditional crossbreeding top five countries in growing transgenic crops
of wheat plants over many years has resulted in 2005 were the United States, Argentina,
in plants that yield two to three times more Brazil, China, and Canada.
grain than previously existing varieties and are Although transgenic plants offer the pos-
more resistant to pests and diseases. Genetic sibility of improving upon what nature has
engineering of plants offers the possibility of provided us, there are significant concerns
doing these same things and additional feats in about these organisms, especially in Europe.
much less time and with more selectivity than Concerns include:
traditional crossbreeding.
• the use of greater quantities of herbicides,
Genetic engineering involves taking a por-
since there is less fear of destroying a crop
tion of the DNA from one species and inserting
from the indiscriminate application of the
it into the DNA of another, unlike species. One
herbicide;
striking example of this technique has been to
take the human DNA (gene) that codes for the • the spread of herbicide resistance to
synthesis of the protein insulin and insert it related plants that become “super weeds”; and
into that of bacteria, thus allowing the bacteria
• the decrease in genetic diversity of crops
to produce insulin. This results in the produc-
as farmers all use the same seeds.
tion of human insulin to be used for medical
purposes. In addition to these concerns, genetically
Transgenic plants have been produced engineered grains have not resulted in sub-
which have enhanced resistance to herbicides, stantial increases in crop yields.
with any common acid) and the phenoxide anion, C6H5O, is produced in the
form of its sodium salt:
OH O Na
NaOH H2O
phenol
The ONa group is a reactive one, and this property can be exploited in
order to prepare molecules containing the C¬O¬C linkage. Thus if an
R¬Cl molecule is heated together with a salt containing the phenoxide ion,
NaCl is eliminated and the phenoxy oxygen links the benzene ring to the
R group:
C6H5ONa Cl¬R ¡ C6H5¬O¬R NaCl
Such a reaction is the most direct commercial route to the large-scale
preparation of the herbicide, introduced in 1944, whose well-known com-
mercial name is 2,4,5-T. Here (in the reaction immediately above) the R group
is acetic acid, CH3COOH, minus one of its methyl group hydrogens, so
that R ¬CH2COOH, and the Cl¬R reactant is Cl¬CH2COOH. Then,
according to the reaction, C6H5¬O¬CH2COOH, called phenoxyacetic
acid, is obtained as an intermediate in the production of the actual
herbicides.
In the commercial herbicides, some of the five remaining hydrogen atoms
of the benzene ring in phenoxyacetic acid are replaced by chlorine atoms.
O O
O 9 CH2 9 C O 9 CH2 9 C
Cl OH Cl OH
Cl
Cl Cl
2,4-D 2,4,5-T
2,4-dichlorophenoxyacetic acid 2,4,5-trichlorophenoxyacetic acid
Note that the numbering scheme for the benzene ring begins at the carbon
attached to the oxygen.
The 2,4-D compound (2,4-dichlorophenoxy acetic acid) is used to kill
broad-leaf weeds in lawns, golf course fairways and greens, and agricultural
Herbicides 459
fields. In contrast, 2,4,5-T (2,4,5-trichlorophenoxy acetic acid) is effective

in clearing brush, for instance, on roadsides and powerline corridors. Like the
P¬O¬C bonds in organophosphates, the O¬C bond to the ¬CH2¬
group in 2,4-D and analogous phenoxy herbicides undergoes a hydrolysis
reaction in the environment, degrading the compound to a phenol
R¬O¬CH2¬COOH H¬OH 9: R¬O¬H HOCH2¬COOH
The herbicide MCPA is 2,4-D with the chlorine in the 2 position
replaced by a methyl group, ¬CH3. The herbicides called dichlorprop, silvex,
and mecoprop are identical to 2,4-D, to 2,4,5-T, and to MCPA, respectively,
except that their molecules have a methyl group replacing one hydrogen
atom of the ¬CH2¬ group in the acid chain; thus they are phenoxy herbi-
cides that are based on propionic acid, CH3¬CH2¬COOH, rather than
on acetic acid. The herbicide dicamba is the same as 2,4-D with a methoxy
group at the 5 position of the benzene ring; it is often used as a weedkiller in
corn fields.
Huge quantities of 2,4-D and its closely related analogs described above
are used in developed countries for the control of weeds in both agricultural
and domestic settings. In some communities, their continued use on lawns
has become a controversial practice because of their suspected effects on
human health. In particular, farmers in the midwestern United States who
mix and apply large quantities of 2,4-D to their crops are found to have an
increased incidence of the cancer known as non-Hodgkin’s lymphoma.
The Degradation of Pesticides

Although some pesticides such as DDT are very long-lived in the environ-
ment, most undergo chemical or biochemical reactions within a few days or
months, producing other compounds. Based upon their typical half-lives in
the environment, the U.S. EPA classifies pesticides as being:
• nonpersistent, if they last less than 30 days;
• moderately persistent for those lasting 30–100 days; and
• persistent for lifetimes greater than 100 days.
Like most organic compounds, pesticides in the environment—whether
present in air, water, or soil—degrade to other compounds, which in turn
decompose further. The complete eventual breakdown of organic com-
pounds to CO2, H2O, and stable inorganic forms of its other elements is
called mineralization.
In air, the degradation process usually begins either with attack on the
organic molecule by the hydroxyl radical, OH, or with a photochemical reac-
tion if the substance absorbs light with wavelength greater than about 285 nm,
in accordance with the principles discussed in Chapter 5.
Photochemical decomposition is possible also for pesticides present in

water or adsorbed onto soil resident at the Earth’s surface. In some instances,
adsorption onto soil particles increases the maximum wavelength of light the
substance absorbs into the range in sunlight—an example is the herbicide
paraquat, which undergoes photolysis more rapidly when adsorbed on clay
than it does in solution. Complexation of organic molecules by metal ions
also usually increases their maximum wavelength of absorption, thereby acti-
vating them for photochemical decomposition by sunlight in some cases.
As we already have discussed several times in this chapter, pesticides in
water and in soil can undergo hydrolysis reactions, especially when the water
is somewhat acidic or somewhat basic, since catalysis by H or OH can
then speed up the processes significantly. Organophosphate insecticides, for
example, hydrolyze in alkaline water and soil owing to attack by OH on the
P¬O¬C link. Even in quite dry soils, hydrated aluminum ions produce
hydrogen ions that in the existing moisture can catalyze hydrolysis.
Al(H2O)63 9: Al(H2O)5OH2 H
For example, in triazine herbicides, hydrolysis can convert their C¬Cl
bonds to C¬OH ones, thereby eliminating their herbicidal activity. Organic
compounds, including pesticides, can also be transformed in water or soil by
oxidation or reduction reactions. Although dissolved O2 itself can oxidize,
its reactions are often accelerated by the presence of dissolved or adsorbed
transition metal ions, which oxidize the pesticide and whose reduced form is
subsequently re-oxidized by O2. For example, Fe3 is a good oxidizing agent
for many organic compounds; the Fe2 state to which it is reduced in the
process is subsequently oxidized by oxygen back to Fe3, thereby completing
the cycle.
Reducing agents are commonly found in anaerobic waters and soil; they
include Fe2 and sulfide ion, S2. For example, pesticides that contain a
C¬Cl unit are dechlorinated by iron when it abstracts an electron from the
C¬Cl bond, thereby releasing Cl and forming Fe3 and a reactive carbon-
based free radical.
Even more important than the chemical processes described above are
degradation reactions facilitated by microbial action in water and soil.
Chemheterotrophs are microorganisms that derive the energy they require from
redox reactions and their carbon from organic compounds. The metabolic
reactions proceed in stepwise fashion, the individual steps usually being oxi-
dation, reduction, or hydrolysis. However, the rates of degradation vary over
a very wide range, depending on the molecular structure of the pesticide and
the properties of the soil. Compounds containing functional groups such as
¬OH, ¬NO2, ¬NH2, and carboxylate degrade most readily in soils since
they contain a site for enzymatic attack and are relatively soluble in water,
whereas highly chlorinated hydrocarbons are much more resistant since there
is no reactive site and their water solubility is very low.
Summary 461
A common example of a microbial oxidation step is enzyme-catalyzed

epoxidation, a process in which an oxygen atom from an O2 molecule is added
to a C“C bond, even one contained within an aromatic benzene ring system:
O2
O
Following epoxidation, the adduct can undergo further reactions, for example,
• rearrangement to a hydroxylated compound, thereby reestablishing the
highly stable aromatic ring; or
• hydrolysis to produce an ortho-dihydroxyl compound; or
• the addition of further oxygen and water to other double bonds within
the aromatic system.
Subsequent reactions at an adjacent pair of carbons having ¬OH groups
often lead to ring cleavage at that site, yielding a dicarboxylic acid.
Summary
In general, there is no pesticide that is completely “safe.” However, the elim-
ination of all synthetic pesticides would lead to an increase in the transmis-
sion of disease by insects and an increase in the cost of food, both of which
would affect human health adversely. Any decision about discontinuing the
production and use of a given pesticide must consider whether cheap, safer
alternatives are available and, if not, what the consequences are of both
action and inaction. The quandary about whether to ban the use of DDT in
tropical developing countries is an excellent illustration.
When a new pesticide, or indeed any other synthetic chemical, is about
to be introduced into the market, many environmental groups and some gov-
ernment agencies have proposed that we should err on the side of being too
cautious and only allow its introduction if there are no signs that problems
could arise. They propose that in such situations, to prevent possible harm to
the health of humans and other organisms, we should employ what is now
known as the precautionary principle. One definition of this principle was
given at the 1992 U.N. Conference in Rio on Environment and Development:
“Where there are threats of serious or irreversible damage, lack of full scien-
tific certainty shall not be used as a reason for postponing cost-effective
measures to prevent environmental degradation.” Opponents of the use of
this principle point out that it is impossible to anticipate all possible conse-
quences, positive or negative, of introducing a new substance and that
consequently we could become frozen into inaction. The best technique for
predicting where a given pesticide will ultimately end up in the environment
is through the calculations described in Box 10-3.
BOX 10-3 The Environmental Distribution of Pollutants
hen a persistent chemical, such as DDT, concentration, C, in that phase:

W is released into the environment, we find
that later some of it has dissolved in natural f C兾Z
bodies of water, some is in the air, some is pres- where Z is the fugacity capacity constant for the
ent in soil and sediments, and some is located substance and the phase. Generally, the higher
in living matter. A constant interchange of the value of Z, the greater the tendency of a chem-
chemical occurs among these various physical ical to concentrate in that phase. (These
phases. It is possible to estimate the amount capacity constants are analogous to the equi-
and concentration of the chemical in each librium constants used in chemical reaction
phase once the release of the chemical has calculations.) If we use x to denote the phase
stopped and sufficient time has passed that of interest, then
equilibrium among the phases has been
achieved. Even when equilibrium conditions fx Cx 兾Zx
are not yet in place, it is of value to determine
the phases where the chemical will ultimately We can determine the concentration in each
be concentrated. phase by rearranging the equation, to give
Recall from your previous background in Cx fx Zx
chemistry that in calculations involving sub-
stances participating in chemical reactions, we At equilibrium, the fx values for all phases are
algebraically combine experimental values of identical, equal to f, say. Thus, if we know f,
equilibrium constants with information con- we can determine the concentration in each
cerning initial concentrations in order to deter- phase from the simplified equation
mine equilibrium concentrations. A somewhat
analogous procedure can be applied to deter- Cx f Zx
mine the distribution of a substance when by
physical processes it has achieved equilibrium As in chemical equilibrium problems, we
between several phases. The condition that usually know the total number of moles, ntotal,
equilibrium has been achieved in its distribu- of the material. As in chemical problems, it is
tion is that the fugacity, f, of the substance, useful to state the mass conservation condi-
which is defined as its tendency to escape from tion: the sum of the equilibrium number of
a given physical phase, is equal for all phases. moles, nx, present in each phase x must add up
Fugacity has units of pressure, e.g., atmospheres to ntotal. By definition, each nx is equal to the
or kilopascals. Thus, for example, when all the concentration Cx times the volume Vx for the
DDT in the environment has distributed itself phase:
among air, water, sediment, biota, etc., the nx Cx Vx
concentrations in each phase are such that its
tendency to escape from any phase (and enter Substitution of the next-to-last equation into
any other) has the same value for all phases. the last one gives
As you might expect, the fugacity of a sub-
stance in a given phase is proportional to its nx f Zx Vx
Summary 463
When we sum the nx values over all phases x for the air phase, 40.3
of interest, we must obtain the total number for the water phase, 3.92 104
of moles. Thus for the sediment phase, 2.25 109
ntotal f Zx Vx In the evaluations of Zx values from experi-
mental data, a temperature of 25°C is usually
Rearrangement of this equation allows us to assumed for simplicity. The Zx values for sedi-
calculate the value of the system fugacity: ment (and biota) are assumed to be proportional
f ntotal 兾 Zx Vx to the octanol–water partition coefficients Kow
discussed earlier in the chapter.
An Example of a Fugacity Calculation After substitution of the values for Zx and
Vx, the value of the fugacity in this case is
As an example of how fugacity calculations
are carried out in practice, consider the distri- f 1.0兾(40.3 1010 3.92 104 7
bution of 1 mole of DDT among three phases: 106 2.25 109 2 104)
air, water, and sediment in a model compart- 1.0兾(4.03 1011 2.74 1011
ment of Earth (Figure 1). As discussed later, 4.5 1013)
we take the volume of air to be 1010 m3, the
2.19 1014 atm
water volume to be 7 106 m3, and the volume
of accessible sediment to be 2 104 m3. The The concentration of the chemical can now
values of the Zx constants for DDT, in units of be computed for each phase:
mol/atm m3, are determined from experimen-
tal data to be Cx f Zx
1 km
1 km Air
1010 m3
10 km
10 m
Soil Water 7 × 106 m3
9 × 103 m3 3 cm
Sediment (includes biota) 2 × 104 m3
FIGURE 1 Model world
parameters used in fugacity
calculations.
BOX 10-3 The Environmental Distribution of Pollutants (continued)
so to be average for the real Earth. The atmo-

DDT concentration in air 2.19 10 14 sphere is taken to be 10 kilometers high, which
40.3 8.8 1013 mol/m3 is a reasonable approximation to the tropo-
sphere. The air volume then is (1000 m
DDT concentration in water 2.19 1014
1000 m) (10,000 m) 1010 m3. The 1-km
3.92 104 8.6 1010 mol/m3
square is assumed to be 70% covered by water
DDT concentration in sediment 2.19 and 30% by soil. The average water depth is
1014 2.25 109 4.9 105 mol/m3 taken to be 10 meters, which is relatively shal-
Notice the preferential concentration of DDT low since we are interested only in the part that
in sediment, which is hydrophobic due to its achieves equilibrium with the air. Thus the
carbon content. water volume is 0.7 (1000 m 1000 m)
The amounts in each phase are given by the 10 m 7 106 m3. The sediment in equilib-
fZV values, i.e., the concentrations multiplied rium with this water is assumed to be only 3
by the respective volumes. Then the number of centimeters deep, giving it a volume of 0.7
moles of DDT 1000 m 1000 m 0.03 m 2.1 104 m3.
in air 8.8 1013 1 1010 0.0088 mol In addition to air, water, and sediment, the
model usually also includes soil, whose effec-
in water 8.6 1010 7 106 0.0060 mol
tive volume is 9 103 m3, plus 35 m3 of solids
in sediment 4.9 105 2 104 0.98 mol suspended in the water, and about 3.5 m3 of
Thus we see that, with air, water, and sediment biota such as fish. The Z values for biota are
accessible to it, 98% of the DDT will be found usually of the same order of magnitude as those
in sediment, and about 1% in air and in water. for sediment, so the concentration of a given
Notice that the concentration of DDT in water chemical in biota is close to that in sediment.
is greater than in air, but the total amount of it
in air exceeds that in water because the air vol-
PROBLEM 1
ume is so much larger. This sort of interchange
in ordering between amount and concentration The Z values for hexachlorobenzene are 4 104
in different phases is common for pollutant in air, 9.5 105 in water, and 2.3 in sediment
chemicals. (and biota). Using the model world volumes
above, calculate the equilibrium concentrations
The Parameters for the Model World when 1 mole of hexachlorobenzene is distributed
in Fugacity Calculations Are Estimates among air, water, and sediment.
The volumes for the various phases used in
the above calculation are based upon a model
PROBLEM 2
“world” (Figure 1) whose components are able
to be in equilibrium with each other. Since In fugacity calculations, the Z values for diel-
only concentrations are obtained in the calcu- drin are 4 104 in air, 2.0 in water, and 2
lations, it is important only that the relative 105 in sediment (and biota). Using the model
volumes, not their absolute values, be used. world volumes above, calculate the equilib-
The model world has an area of 1 kilometer by rium concentrations when 1 mole of dieldrin is
1 kilometer, whose characteristics are assumed distributed among air, water, and sediment.
Review Questions
1. What are the three main categories of pesti- 16. Sketch a typical dose–response curve rela-
cides? What types of organisms are killed by each tionship for a toxic chemical using (a) a linear,
category? and (b) a logarithmic scale for doses.
2. What is meant by the term fumigant? 17. Define the terms LD50 and LOD50.
3. Name three important properties shared by 18. What are the general structures of the three
organochlorine pesticides. main subclasses of organophosphate insecticides?
Give the name of one insecticide in each sub-
4. Draw the structure of DDT, and state what the
class. Explain how organophosphates function as
initials stand for.
insecticides.
5. What units are usually used to state the con-
19. In what way are organophosphate insecticides
centrations of trace contaminants in water?
considered superior to organochlorines as pesti-
6. What were the main uses of DDT? Explain why cides? In what way are they more dangerous?
it is no longer used in many developed countries
20. What is the general structure of carbamate
and why some developing countries wish to con-
insecticides? Name one example.
tinue using it.
21. What are five of the pest control methods that
7. Explain how DDT functions as an insecticide.
are used in pest control management?
8. Draw the structure of DDE. Is it a pesticide or
22. What is the function of an herbicide? Name a
not? Explain.
few “old-fashioned” insecticides.
9. Explain what is meant by the terms bioconcen-
23. What is the general structure of a triazine
tration and bioconcentration factor (BCF).
herbicide? Name two commercial examples.
10. Explain what is meant by the term biomagni-
24. What is the general structure of chloro-
fication, and how it differs from bioconcentration.
acetamide herbicides? Name one example.
11. Write the defining equation for the partition
25. What is the formula of gyphosate? What are
coefficient Kow. How is it related to a compound’s
its advantages over other herbicides?
BCF? What is octanol supposed to be a surrogate
for in this experiment? 26. What is phenol? Draw its structure and that of
2,4-dichlorophenol.
12. Describe one analog of DDT that works in the
same fashion but does not bioaccumulate. 27. Draw the structures, and write out the names,
of the two most important phenoxy herbicides.
13. In general terms, explain what toxaphene is
and why it is no longer in use. 28. What is meant by the precautionary principle?
14. Draw the structure of cyclopentadiene. Name 29. Write out three examples of hydrolysis
at least three insecticides produced from it. reactions by which pesticides are degraded in
the environment.
15. Define the terms acute toxicity and dose.

See the discussion of focus areas and the principles 4. How do Confirm, Mach2, and Intrepid act to
of green chemistry in the Introduction before only target specific insects?
attempting these questions.
5. The development of the Sentricon system won
1. The development of the insecticides Confirm, a Presidential Green Chemistry Challenge Award.
Mach2, and Intrepid won a Presidential Green (a) Into which of the three focus areas for these
Chemistry Challenge Award. awards does this award best fit?
(a) Into which of the three focus areas for these (b) List two of the twelve principles of green
awards does this award best fit? chemistry that are addressed by the hexaflumuron/
(b) List one of the twelve principles of green chem- Sentricon system?
istry that are addressed by these new pesticides. 6. What environmental advantages does the
2. What environmental advantage do Confirm, hexaflumuron/Sentricon system offer compared
Mach2, and Intrepid offer compared to to conventional termite control pesticide
conventional pesticides? methods?
7. Which categories under the reduced-risk
3. (a) What is a U.S. EPA reduced-risk pesticide? criteria does the hexaflumuron/Sentricon
(b) Which categories under the reduced-risk crite- system meet?
ria do Confirm, Mach2, and Intrepid meet?
Additional Problems
1. The threshold/NOEL level found for a particular (b) Both from your graphs and by solving the
chemical from animal studies is 0.004 mg/kg body equation above analytically, find the dose corre-
weight per day. The only source for the chemical is sponding to LD50.
freshwater fish, where it occurs at an average level (c) Does the function R have a nonzero threshold
of 0.2 ppm. What is the maximum average daily at low doses? Can you confidently predict the
consumption of such fish that would keep exposure answer to this from inspecting your logarithmic
level below the ADI or RfD for the compound? dose–response curve?
2. An approximate mathematical fit to the form 3. The fat (lipid) content of breast milk averages
of the dose–response curve of Figure 10-5a is about 4.2 g/100 mL. Based on Figure 10-1b,
R 1 ed calculate the mass of DDE that would have been
ingested by a typical breast-fed Swedish infant in
where R is the fractional response and d is the dose.
1972 consuming 250 mL of breast milk.
(a) Plot R versus d for values of d ranging from
0 to 5 on both linear and logarithmic scales for d. 4. The BCF for a substance in a particular aquatic
(Be sure to include some small values of d, from species (not just its fat tissues) can be estimated as
0.01 to 0.10, in the logarithmic plot to ensure that the Kow value for the substance times the fraction
the form of the curve near zero is displayed.) Do of body fat in the species of interest. Rainbow trout,
the forms of the curves resemble those in which average 5.0% body fat, taken from a particular
Figures 10-5a and 10-5b, respectively? lake were found to contain 22 ppb in their tissues.
Use the information in Table 10-3 to determine the washed 35% of it into a nearby lake having a
concentration of parathion in the lake. surface area of 30,000 m2 and an average depth
of 0.5 m. Would the pesticide concentration
5. The pesticide azinphos-methyl has a 96-hour
in the lake water have been sufficient to kill a
LC50 value of 3 ppb for rainbow trout. In an
significant fraction of the rainbow trout in
unfortunate incident, 200 g of this pesticide was
the lake?
sprayed on a field, and a subsequent heavy rainfall
Further Readings
1. V. Turusov et al., “DDT: Ubiquity, Persistence, 6. (a) C. Lu et al., “A Longitudinal Approach to
and Risks,” Environmental Health Perspectives 110 Assessing Urban and Suburban Children’s Exposure
(2002): 125. to Pyrethroid Pesticides,” Environmental Health
Perspectives 114 (2006): 1419. (b) C. Lu et al.,
2. B. Hileman, “Reexamining Pesticide Risk,”
“Organic Diets Significantly Lower Children’s
Chemical and Engineering News (17 July 2000): 34.
Dietary Exposure to Organophosphate Pesticides,”
3. G. Santaoro, “Silent Summer,” Discover Environmental Health Perspectives 114 (2006): 260.
(July 2000): 76.
7. G. M. Williams et al., “Safety Evaluation and
4. M. Lopez-Cervantes et al., “Dichlorodiphenyl- Risk Assessment of the Herbicide Roundup and
trichlorethane Burden and Breast Cancer Risk: A Its Active Ingredient, Glyphosate, for Humans,”
Meta-Analysis of the Epidemiological Evidence,” Regulatory Toxicology and Pharmacology
Environmental Health Perspectives 112 (2004): 207. 31 (2000): 117.
5. K. Noren and D. Meironyte, “Certain 8. T. P. Brown et al., “Pesticides and Parkinson’s
Organochlorine and Organobromine Contami- Disease—Is There a Link ?” Environmental Health
nants in Swedish Milk in Perspective of Past Perspectives 114 (2006): 156.
20–30 Years,” Chemosphere 40 (2000): 1111.
C H A P T E R
11
DIOXINS, FURANS, AND PCBs
topics are used:
 Elementary organic chemistry (as in the Appendix in
this book)
 First-order kinetics rate law
 Concept of vapor pressure
Background from previous chapters used in this

chapter:
 Structure of phenols (Chapter 10)
 Carcinogens and toxicology concepts, including LD50
(Chapter 10)
 Concept of adsorption (Chapter 4)
Introduction
As we have seen in Chapter 10, compounds used as pesticides are somewhat
toxic to humans, and can bioaccumulate and cause environmental problems.
But sometimes it is the highly toxic trace impurities in commercial lots of
such substances that are the principal concern regarding human health. In
this chapter, we shall analyze how such hazardous by-products, especially
dioxins, arise in the environment, not only from pesticide manufacture but
from other anthropogenic processes as well. Also considered are PCBs, indus-
trial chemicals of widespread environmental concern with respect to both
their own properties and those of their contaminants. As we shall see, the
toxicity mechanisms by which these contaminants, the PCBs themselves,
and dioxins operate all are quite similar.
Dioxins
Dioxins are not articles of commerce, nor are they normally produced delib-
erately for purposes other than scientific investigation. They arise as by-products
469
470 Chapter 11 Dioxins, Furans, and PCBs
in the production of certain herbicides and in some other processes, as we

shall see below.
Dioxin Production in the Preparation of 2,4,5-T

Traditionally, the industrial synthesis of the herbicide called 2,4,5-T (dis-
cussed in Chapter 10) started with 2,4,5-trichlorophenol, which itself was pro-
duced by reacting NaOH with the appropriate tetrachlorobenzene. The OH
group replaces one chlorine atom in the process. Unfortunately, during this
synthesis there occurs an additional reaction that converts a very small por-
tion of the trichlorophenol product into “dioxin.” In this side reaction, two
trichlorophenoxy anions react with each other, resulting in the elimination of
two chloride ions:
Cl O Cl Cl Cl O Cl
heat
2 Cl
Cl Cl O Cl Cl O Cl
‘‘dioxin’’
(tetrachlorodibenzo-p-dioxin)
In this process a new six-membered ring is formed which links the two chlo-
rinated benzene rings. This central ring has two oxygen atoms located para
(i.e., opposite) to each other, as is found in the simple molecule 1,4-dioxin or
para-dioxin (p-dioxin).
O
1,4-dioxin
Although the molecule labeled “dioxin” above is correctly known as a

tetrachlorodibenzo-p-dioxin, it has become popularly known simply as
“dioxin,” with the understanding that it is the most toxic of a class of
related compounds.
The side reaction that produces dioxin as a by-product is kinetically
second-order in chlorophenoxide. In other words, the rate of the reaction
depends on the square (or second power) of the ion’s concentration. Conse-
quently, the rate of dioxin production increases dramatically as the initial
chlorophenoxide ion concentration increases. Also, the rate of this side
reaction increases more rapidly with increasing reaction temperature than
does the main reaction. Therefore, the extent to which the trichlorophenol
and consequently the commercial herbicide become contaminated with the
Dioxins 471
dioxin by-product can be minimized by controlling concentration and tem-

perature in the preparation of the original trichlorophenol. Today, the
contamination of commercial 2,4,5-T by this dioxin can be kept to less
than 0.1 ppm by keeping both the phenoxide concentration and the tem-
perature low. Nevertheless, its manufacture and use in North America were
phased out in the mid-1980s because of concerns about its dioxin content,
however small.
A 1:1 mixture of the herbicides 2,4-D and 2,4,5-T called Agent Orange
was used extensively as a defoliant during the Vietnam War. Since the mix-
ture contained dioxin levels of about 10 ppm, it is clear that the reaction used
to produce the trichlorophenol used for 2,4,5-T preparation was not carefully
controlled so as to minimize contamination. As a result, the soil in southern
Vietnam is contaminated by dioxins. The consequences of this contamination
for the residents, and for the American troops who were exposed while spraying
was underway, are still controversial. There is some evidence that the rate of
melanoma has increased in Air Force personnel who were involved in the
spraying. It was realized recently that the defoliation potential of Agent
Orange was originally tested in the 1960s by the U.S. armed forces near
Gagetown, New Brunswick, Canada, and that the soil in the area is polluted
by the substance.
Environmental contamination by dioxin also occurred as the result of an
explosion in a chemical factory in Seveso, Italy, in 1976. The factory pro-
duced 2,4,5-trichlorophenol from tetrachlorobenzene, as described above.
On one occasion the reaction was not brought to a complete halt before the
workers left for the weekend. The reaction continued unmonitored, and the
heat subsequently released by the reaction eventually resulted in an explo-
sion. Since the trichlorophenol had been heated to a high temperature, a
considerable amount of dioxin—probably several kilograms—was produced.
The explosion distributed the toxin into the environment, and many wildlife
deaths resulted from the contamination. Although a large number of
humans, both adults and children, were also exposed to the chemical as a
result of this explosion, no serious health effects to humans were found for
many years. Recent studies, however, have established that the rates of
several types of cancers are elevated in people who lived in the zones most
exposed to dioxin from the explosion. Specifically, the risk of contracting
breast cancer increased in proportion to the dioxin exposure, as measured by
the level of the substance in women’s blood samples taken soon after the
explosion.
Dioxin Numbering System

The nomenclature and numbering system used for ring systems like the diox-
ins is a little unusual. Since the central dioxin ring is connected on either side
to benzene rings, the three-ring unit is properly known as dibenzo-p-dioxin.
The chlorine substitution on the outer rings also should be recognized, so the
dioxin shown below is a tetrachlorodibenzo-p-dioxin, or TCDD.
10
9 1
Cl O Cl
8 2
3
7
Cl 6
O 4
Cl
5
2,3,7,8-tetrachlorodibenzo-p-dioxin
(2,3,7,8-TCDD)
The numbering scheme for the ring carbons in dioxins takes into account
the fact that the carbons shared between two rings carry no hydrogen atoms
and so need not be numbered. Thus C-1 is the carbon next to one joining the
rings, and the numbering follows a direct path from there. By convention, the
oxygen atoms are also part of the numbered sequence in this scheme, although
their locations are not used in naming any of this family of compounds. The
initial (C-1) position for the numbering system is chosen to give the lowest
possible value to the first substituent; if there is a choice after this criterion has
been applied, then that which gives the lowest number to the second sub-
stituent is used, etc. Applying these rules, the dioxin shown above is named
2,3,7,8-TCDD, or to give it its full title 2,3,7,8-tetrachlorodibenzo-p-dioxin.
No wonder it is simply called “dioxin” in the press!
There are actually 75 different chlorinated dibenzo-p-dioxin compounds,
when one includes all the possibilities having between one and eight chlorines,
given that a number of isomers exist for most of these eight types. Different
members of a chemical family that differ only in the number and position of the
same substituent are called congeners.
All dioxin congeners are planar: All carbon, oxygen, hydrogen, and chlo-
rine atoms lie in the same plane. For convenience, we refer to the carbon
atoms closest to the central dioxin ring as alpha carbons, and the outer ones
as beta carbons:
a a
O
b b
b b
a O a
The unsubstituted dibenzo-p-dioxin molecule has two types of symmetry that

are useful when considering substitution patterns. First there is lateral, or
left–right, symmetry: The carbon atom labeled b at the top of the left-side ring
is equivalent to the b carbon at the top of the ring at the right side, and sim-
ilarly for the two b carbons at the bottom. The dioxin ring also has up–down
Dioxins 473
symmetry: The carbon atom labeled b at the top of the left-side ring is equiv-
alent to the b carbon at the bottom of that ring, and similarly for the two
b carbons of the right-side ring. Thus all the four b carbons are equiv-
alent in the unsubstituted dioxin. Similarly, the four a carbons all denote
equivalent positions. Consequently, for example, there are only two unique
monochlorodibenzo-p-dioxins; due to the equivalence of the four a positions,
those that would otherwise be numbered 4-, 6-, and 9-chlorodibenzo-
p-dioxin are all equivalent to the 1- molecule. Similarly, 3-, 7-, and
8-chlorodibenzo-p-dioxins are all equivalent to the 2- molecule due to the
equivalence of the b positions. Some or all of the equivalences can be lost
when multiple substitution occurs.
P R O B L E M 11-1
By drawing the structures and comparing them, decide whether 1,3-, 2,4-,
6,8-, and 7,9-dichlorodibenzo-p-dioxins are all unique compounds or whether
they are all really the same compound. Are 1,2- and 1,8-dichlorodibenzo-p-
dioxins unique compounds? Using a systematic procedure, deduce the struc-
tures of all unique dichlorodibenzo-p-dioxins, keeping in mind that before
substitution the two rings are equivalent and that the molecule has up–down
symmetry.
Chlorophenols as Pesticides
In addition to their use as starting materials in the production of herbicides,
chlorophenols find use as wood preservatives (fungicides) and as slimicides.
The most common preservative, in use since 1936, is pentachlorophenol
(PCP, though not the “angel dust” compound known by the same initials); all
the benzene’s six hydrogens have been substituted in this compound:
OH
Cl Cl
Cl Cl
Cl
pentachlorophenol (PCP)
Commercial PCP is not pure pentachlorophenol but is significantly contam-

inated with 2,3,4,6-tetrachlorophenol. This mixture has many pesticidal appli-
cations: It is used as a herbicide (e.g., as a preharvest defoliant), an insecticide
(termite control), a fungicide (wood preservation and seed treatment), and a
molluscicide (snail control). Some trichlorophenol isomers and some tetra-
chlorophenol isomers are also sold as wood preservatives.
Unfortunately, if wood treated with such preservatives is eventually

burned, a fraction of the chlorophenols can react to eliminate HCl, thereby
producing members of the chlorinated dioxin family. Thus octachlorodibenzo-
p-dioxin, OCDD, is produced as an unwanted by-product in the incomplete
combustion of pentachlorophenol products:
Cl Cl Cl Cl
Cl OH Cl Cl Cl O Cl
heat
2 HCl
Cl Cl HO Cl Cl O Cl
Cl Cl Cl Cl
PCP PCP OCDD
OCDD is the most prevalent dioxin congener found in human fat and in
many environmental samples.
Indeed, pentachlorophenols are one of the largest chemical sources of
dioxins to the environment; however, the main dioxin they contain, OCDD,
is not particularly toxic, as discussed in a later section. Commercial supplies
of chlorinated phenols themselves are contaminated with various dioxins.
P R O B L E M 11-2
In naming OCDD and pentachlorophenol, no numbers are used to specify
the positions of the chlorine substituents. Why is that not necessary here,
whereas it is required in, e.g., 2,3,7,8-TCDD?
In general, any two phenol molecules that each have a chlorine on a

carbon atom that is next to that having an OH group can combine to produce
a dibenzo-p-dioxin molecule. The two phenols that combine need not be
identical but simply need to make contact when they have been heated
sufficiently to facilitate HCl elimination and dioxin formation. Similarly,
coupling of phenoxide anions can occur with Cl elimination, as discussed
previously in the case of 2,4,5-T synthesis. The methodology of problem solv-
ing that can be used to deduce the chlorophenolic origin of environmental
dioxins is discussed in Box 11-1.
P R O B L E M 11-3
(a) Deduce the structures and the correct numbering for the two tetra-
chlorophenol isomers that exist in addition to the 2,3,4,6 isomer mentioned
in the text. (b) For each of these two isomers, deduce the structure and names
of the dioxin(s) that would result if two molecules of that isomer were to react
together.
Dioxins 475
BOX 11-1 Deducing the Probable Chlorophenolic Origins of a Dioxin
he chlorophenolic source of dioxins dioxin structure came from the chlorophenol

T found in environmental samples can be
deduced by reversing the logic used in the text
on the right side of the molecule and the
bottom oxygen from the chlorophenol on
to deduce which dioxin would be produced by the left, leads to the possibility that the
the coupling of two specific chlorophenols. trichlorophenol molecules that combined
Consider the congener 1,2,7,8-tetra- were the 2,4,5 and the 2,3,6 congeners. Thus
chlorodibenzo-p-dioxin; it could have been a 1,2,7,8-tetrachlorodibenzo-p-dioxin mole-
formed by elimination of two HCl molecules cule in the environment could have arisen
from two chlorophenol molecules in the by combination of a 2,4,5-trichlorophenol
following two ways (here T stands for molecule with either a 2,3,4- or a 2,3,6-
trichlorophenol). substituted congener.
Cl
Cl OH Cl Cl
2 HCl

Cl heat
Cl O Cl Cl Cl HO
2,4,5-T 2,3,4-T
Cl
Cl O
2 HCl Cl Cl HO Cl
1,2,7,8-TCDD
heat

Cl OH Cl
2,4,5-T 2,3,6-T
If it is assumed that the oxygen atom at the Unfortunately, some dioxins undergo rearrange-
top of the dioxin congener originates with ment of substituents during their formation, so
the chlorophenol congener on the left side such a “retrosynthesis” approach is not an infal-
of the dioxin molecule, then the bottom lible guide to the origin of dioxins discovered
oxygen must come from the chlorophenol in the environment.
on the right side of the dioxin molecule;
with this set of assumptions, the original
PROBLEM 1
reactants must have been 2,4,5- and 2,3,4-
trichlorophenol. (Notice in the diagram Deduce the two possible combinations of
above that the chlorine atoms eliminated polychlorophenol molecules that, when
must have arisen from positions adjacent to coupled together through loss of two HCl
the oxygen atoms.) The alternative possi- molecules, would produce a molecule of
bility, that the oxygen atom at the top of the 1,2,9-trichlorodibenzo-p-dioxin.
When both carbon atoms adjacent to the one bonded to 9OH or O

bear chlorine atoms on one (or both) of the chlorophenol molecules or
chlorophenoxy ions, several possible dioxins can be formed in some cases.
Consider, for example, the possible couplings of 2,3,6-trichlorophenol with
2-chlorophenol. The two possible orientations of the trichlorophenol with
respect to the chlorophenol are illustrated below. The lower one corresponds
to the upper one rotated by 180° about the axis (dashed green line) running
through the O atom and the carbon atom that is para to it. Thus we see that
both 1,4- and 1,2-dichlorodibenzo-p-dioxins can be produced, depending
upon orientation. In practice, an almost equal mixture of the two isomers will
be formed. (See Additional Problem 2.)
Cl Cl
OH Cl O
Cl HO O
Cl Cl
1,4-dichloro isomer
Cl Cl
Cl OH Cl Cl O
Cl HO O
1,2-dichloro isomer
P R O B L E M 11-4
Deduce what dioxin(s) would be produced in side reactions if 2,4-D were to
be synthesized from 2,4-dichlorophenol.
Detecting Dioxins in Food and Water

As a consequence of their widespread occurrence in the environment and
their tendency to dissolve in fatty matter, dioxins bioaccumulate in the food
chain. More than 90% of human exposure to dioxins is attributable to the
food we eat, particularly meat, fish, and dairy products. Typically, dioxins
and furans (a group of compounds resembling the dioxins in structure,
which we’ll discuss later) are present in fish and meat at levels of tens or
hundreds of picograms (pg, or 1012 gram) per gram of the food; in other
words, they occur at levels of tens or hundreds of parts per trillion. How-
ever, the bulk of dioxins and furans in nature are not present in biological
PCBs 477
systems: Attachments to soil and to sediments of rivers, lakes, and oceans

are their most common sinks.
The ability of chemists to detect TCDD and other organochlorines in
environmental samples has improved by orders of magnitude over the past
few decades. In the early 1960s, when Carson’s Silent Spring was published,
the lower limit for analysis of DDT and other such compounds was the parts-
per-million level. Ten years later, detecting such substances at the parts-per-
billion level was possible but not common or easy. By 1990, parts-per-trillion
detection was possible in soil or biota samples, and parts-per-quadrillion was
possible for water samples. Today, a few labs detect some substances at limits
up to 1000 times lower than these! At these latter levels, many organochlorines
are found in every environmental sample, no matter how “clean” an environ-
ment it came from. By the late 1990s, researchers at the Centers for Disease
Control in Atlanta were able to detect as little as 1016 grams of TCDD in
human serum samples.
The potential impact on human health of exposure to dioxins is docu-
mented later, following a discussion of the properties of PCBs and furans, two
types of chemicals with which dioxins share many properties.
P R O B L E M 11-5
Given its formula and Avogadro’s constant (6.02 1023 molecules/mol),
deduce how many molecules are present in 1016 grams of TCDD.
PCBs
The well-known acronym PCBs stands for polychlorinated biphenyls, a
group of industrial organochlorine chemicals that became a major environ-
mental concern in the 1980s and 1990s. Although not pesticides, they found
a wide variety of applications in modern society because of certain other
properties they possess. Since the late 1950s, over 1 million metric tons of
PCBs have been produced, about half in the United States and the rest
mainly in France, Japan, and the former Eastern bloc nations. Like many
other organochlorines, they are very persistent in the environment and they
bioaccumulate in living systems. As a result of careless disposal practices,
they have become a major environmental pollutant in many areas of the world.
More than 95% of the entire U.S. population has detectable concentrations
of PCBs in their bodies. Due both to their own toxicity and to that of their
“furan” contaminants, PCBs in the environment have become a cause for
concern because of their potential impact on human health, particularly with
regard to growth and development.
In the following sections, we consider what PCBs are, how they are
made, what they are used for, and how they become contaminated and
released into the environment.
The Structure of PCB Molecules

Biphenyl molecules consist of two benzene rings linked by a single bond
formed between two carbons that have each lost their hydrogen atom:
biphenyl
Like benzene, if biphenyl reacts with Cl2 in the presence of a ferric chloride
(FeCl3) catalyst, some of its hydrogen atoms are replaced by chlorine atoms.
The more chlorine initially present and the longer the reaction is allowed to
proceed, the greater the extent (on average) of chlorination of the biphenyl
molecule. The products are polychlorinated biphenyls, PCBs. The reaction of
biphenyl with chlorine produces a mixture of many of the 209 congeners of
the PCB family; the exact proportions depend upon the ratio of chlorine to
biphenyl, the reaction time, and the reaction temperature. An example of a
PCB molecule is shown below:
Cl Cl
Cl
Cl
2,3
,4
,5
-tetrachlorobiphenyl
Although many individual PCB compounds are solids, the mixtures are liq-
uids or are solids with low melting points. Commercially, individual PCB
compounds were not isolated; rather they were sold as partially separated
mixtures, with the average chlorine content in different products ranging
from 21% to 68%.
P R O B L E M 11-6
The general formula for any PCB congener is C12H10nCln, where n ranges
from 1 to 10. Calculate the average number of chlorine atoms per PCB
molecule in a mixture of congeners that is 60% chlorine by mass, a common
value for commercial samples.
The Numbering Systems for PCBs

The numbering scheme used for individual PCB congeners begins with the
carbon that is joined to a carbon in the other ring; it is given the number 1,
PCBs 479
and the other carbons around the ring are numbered sequentially. As illustrated
below, the positions in the second ring are also numbered 1 through 6, starting
with the ring-joining carbon, but are distinguished by primes. By convention,
the 2
position in the second ring lies on the same side of the C9C bond
joining the rings as does the 2 position in the first ring, and so on.
3 2 2
3
1 1
4 4
5 6 6
5
In most instances, the two rings in a chlorinated biphenyl molecule are not
equivalent since the patterns of substitution differ. The unprimed ring is cho-
sen to be the one that will give a substituent with the lowest-numbered car-
bon. Using all these rules, we can deduce that the name of the PCB molecule
shown on page 478 is 2,3
,4
,5
-tetrachlorobiphenyl.
Very rapid rotation occurs around carbon–carbon single bonds in most
organic molecules, including the C9C link joining the two rings in biphenyl
and in most PCBs. Thus it is not normally possible to isolate compounds
corresponding to different relative orientations of the two rings (“rotamers”)
in a PCB. For example, 3,3
- and 3,5
-dichlorobiphenyl are not individually
isolatable compounds, since one form is constantly being converted into
the other and back again by rapid rotation about the C9C bond linking the
rings:
Cl Cl Cl
Cl
3,3
-dichlorobiphenyl 3,5
-dichlorobiphenyl
The name used for such a compound is that which has the lowest number for
the second chlorine, so the system shown above is called the 3,3
isomer.
Although the rings rotate rapidly with respect to each other, the energetically
optimum orientation is the one having the rings coplanar or close to it, except,
as we shall see later, when large atoms or groups occupy the 2 and 6 positions.
P R O B L E M 11-7
Using a systematic procedure, draw the structures of all unique dichloro-
biphenyls, assuming first that free rotation about the bond joining the rings
does not occur. Then deduce which pairs of structures become identical if free
rotation does occur.
Commercial Uses of PCBs

All PCBs are practically insoluble in water but are soluble in hydrophobic
media, such as fatty or oily substances. Commercially, they were attractive
because they
• are chemically inert liquids and are difficult to burn,
• have low vapor pressures,
• are inexpensive to produce, and
• are excellent electrical insulators.
As a result of these properties, they were used extensively as the coolant
fluids in power transformers and capacitors. Later, they were also employed as
plasticizers, i.e., agents used to make plastic materials such as PVC products
more flexible, in carbonless copy paper, as de-inking solvents for recycling
newsprint, as heat transfer fluids in machinery, as waterproofing agents, and
so on.
Because of their stability and extensive usage, together with careless dis-
posal practices, PCBs became widespread and persistent environmental con-
taminants. When their accumulation and harmful effects became recognized,
open uses—i.e., those for which their disposal could not be controlled—were
terminated. Although North American production of PCBs was halted in
1977, the substances remain in use in some electrical transformers currently
in service. As these units are gradually decommissioned, their PCB content
usually is stored in order to prevent further contamination of the environ-
ment. In the United States, the EPA expected a 90% reduction of PCB use in
electrical equipment by 2006. Canada has proposed a phase-out of all PCB
uses by 2008. In some locales, stored PCBs are destroyed by incineration,
using techniques discussed in Chapter 16. Previously, PCB-containing trans-
formers and capacitors were often just dumped into landfills, and their PCB
content was allowed to leak into the ground. Indeed, PCBs were inadver-
tently released into the environment during their production, their use, their
storage, and their disposal.
PCBs Cycling Among Air, Water, and Sediments

If released into the environment, PCBs persist for many years because they
are so resistant to breakdown by chemical or biological agents. Although
their solubility in water is very slight—indeed they are more likely to be
adsorbed onto suspended particles in the water than dissolved in it—the tiny
amounts of PCBs in surface waters are constantly being volatilized and subse-
quently redeposited on land or in water after traveling in air for a few days. By
such mechanisms, PCBs have been transported worldwide. There are measur-
able background levels of PCBs even in polar regions and at the bottom of
oceans. Indeed, the ultimate sinks for PCBs that are mobile are in the deep
PCBs 481
sediments of oceans and large lakes. This environmental load of PCBs will
continue to be recycled among air, land, and water, including the biosphere,
for decades to come, as analyzed in greater detail in Chapter 12. Only a
minority of PCBs manufactured in the past are currently found in the envi-
ronment or have been destroyed; much of the production lingers in storage or
old electrical equipment and may ultimately be released. Recent research has
found that PCB releases from older consumer products into indoor air, which
then is eventually vented outside, is a major source of PCBs in urban air.
A quantitative measure of the recycling of substances within a water
body is provided by the mass balance of its current annual inputs and outputs
of the compounds. The PCB mass balance for a very large, relatively clean
water body—Lake Superior—is illustrated in Figure 11-1. Although it is the
least polluted of the Great Lakes, Lake Superior’s burden of PCBs in its water
and its sediments is substantial. Currently, almost all the input of PCBs
occurs from the air, with relatively little added from industries or via tributary
rivers (Figure 11-1). Overall, Lake Superior is now gradually “exhaling” its
historical load of PCBs into the air, the output to air being much greater than
the annual input from the atmosphere. Little of Lake Superior’s PCB content
457 2200
(405) (2000) Air
140
60 (13)
Tributaries
38 River outflow
Direct Water
discharges Water column total
= 10,100 kg in 1986
Net loss/year
= 1735 (1540) kg
110
Sediment
Sediment total
= 4900 kg (1986)
FIGURE 11-1 Mass

Notes: 1. Data are for 1986; where data for 1992 differ from 1986, they are
shown in parentheses. balance of PCBs in Lake
2. Note that burial in sediment represents the small difference Superior, in kilograms per
between large deposition and resuspension from surface sediments. year. [Source: The State of
Canada’s Environment 1996
(Ottawa: Government of
Canada, 1996).]
is now being lost to sediments; about as much is redissolved from them as is

deposited onto them each year.
By contrast, the mass balance of PCBs in Lake Ontario, another of the
Great Lakes, is quite different from that of Lake Superior. The PCB concentra-
tion in Lake Ontario water substantially exceeds that of Lake Superior, since it
is located in a much more industrialized area. In Lake Ontario, the greatest
current input comes from land-based sources such as waste dumps that still
leach PCBs into the lake and its tributaries. About the same quantity of PCBs
are present in the water flowing out of the lake. Approximately equal amounts
are lost annually to sediments and to the atmosphere; about one-third of such
losses are canceled by new inputs from the sediments and the air.
P R O B L E M 11-8
The PCB concentration in Lake Michigan is declining according to a first-
order rate law having a rate constant of 0.078/year. If the PCB concentration
in Lake Michigan averaged 0.047 ppt in 1994, what will it be in 2010? In
what year will the concentration fall to 0.010 ppt? What is the half-life period
of PCBs in this lake? [Hint: Recall that for first-order processes, the fraction f of
any sample that still remains after time t has passed is f ekt.]
Because of their persistence and their solubility in fatty tissue, PCBs in

food chains undergo biomagnification; an example is shown in Figure 11-2.
Herring gull eggs

124 ppm
Lake trout
4.83 ppm
Rainbow smelt
1.04 ppm
Zooplankton
FIGURE 11-2 The bio- 0.123 ppm
magnification of PCBs in
the Great Lakes aquatic
food chain. [Source: The
Phytoplankton
0.0025 ppm
State of Canada’s Environment
1996 (Ottawa: Government of
Canada, 1991).]
PCBs 483
Notice that the ratio of PCBs in the eggs of herring gulls in the Great Lakes was
50,000 times that in the phytoplankton in the water at the time of these mea-
surements. The good news is that the average level of PCBs in such eggs has
fallen with time in many locations, as the data in Figure 11-3a illustrate for
(a)
1000
Observed
Predicted
Concentration (ppm)
100
10
0
’74 ’76 ’78 ’80 ’82 ’84 ’86 ’88 ’90 ’92 ’94 ’96 ’98 ’00 ’02
Year
(b)
4000
3500
3000
2500
PCBs ( mg/kg)
2000
1500
1000
500
0
’77 ’79 ’81 ’83 ’85 ’87 ’89 ’91 ’93 ’95 ’97 ’99
Year
FIGURE 11-3 (a) PCB concentrations in herring gull eggs in Toronto Harbor, 1974–2002. The predicted curves correspond
to exponential decay in those time periods. [Source: Dr. Chip Weseloh, Environment Canada.] (b) PCB concentrations in 65-cm
coho salmon from Lake Ontario. [Source: Ontario Ministry of the Environment.]
gull colonies in Lake Ontario around Toronto. The concentrations are plotted
in the figure on a logarithmic scale, and the data seem to fit two intersecting
straight lines, corresponding to first-order decay sequences with half-lives of
first five years and more recently seven years. This complicated behavior may
arise because of continuing sources of PCBs to the system. PCB levels in fish at
the top of the Lake Ontario food chain have also declined since the 1970s, but
the current rate of decrease is slow and erratic (see Figure 11-3b).
The relative concentrations of the congeners of a PCB mixture begin to
change once they enter the environment. Microorganisms in soils and sedi-
ments and large organisms such as fish both preferentially metabolize con-
geners having relatively few chlorine atoms. Thus the relative concentrations
of the more heavily chlorinated congeners increases with time since they are
degraded much more slowly. Thus, for example, between 1977 and 1993, the
proportion of PCB molecules with four or five chlorine atoms decreased by
6% each in trout in Lake Ontario, whereas those with seven or eight chlorines
increased by 7% and 4%, respectively. However, PCBs present in anaerobic
soil are eventually dechlorinated microbially at their meta and para positions,
leaving congeners that are only chlorinated at ortho positions. Aerobic
degradation occurs with congeners having adjacent carbons (ortho meta, or
meta para) chlorine-free.
PCB Contamination by Furans

Strong heating of PCBs in the presence of a source of oxygen can result in the
production of small amounts of furans. These compounds are structurally sim-
ilar to dioxins; they differ only in that the molecules are missing one oxygen
atom in the central ring. The furan ring contains five atoms, one of which is
oxygen and the other four of which are carbon atoms that participate in
double bonds:
O
furan
The dibenzofurans (DFs) have a benzene ring fused to opposite sides of the
furan ring:
O
dibenzofuran
As with dioxins, all chlorinated dibenzofuran congeners are planar;

i.e., all C, O, H, and Cl atoms lie in the same plane. They are formed from
PCBs 485
PCBs by the elimination of the atoms X and Y bonded to two carbons that are
ortho in position to those that link the rings and that lie on the same side of
the C9C link between the rings:
oxygen
XY
heat
O
X Y
PCB dibenzofuran
The atoms X and Y can both be chlorine, or one can be hydrogen and the
other one chlorine, so the molecule eliminated can be Cl2 or ClH (i.e., HCl),
respectively. A more detailed analysis of the nature of the specific furans that
result from particular PCB congeners is given in Box 11-2.
Most of the chlorine in the original PCB molecule is still present in
the dibenzofuran; polychlorinated dibenzofurans are known commonly
as PCDFs. The numbering scheme for substituents is the same as that
for dioxins (PCDDs); note, however, that by convention the numbering
starts next to a carbon that forms the single C9C bond opposite the
oxygen.
9 1
8 2
7 3
6
O 4
While there exist 75 different chlorine-substituted dibenzo-p-dioxins,

there are 135 dibenzofuran congeners, since the symmetry of the ring
system is lower for furans. In particular, although the furans have the
same left–right symmetry as dioxins, they do not have their up–down
symmetry.
P R O B L E M 11-9
Draw the structures of all the 16 unique dichlorodibenzofurans, and deduce
the numbering required in their names. [Hint: Use a systematic procedure to
generate all, but include only those congeners that correspond to unique molecules;
i.e., be careful to eliminate duplicates. For example, start by placing one chlorine at
C-1 and then generate all the possible isomers corresponding to different positions for
the second chlorine. Then place the first chlorine at C-2 and repeat the procedure,
noting that the 1,2-dichloro isomer is generated both times. Continue the procedure
with the first chlorine at C-3, etc.]
BOX 11-2 Predicting the Furans That Will Form from a Given PCB
n deducing the nature of the polychlori- At the high temperatures of this reaction,
I nated dibenzofuran (PCDF) that would
be formed from a particular PCB, it should be
some interchange of the adjacent substituents
in the 2 and 3 positions (ortho and meta)
remembered that free rotation occurs about of any given ring can occur as a prelude to
the single bond joining the two rings in the HCl elimination; in particular chlorine can
original biphenyl in all PCBs at the elevated move from an ortho to a meta position, and
temperatures of the reaction. Thus HCl elimi- hydrogen from meta to ortho, preceding HCl
nation in 2,3
-dichlorobiphenyl gives both elimination. For example, when 2,6,2
,6
-
4- and 2-chlorodibenzofuran. tetrachlorobiphenyl (see next page) is heated
in air, some of its molecules lose a pair of
ortho chlorines to give a dichlorodibenzofu-
ran, and some first interchange Cl and H in
one ring to eliminate HCl and produce a
trichlorodibenzofuran. Free rotation about the
Cl H Cl C 9 C bond does not occur after the inter-
rotation change, as presumably the elimination occurs
heat
O2
HCl immediately.
H Cl
O
Cl Cl
4-chlorodibenzofuran heat
HCl
O2
Cl
2-chlorodibenzofuran
Almost all commercial PCB samples are contaminated with some

PCDFs, but this usually amounts to only a few ppm in the originally manufac-
tured liquids. However, if the PCBs are heated to high temperatures and if
some oxygen is present, conversion of PCBs to PCDFs increases the level of
contamination by orders of magnitude. The furan concentration in used PCB
cooling fluids is found to be greater than in the virgin materials, presumably
due to the moderate heating that the fluid undergoes during its normal use.
Cl Cl Cl Cl Cl Cl
heat HCl
heat
O2 O
Cl Cl H Cl H Cl Cl
2,6,2
,6
-tetrachlorobiphenyl 1,4,9-trichlorodibenzofuran
heat
Cl2
O2
Cl Cl
O
1,9-dichlorodibenzofuran
PROBLEM 1 PROBLEM 2
For each PCB shown below, deduce which Recently it has been discovered that upon
furans would be expected to be produced by strong heating in air PCBs can also react by
Cl2 or HCl elimination when the PCB is elimination of two ortho hydrogen atoms (one
heated in air. Write the correct name for each on each ring) as H2. Decide which, if any,
PCDF. additional PCDFs will be produced if the
PCBs in Problem 1 can eliminate H2.
Cl Cl
Cl Cl Cl
Furan production also occurs if one attempts to burn PCBs with anything but
an unusually hot flame.
Other Sources of Dioxins and Furans

In addition to the sources discussed above, polychlorinated dibenzofurans and
dibenzo-p-dioxins are also produced as by-products in a myriad of processes,
including the bleaching of pulp, the incineration of garbage and hospital waste,
the recycling of metals and sintering of iron ore, and the production of com-
mon solvents such as tri- and perchloroethene.
Pulp-and-Paper Mills
Pulp-and-paper mills that use elemental chlorine, Cl2, to bleach pulp are
dioxin and furan sources. These contaminants, among many other chlori-
nated compounds, result from the reaction of the chlorine with some of
the organic molecules released by the pulp. The tan color of the pulp that
has undergone the initial stages of processing is due to the light-absorbing
properties of the lignin component of the original wood fibers. A generalized
structure for lignin is shown in Figure 11-4. In order to make white paper, the
residual (⬃10%) component of the lignin still present after initial processing
must be removed, usually by bleaching the pulp with oxidizing agents. If
you examine the generalized structure of lignin in Figure 11-4, you can
observe several sites of monosubstituted phenols and phenolic ethers as well as
ortho-substituted phenyl diethers. From these structural components, it is not
difficult to imagine how lignin can serve as a precursor to furans and dioxins
when it reacts with chlorinating agents such as Cl2.
HO
O O CH3
OH
O H3C O
H3C O OH O
O OH
H3C O
OH O
HO O CH3
O
OH
O O O
H 3C O
OH
OH
HO O CH3 OH
O
HO O O CH3
O
CH3
O O O O O
OH
O O O
OH CH3
H3C O HO O CH3
HO
FIGURE 11-4 Generalized structure of lignin. [Source: M. C. Cann and M. E. Connelly, Real-World
Cases in Green Chemistry (Washington D.C.: American Chemical Society, 2000).]
More furans than dioxins are formed in the bleaching of pulp by elemen-
tal chlorine. The furan congeners of highest concentrations in the pulp are
1,2,7,8-TCDF and the more toxic 2,3,7,8-TCDF. Unfortunately, the most
abundant dioxin produced by the pulp-and-paper bleaching process is the
highly toxic 2,3,7,8-TCDD congener. The paper and effluent contain dioxins
at parts-per-trillion levels, which resulted in total releases in the past, in
North America, of several hundred grams of 2,3,7,8-TCDD annually.
Because of the problems of producing dioxins and furans, the use of
elemental chlorine as a bleaching agent for paper was banned in the United
States as of April 2001. Most pulp-and-paper mills there and in other devel-
oped countries switched their bleaching agent from elemental chlorine to chlo-
rine dioxide, ClO2, from which the furan and dioxin output is much smaller,
even undetectable in many cases. The difference is due to the mechanism by
which the compounds attack the pulp’s residual lignin. Elemental chlorine
reacts to insert chlorine as a substituent on the aromatic rings in lignin, yield-
ing products that are soluble in alkali and that can then be washed away. Exper-
iments suggest that during the oxidation of the lignin, two of the component
benzene rings can couple together to form a dibenzofuran or dibenzo-p-dioxin
system that subsequently is chlorinated and in the process becomes detached
from the lignin system. In contrast, chlorine dioxide destroys the aromaticity
of the benzene rings by free-radical processes and therefore produces fewer
chlorinated products that contain six-membered rings.
Some mills now produce paper pulp without any use of chlorine com-
pounds. Ozone, hydrogen peroxide, and even high-pressure oxygen are the
alternative bleaching agents used in these totally chlorine free (TCF) pulp
mills. Mills that still use chlorine to bleach now remove contaminants from
wastewater by treatments such as reverse osmosis (see Chapter 14).
The use of chlorine to disinfect drinking water and the chlorinated by-
products that are formed in the process are discussed in Chapter 14.
Green Chemistry: H2O2, an Environmentally Benign

Bleaching Agent for the Production of Paper
TCF bleaching agents for paper such as hydrogen peroxide (H2O2), ozone,
and diatomic oxygen have been developed. While TCF agents eliminate the
formation of dioxins and furans, these methods in general are problematic
because these oxidizing agents are not as strong as elemental chlorine or chlo-
rine dioxide. Thus they generally require longer reaction times and higher
temperatures (more energy input), and they lead to significant breakdown
of the cellulose fibers, which weakens the paper, requiring more wood to
produce the same amount of paper.
Terry Collins of Carnegie Mellon University earned a Presidential Green
Chemistry Challenge Award in 1999 for his development of compounds
O OH2 known as tetraamido-macrocyclic ligands (TAMLs,

O Figure 11-5), which enhance the oxidizing strength of
N Fe
N R hydrogen peroxide. Hydrogen peroxide is a particu-
N N R larly enticing oxidizing reagent since its by-products
are water and oxygen, which are environmentally
O benign. The use of TAML in conjunction with hydro-
O
gen peroxide reduces the temperature and reaction
FIGURE 11-5 Tetraamido-
macrocyclic ligands
times normally required for bleaching paper with hydrogen peroxide, thus
(TAML): activators for making hydrogen peroxide a viable alternative for this process. See also the
hydrogen peroxide. feature article “Little Green Molecules” immediately following the Intro-
[Source: M. C. Cann and M. E. duction to this book.
Connelly, Real-World Cases in The TAMLs can be modified by varying the alkyl groups (R) on the right
Green Chemistry (Washington
D.C.: American Chemical
side of the structure in Figure 11-5. Changing these groups influences the life-
Society, 2000).] time of these catalysts. In uses such as the bleaching of paper it is important for
the TAML catalysts to decompose in a relatively short period of time so they
do not become a burden to the environment. However, they must last long
enough to fulfill their role as catalysts for hydrogen peroxide. TAML catalysts
not only offer significant promise for the bleaching of paper, they are also
being considered for use in laundry applications, the disinfection of water, and
the decontamination of biological warfare agents such as anthrax.
Fires and Incineration as Sources of Dioxins and Furans

Fires of many kinds, including forest fires and those in incinerators, release
various congeners of the dioxin and furan families into the environment;
these chemicals are produced as minor by-products from the chlorine and
organic matter in the fuel. Dioxin and furan production seem unavoidable
whenever combustion of organic matter occurs in the presence of chlorine,
unless steps are taken to ensure complete combustion by using very high
flame temperatures. Some environmentalists worry particularly about the
dioxin emissions when the chlorine-containing plastic PVC is incinerated or
involved in other fires. Indeed, research on the combustion of newspapers
indicates that chlorinated dioxin and furan production rises as the amount of
salt or PVC present also increases. In many environmental samples of com-
bustion products, several dozen different dioxin congeners are found, all in
comparable amounts. Congeners with relatively high numbers of chlorine
substituents usually are the most prevalent.
Incinerators now are the largest anthropogenic source of dioxins in the
environment. Dioxins and furans are formed in the postcombustion zone of
incinerators, where the temperature is much lower (250–500°C) than in the
flame itself (see Chapter 16). They are formed during the oxidative degradation
of the graphite-like structures in the soot particles that were produced during
the incomplete combustion of the waste. Trace metal ions in the original waste
probably catalyze the process. The small amounts of chlorine in the waste pro-
vide more than enough of this element required to partially chlorinate the
furans and dioxins. The dibenzofuran and dibenzo-p-dioxin ring systems are
formed at high temperatures ( 650°C); chlorination progressively occurs
when the temperature cools below 650°C and gradually is reduced to 200°C.
Characteristically, incineration produces a greater mass of furans than
dioxins. The yields of specific dioxin congeners increase with the degree of
chlorination through to OCDD, whereas the peak production of furans
occurs with four to six chlorines. In contrast to waste incineration, industrial
coal combustion generates little dioxin because it burns much more com-
pletely, generating little soot to decompose later into dioxins and furans.
Chlorine Content of Dioxin and Furan Emissions

The profile of estimated annual global PCDF and PCDD emissions for the
congeners with four to eight chlorines, i.e., those believed to be toxic, is
shown in Figure 11-6a. As discussed previously, furans outnumber dioxins,
and furans peak with congeners having four chlorines, whereas the dioxin
(a)
500
400
Amount (kg/year)
300
200
100
0
F4 F5 F6 F7 F8 D4 D5 D6 D7 D8
FIGURE 11-6 Annual
(b) PCDD and PCDF (a) emis-
500 sions and (b) deposition
rates after reactions with
400 the hydroxyl radical OH.
The letters F and D repre-
Amount (kg/year)
sent furans and dioxins;

300 the numbers indicate the
number of chlorine atoms
200 per molecule. [Source: J. I.
Baker and R. A. Hites, “Is
Combustion a Major Source of
100
Polychlorinated Dibenzo-p-
Dioxins and Dibenzofurans
0 to the Environment?”
F4 F5 F6 F7 F8 D4 D5 D6 D7 D8
Environmental Science and
Technology 34 (2000): 2879.]
peak is less pronounced and occurs with about six chlorines. Furans with
these intermediate amounts of chlorine have toxicities similar to that of
2,3,7,8-TCDD, whereas fully chlorinated dioxin molecules have low toxici-
ties. Consequently, the threat to human health from furans in the environ-
ment may exceed that from dioxins.
The mass of the dioxin and furan compounds that are eventually
deposited from air onto soil and sediments, the primary mechanism by which
dioxins eventually enter the food chain, is shown in Figure 11-6b. The loss in
mass between emission and deposition is greater the fewer the number of
chlorines present; hence the significant difference between amounts emitted
and deposited for the tetrachloro and pentachloro congeners, but not those
more heavily chlorinated, in Figure 11-6. This differentiation occurs because
the principal loss mechanism is attacked at an unsubstituted carbon by
the hydroxyl free radical, OH (followed by atmospheric oxidation of the
resulting radical, as expected from the principles discussed in Chapters 3 and 5),
and the rate of this initial reaction is greater the fewer the chlorines present.
The amount of OCDD, the octachloro congener of dioxin, that is found to be
deposited greatly exceeds the estimate from this figure, which is based mainly
on combustion sources. Some scientists believe that the discrepancy arises
because much additional OCDD is created in water droplets in air by the sun-
light-initiated photochemical decomposition of PCP, pentachlorophenol,
which eventually results in coupling of two PCPs to produce OCDD.
Very small concentrations of dioxins—particularly highly chlorinated
ones—were present in the environment in the preindustrial era, presumably as
a result of forest fires, volcanoes, etc. Indeed, forest fires are still probably
Canada’s largest source of dioxins. According to the analysis of soils and the
sediments in lakes, the greatest anthropogenic input of dioxins and furans to
the environment in developed countries began in the 1930s and 1940s, and
peaked in the 1960s and 1970s. The principal sources were combustion/
incineration, the smelting and processing of metals, the chemical industry,
and existing environmental reservoirs. Inadvertent production of dioxins con-
tinues today, but at a slower rate—about half of the maximum, according to
some sediment samples. The decrease in emissions resulted from deliberate
steps taken by industrialized nations to reduce the production and dispersal of
these toxic by-products. In particular, dioxin emissions from large sources in
the United States declined by 75% from 1987 to 1995 alone, primarily due to
reductions in air emissions from municipal and medical waste incinerators.
New regulations should increase the reduction to 95%. However, uncon-
trolled combustion of nonpoint sources such as rural backyard trash burning in
barrels—especially when plastics such as PVC are included in the mix—has
not yet been brought under control.
Once created, dioxins and furans are transported from place to place
mainly via the atmosphere (Chapter 12). Eventually they are deposited and
can enter the food chain, becoming bioaccumulated in plants and animals.
As previously mentioned, our exposure to them arises almost entirely through
the foods that we eat. In the next section, we try to answer the question of
what effects, if any, this exposure has on our health.
The Health Effects of Dioxins, Furans, and PCBs

Over a billion dollars has been spent on research to determine the extent to
which dioxins, furans, and PCBs cause toxic reactions in humans. Neverthe-
less, conclusions about this issue are still tentative and controversial. Evi-
dence about toxicity is derived from two sources:
• toxicological experiments on animals that have been deliberately
exposed to the chemicals; and
• epidemiological studies of humans who have been accidentally exposed.
It is generally agreed that most PCBs are not acutely toxic to humans: The
LD50 values of most congeners are large. In high doses, PCBs cause cancer in
test animals, and consequently they are listed as a “probable human carcino-
gen” by the U.S. EPA. However, studies of humans exposed to them have pro-
duced inconsistent results. Most groups of people who have been exposed to
relatively high concentrations of PCBs—e.g., as a result of their employment
in electrical capacitor plants—have not experienced a higher overall death
rate. (See, however, the comments about human cancer in Chapter 12.) The
most common reaction to exposure to PCBs is chloracne, a biological response
by humans to exposure to many types of organochlorine compounds.
Inadvertent PCB Poisonings

The most dramatic effects observed to human health from exposure to PCB
mixtures occurred when two sets of people, one in Japan in 1968 and the
other in Taiwan in 1979, unintentionally consumed PCBs that had acciden-
tally been mixed with cooking oil. In the Japanese incident, and probably in
the Taiwanese case as well, the PCBs had been used as a heat exchanger
fluid in the deodorization process for the oil. Since the PCB-contaminated
oils had been heated, their level of PCDF contamination was much greater
than occurs in freshly prepared commercial PCBs. The thousands of Japanese
and the Taiwanese people who consumed the contaminated oils suffered
health effects far worse than has been found for workers at PCB manufactur-
ing and handling plants, even though the resulting PCB levels in their bod-
ies were about the same. From this difference, it has been concluded that the
main toxic agents in the poisonings were the PCDFs and that they and dioxins
were collectively responsible for about two-thirds of the health effects, with
the PCBs themselves responsible for the remainder. Indeed, studies on labo-
ratory animals indicate that the furans involved in these incidents are more
than 500 times as toxic on a gram-for-gram basis than are pure PCBs. Cog-
nitive development, as measured by IQ scores, of children born to the most
highly exposed Taiwanese mothers—even if births occurred long after the
consumption of the contaminated oil—was found to be significantly lower

than that of their siblings born before the accident occurred and for children of
unexposed mothers. Interestingly, children whose fathers but not their mothers
had consumed the oil showed no detrimental effects. Further effects of this
incident are discussed in Chapter 12 (Environmental Estrogens section).
An incident comparable to the Asian cooking oil poisonings occurred in
early 1999 in Belgium. Several kilograms of a mixture of PCBs that had pre-
viously been heated to a high temperature—converting a tiny fraction of the
PCBs to furans—were put into an 80,000-kg batch of animal fat, which was
then mixed with animal feed and shipped to about 1000 farmers. Poultry pro-
ducers subsequently noticed a sudden drop in egg production and in egg hatch-
ability, and high concentrations of dioxins were subsequently found in chicken
meat. The contaminated food was withdrawn from the market and destroyed.
Effects of in Utero Exposure to PCBs

Are humans who have been exposed to PCBs through their diets especially
susceptible to reproductive problems? To answer this question, Sandra and
Joseph Jacobson and their co-workers at Wayne State University in Detroit
have spent more than two decades studying the offspring of people from the
Lake Michigan area, including children whose mothers regularly eat fish from
the lake and who, as a result, are expected to have elevated levels of PCBs in
their bodies. They have discovered statistically significant differences in chil-
dren born to women who have high levels of PCBs; these differences were
present not only at birth but persisted to the age of at least eleven years.
The prenatal (i.e., prebirth) exposure of the infants to PCBs was deter-
mined by analyzing the blood of their umbilical cords for these chemicals
after birth. Because analytical techniques in the early 1980s were not suffi-
ciently sensitive to detect the amounts of PCBs in all the umbilical cord sam-
ples, exposure for many infants was estimated from the PCB levels in their
mother’s blood and breast milk. The postnatal exposure of the children was
assessed by analyzing their mother’s breast milk and also by analyzing blood
samples from the children at the age of four years.
The Jacobsons discovered that, at birth, the children of mothers who had
transmitted the highest amounts of PCBs to the children before birth had, on
average, a slightly lower birth weight and a slightly smaller head circumference;
they were also on average slightly more premature than those born to women
who passed along lower amounts. The severity of these deficits was larger the
greater their prenatal exposure to PCBs. When tested at the age of seven
months, many of the affected children displayed small difficulties with visual
recognition memory, again with the extent of the problem increasing with pre-
natal transmission of PCBs. At the age of four years, the lower body weight
observed at birth for highly exposed infants still lingered. More serious was the
observation that the four-year-olds displayed progressively lower scores on
several tests of mental functioning (with

respect to verbal and memory abilities) the (a)
118
greater their prenatal PCB exposure. A
comparable study in Holland, using more 116
Overall cognitive scale

modern analytical instrumentation, found
similar results (see Figure 11-7a). 114
At eleven years of age, the effects of
112
the prenatal PCBs were still apparent: the
IQ scores of the part of the group that had 110
been the most highly exposed before birth
averaged 6 points below the others; the 108
most affected mental functions were mem-
ory and attention span. However, prenatal <1.5 1.5–1.99 2.0–2.49 2.5–2.99 ≥3.0
PCB exposure at any but the highest levels Sum PCB level in maternal plasma (μg/L)
did not appear to have affected the IQ of (b)
the eleven-year-olds (see Figure 11-7b). 112
Interestingly, at both four and eleven
110
years of age, the children’s total body con-
tent of PCBs, which is determined mainly 108
from the breast milk they consumed as
infants and to a lesser extent by the fish in 106
their diet rather than from any prenatal
Full-scale IQ
transmission of the chemicals, was not the 104

relevant factor in determining these phys- 102
ical and mental deficits. Rather, it was the
smaller amounts of PCBs that had been 100
transmitted from mother to fetus that were
important. Thus PCBs appear to interfere 98
with the proper prenatal development of
96
the brain and with the mechanisms that
ultimately determine physical size.
The study by the Jacobsons is one of the <0.5 0.5– 0.75– 1.0– >1.25
0.749 0.99 1.249
clearest examples available concerning the
Prenatal PCB exposure (μg/g)
influence of toxic environmental chemicals
on the health of human beings. It is impor-
tant to realize that the highest levels of FIGURE 11-7 The effect on the intelligence of
PCBs to which the children in this group children of receiving PCBs prenatally: (a) overall
were exposed before birth are not much cognitive abilities at 31⁄2 years of age, (b) full-scale IQ
at 11 years. [Sources: (a) S. Patandin et al., “Effects of
greater than those to which the majority of
Environmental Exposure to Polychlorinated Biphenyls and
unborn children in the general population Dioxins on Cognative Abilities in Dutch Children at 42 Months
were subjected a few decades ago. And while of Age,” Journal of Pediatrics 134 (1999): 33. (b) J. L. Jacobson
the chemicals did not produce gross birth et al., “A Benchmark Dose Analysis of Prenatal Exposure to
defects in the children, they did result in Polychlorinated Biphenyls,” Environmental Health Perspectives
110 (2002): 393.]
small and consistent deficits of several kinds.
Studies of infants in North Carolina and in upper New York State have
produced similar results to those found by the Jacobsons. Nevertheless,
some doubt has been cast on the Jacobsons’ results by an analysis that
pointed out the difficulties in establishing the original in utero exposures. A
more recent study in the Netherlands overcame these analytical difficulties,
since the ability to detect very low levels of chemicals such as PCBs in
blood serum has improved dramatically. The ongoing Dutch study has sup-
ported the Jacobsons’ findings. It found that prenatal exposure to PCBs is
more important than postnatal exposure and produces lower birth and
growth weight and lesser cognitive abilities in young children, although the
latter deficit was found for all but the least exposed fraction of children,
rather than only the most highly exposed fraction. Negative effects on the
IQs of three-year-old children by postnatal exposure to PCBs, as measured
by blood levels, has recently been discovered by researchers in Germany.
Subtle cognitive deficits have also been found in children in northern
Quebec whose PCB concentrations are high due to the long-range air trans-
port and subsequent deposition and entry into the food chain of the com-
pounds (as discussed in Chapter 12). Dutch researchers also found that
PCBs and dioxins transmitted to babies during gestation and via breast milk
weakened their immune systems, contributing to more infections in the first
few years of life.
The Toxicity Patterns of Dioxins, Furans, and PCBs

Research has shown that single doses of 2,3,7,8-TCDD administered to preg-
nant laboratory animals cause reproductive effects in their offspring. These
results have raised some alarm about the potential effects of dioxins on
human reproduction. In this connection, many scientists are worried about
the dangers posed by environmental chemicals such as dioxins, furans, PCBs,
and other organochlorines that can affect sex hormones, as discussed in
Chapter 12.
Test results from studies of animals indicate that the acute toxicity of
dioxins, furans, and PCBs depends to an extraordinary degree on the extent
and pattern of chlorine substitution. The following generalization can be
made: the very toxic dioxins are those with four beta chlorine atoms, and few
if any alpha chlorines (see diagram on page xxx for definitions of the alpha
and beta positions). Thus the most toxic is 2,3,7,8-TCDD, which has the
maximum number (four) of beta chlorines and no alpha chlorines.
Cl O Cl
Cl O Cl
2,3,7,8-TCDD
Dioxin congeners that have three beta chlorines, but no (or only one)
alpha chlorine, are appreciably toxic, but less so than the 2,3,7,8 compound.
Fully chlorinated dioxin, that is, octachlorodibenzo-p-dioxin (OCDD), has a
very low toxicity since all the alpha positions are also occupied by chlorine.
Cl Cl
Cl O Cl
Cl O Cl
Cl Cl
OCDD
Similarly, mono- and dichloro dioxins are usually not considered highly toxic,
even if the chlorines are present in beta positions.
P R O B L E M 11-10
Predict the order of relative toxicities of the following three dioxin congeners,
given that, for systems not too dissimilar to TCDD, the presence of an alpha
chlorine reduces the toxicity less than does the absence of a beta chlorine:
2,3,7-trichlorodibenzo-p-dioxin
1,2,3-trichlorodibenzo-p-dioxin
1,2,3,7,8-pentachlorodibenzo-p-dioxin
The toxicity pattern for furans is similar though not identical to that for
dioxins in that the most toxic congeners have chlorines in all the beta posi-
tions. However, the most toxic furan, the 2,3,4,7,8 congener, does have one
chlorine atom in an alpha position.
According to animal tests, the most acutely toxic PCBs are those having
no chlorine atoms (or at most one) in the positions that are ortho to the car-
bons that join the rings, that is, on the 2, 2
, 6, and 6
carbons. Without ortho
chlorines, the two benzene rings can easily adopt an almost coplanar config-
uration, and rotation about the C9C bond joining the rings is rapid. How-
ever, because of the large size of chlorine atoms, they get in each other’s way
if they are present in both ortho positions on the same side of the two rings;
this interaction forces the rings to twist away from each other, preventing
such rings from adopting the coplanar geometry:
Cl Cl
Consequently, PCB molecules with chlorines at three or four of the ortho

positions cannot adopt a coplanar geometry.
If the rings are not kept from coplanarity by interference between chlo-
rine atoms, and if the hydrogen atoms at certain meta and para carbons are
replaced by chlorine, then the PCB molecule can readily attain a coplanar
geometry that is similar in size and shape to 2,3,7,8-TCDD. Such PCB mole-
cules are found to be highly toxic. Apparently 2,3,7,8-TCDD and other mol-
ecules of its size and shape readily fit into the same cavity in a specific
biological receptor; the complex of the molecule and the receptor can pass
through cell membranes and thereby initiate toxic action. By comparing
molecular models, it is not difficult to see, e.g., that the most toxic PCB,
namely 3,3
,4,4
,5
-pentachlorobiphenyl, is almost the same size and shape as
2,3,7,8-TCDD. It is believed that some of the toxicity of the cooking-oil inci-
dents arose from coplanar PCBs.
Only a very small fraction of commercial PCB mixtures corresponds to
coplanar PCBs having no ortho chlorines. Although individually less toxic,
PCBs with one ortho chlorine, and with chlorines in both para and at
least one meta position, contribute substantially to the overall toxicity of
PCB mixtures since they are far more prevalent than those having no ortho
chlorines.
In humans, the more highly chlorinated furans, dioxins, and PCBs are
stored in fatty tissues and are neither readily metabolized nor excreted. This
persistence is a consequence of their structure: Few of them contain hydrogen
atoms on adjacent pairs of carbons at which hydroxyl groups, OH, can read-
ily be added in the biochemical reactions that are necessary for their elimina-
tion. In contrast, those compounds with few chlorines always contain one or
more such adjacent pairs of hydrogens and tend to be excreted after hydrox-
ylation, rather than stored for a long time.
The TEQ Scale

Since most organisms, including humans, have a mixture of many dioxins,
furans, and PCBs stored in their body fat, and since all these compounds act
qualitatively in the same way, it is useful to have a measure of the net toxicity
of the mixture. To this end, scientists often report concentrations of these
organochlorines in terms of the equivalent amount of 2,3,7,8-TCDD that, if
present alone, would produce the same toxic effect. An international toxicity
equivalency factor, or TEQ, has been devised that rates each dioxin, furan,
and PCB congener’s toxicity relative to that of 2,3,7,8-TCDD, which is
arbitrarily assigned a value of 1.0. Recently, polybrominated biphenyls have also
been added to this scale.
A summary of the TEQ values for some of the more toxic dioxins, furans,
and PCBs is given in Table 11-1. As an example, consider an individual who
ingests 30 pg (picograms) of 2,3,7,8-TCDD, 60 pg of 1,2,3,7,8-PCDF, and
Toxicity Equivalence Factors (TEQ) for Some

TABLE 11-1 Important Dioxins, Furans, and PCBs
Dioxin or Furan or PCB Toxicity Equivalency Factor
2,3,7,8-Tetrachlorodibenzo-p-dioxin 1
1,2,3,7,8-Pentachlorodibenzo-p-dioxin 0.5
}
1,2,3,4,7,8-Hexachlorodibenzo-p-dioxin
1,2,3,7,8,9-Hexachlorodibenzo-p-dioxin 0.1
1,2,3,6,7,8-Hexachlorodibenzo-p-dioxin
1,2,3,4,6,7,8-Heptachlorodibenzo-p-dioxin 0.01
Octachlorodibenzo-p-dioxin 0.001
2,3,7,8-Tetrachlorodibenzofuran 0.1
2,3,4,7,8-Pentachlorodibenzofuran 0.5
1,2,3,7,8-Pentachlorodibenzofuran 0.05
}
1,2,3,4,7,8-Hexachlorodibenzofuran
0.1
1,2,3,4,6,7,8-Heptachlorodibenzofuran
1,2,3,4,7,8,9-Heptachlorodibenzofuran } 0.01
Octachlorodibenzofuran 0.001
3,3
,4,4
,5-Pentachlorobiphenyl 0.1
3,3
,4,4
,5,5
-Hexachlorobiphenyl 0.01
200 pg of OCDD. Since the TEQ factors for these three substances are,
respectively, 1.0, 0.05, and 0.001, the intake is equivalent to
(30 pg 1.0) (60 pg 0.05) (200 pg 0.001) 33.2 pg
Thus, even though a total of 290 pg of dioxins and furans were ingested
by this person, the mixture is equivalent in its toxicity to an intake of only
33.2 pg of 2,3,7,8-TCDD.
P R O B L E M 11-11
Using the TEQ values in Table 11-1, calculate the number of equivalent
picograms of 2,3,7,8-TCDD that corresponds to an intake of a mixture
of 24 pg of 1,2,3,7,8,9-hexachlorodibenzo-p-dioxin, 52 pg of 2,3,4,7,8-
pentachlorodibenzofuran, and 200 pg of octachlorodibenzofuran.
The TEQ values for environmental samples are sometimes reported in

the media as if they represent the concentration of 2,3,7,8-TCDD itself.
However, this compound often is not even the dominant contributor to
the TEQ toxicity. As discussed previously, combustion of organic matter
produces relatively few toxic dioxins; the TEQ from such sources is often
dominated by penta- and hexachlorinated furans. Similarly, the TEQ arising
from the use of chlorination in bleaching paper is dominated by toxicity from
tetrachlorinated furans.
Dioxins, Furans, and PCBs in Food

About 95% of human exposure to dioxins and furans arises from the presence
of the compounds in food. A bar graph showing the TEQ values for contam-
ination of various types of foods purchased in U.S. supermarkets in the 1990s
is shown in Figure 11-8. Notice that fresh-water fish contained the highest
levels of both PCB and furan toxicity. Recently, average TEQ levels of several
ppt have been found for farmed salmon; these high levels originate with the
fishmeal and fish oil the growing salmon had been fed. However, the TEQ
levels in young chickens and turkeys and in hogs sold in the United States
has declined significantly—by 20 to 80%—in recent years. The composite
vegan diet (i.e., all vegetable, fruit, and grain, with no animal products at
all) has a very low TEQ compared to that from animal-based components.
1.60
PCB TEQ 1.43
1.40
PCDF TEQ
1.20
1.07
PCDD TEQ
1.00
TEQ (ppt)
0.80
0.60 0.54
0.47
0.38 0.40
FIGURE 11-8 TEQ values 0.40 0.32 0.32 0.34 0.33
for foods collected from
U.S. supermarkets. 0.20 0.12
0.07
[Source: A. Schecter et al.,
“Levels of Dioxins, Dibenzofu- 0.00
rans, PCB and DDE Congeners
et
ef
rk
gs
Ve ish
se
am
ilk
tte
gn
ke
fis
di
Be
Po
ee
Eg
re
M
Bu
ic
lo
in Pooled Food Samples

Ch
an
er
ec
Ch
ga
at
ce
/b
Ic
w
Collected in 1995 at
gs
h-
do
es
Supermarkets Across the

Fr
ot
H
United States,” Chemosphere

34 (1997): 1437.]
A 2003 report by the U.S. Institute of Medicine recommended that girls

should reduce their consumption of animal products in order to reduce the
amount of dioxins that build up in their body fat and that could subsequently
affect any children they might have in the future.
P R O B L E M 11-12
Given that the average TEQ of animal-based foods was about 0.4 pg of TCDD
equivalent per gram when the data in Figure 11-8 were collected, and that
the LD50 for 2,3,7,8-TCDD is about 0.001 mg/kg body weight, what mass of
animal-based food would you have had to consume to ingest a fatal dose of it?
In the mid-1980s, the average total concentration of all dioxins and

furans in the fat tissue of adult North Americans was about 1000 ppt. How-
ever, because highly chlorinated and therefore less toxic congeners pre-
dominated, the TEQ value was much less: about 40 ppt of 2,3,7,8-TCDD
equivalent. By the 1990s, the TEQ in human fat had fallen to about 15 ppt.
The historical maximum TEQ levels, about 75 ppt, were reached in the
1970s. The variation with time of stored dioxins and furans fits a model in
which the daily TEQ dose amounted to about 0.5 pg/kg body weight in the
early decades of the twentieth century, rose to over 6 pg/kg in the 1940s to
1970s, and has now declined again to 0.5 pg/kg.
The average North American adult’s body contains about 15 kg of fat,
so his or her total body burden of 2,3,7,8-TCDD equivalents now amounts
to about 0.2 mg. Given that the average residence time tavg of dioxins and
furans in the human body is about seven years, and using the relationship from
Chapter 6 connecting tavg to the total amount C and the input rate R, i.e.,
tavg C兾R
then the average human rate of intake of 2,3,7,8-TCDD equivalents is calcu-
lated to be
R C兾tavg 0.2 mg兾7 y 0.03 mg兾y
This value, which corresponds to about 1 pg per kilogram body weight per
day, is close to the intake estimated over the last few years from the model
discussed previously.
Dioxins as Probable Human Carcinogens

Although there is little argument as to the relative acute toxicities of various
dioxin and furan congeners, their absolute risk to humans is very controver-
sial. The amount of 2,3,7,8-TCDD per kilogram body weight required to
kill a guinea pig is extraordinarily small—about 1 mg—making it the most
toxic synthetic chemical known for that species. However, the LD50 required
to kill many other types of animals is hundreds or thousands of times this
amount—e.g., the LOD50 for hamsters 1200 mg/kg; for frogs, 1000 mg/kg; for
rabbits and mice, 115 mg/kg; for monkeys, 70 mg/kg; and for dogs, it may be as
low as 30 mg/kg. A 2000 EPA report on dioxin suggests that humans fall in
the middle range for acute susceptibility to dioxins; humans given doses of
100 mg/kg suffered no apparent ill effects beyond chloroacne.
Another widespread exposure of humans to 2,3,7,8-TCDD occurred in
the early 1970s in and around Times Beach, Missouri. Waste oil containing
PCBs and 2,3,7,8-TCDD from the manufacture of 2,4,5-trichlorophenol was
used for dust control on gravel roads. Some horses died due to exposure in an
area where the dioxin contamination was particularly high, and some chil-
dren became ill. A decade later, widespread contamination of the soil in the
town was discovered. In 1997, over 200,000 tonnes of soil from this town and
26 other affected sites in eastern Missouri that had soil 2,3,7,8-TCDD levels
of 30–200 ppb were excavated and incinerated in order to remediate the
problem. (The town of Times Beach was abandoned in 1982 due in part to a
severe flash flood.) Although exposure to the chemical seems to have nega-
tively affected their immune systems, a major study in 1986 did not find evi-
dence of increased disease prevalence in the exposed group of Times Beach
residents. Less formal studies and anecdotal evidence, however, indicate
problems with seizures and congenital abnormalities, and so the issue remains
controversial.
Scientists are more concerned about the long-term effects of exposure to
dioxins than about their acute toxicities. The Seveso study discussed previ-
ously was the first to show an increased rate of cancer among people exposed
accidentally to TCDD. A recent analysis of the health of American workers
who were employed in industries that produced chemicals contaminated
with 2,3,7,8-TCDD indicates that exposure to it at relatively high levels
may cause cancer. The current theory concerning the action of dioxin pre-
dicts that there should be a threshold below which no toxic effects will
occur, and recent studies of workers exposed to 2,3,7,8-TCDD supports this
hypothesis.
In animal studies, a threshold of about 1000 pg (i.e., 1 ng) of 2,3,7,8-
TCDD equivalent per kilogram of body weight per day is observed with
respect to the cancer-causing ability of dioxins and furans. In determining
the maximum tolerable human exposure to such compounds, many govern-
ments apply a safety factor of 100, resulting in a guideline for maximum
exposure of 10 pg/kg/day averaged over a lifetime. Currently, the average
American ingests only about one-tenth this amount from animal fats in his
or her food supply. Exposure levels near the guideline limit are expected
for persons consuming large amounts of fish that have elevated dioxin and
furan levels.
The U.S. EPA draft report of 2000 concerning the health risks of dioxins
concluded that 2,3,7,8-TCDD is a (known) human carcinogen—although
this characterization was a point of controversy among members of the expert
committee that reviewed the report—and that the mixtures of dioxins to

which people are exposed is a “likely human carcinogen.” The International
Agency for Research on Cancer of the World Health Organization had previously
classified TCDD as a known human carcinogen. Experiments had indicated
that 2,3,7,8-TCDD was the most potent multisite carcinogen known in test
animals. The EPA estimates that the most sensitive and most highly exposed
Americans stand at least a 1-in-1000 chance of developing cancer from
dioxin. The report notes that noncancer effects of dioxin are at least as
important as cancer.
However, there is currently no clear indication that the level of cancer
has risen in the general American population due to dioxins, though this
could well be due to the inability to relate effects to exposure at current
levels. In addition to cancer, the report concludes that dioxins adversely
affect the endocrine and immune systems and the development of fetuses, as
will be discussed in Chapter 12.
For furans, direct evidence of human susceptibility is available from
the incidents of PCB-contaminated cooking-oil consumption mentioned
above. The most common symptoms observed in these groups were chloracne
and other skin problems. Unusual pigmentation occurred in the skin of
babies born to some of the mothers who had been exposed. The children
also often had low birth weight and experienced a rather high infant mor-
tality rate. Children who directly consumed the oil showed retarded growth
and abnormal tooth development. Many of the victims also reported aching
or numbness in various parts of their bodies and frequent bronchial prob-
lems. Other than chloracne, such symptoms are not observed in workers
who are occupationally exposed to PCBs and whose body burdens of PCBs
are comparable to those who consumed the contaminated oil, but in which
the PCDF concentration is orders of magnitude lower. However, some chil-
dren of these workers had mild cases of the less serious problems seen in the
poisoned group.
Ukrainian president Viktor Yushchenko was apparently the recent
victim of deliberate dioxin poisoning. Since September 2004, he has suffered
from ulcers in his stomach and intestines, problems with his liver and spleen,
and disfiguring facial cysts that have left him looking far older than he is
(Figure 11-9).
Human Exposure to Dioxins, Furans, and PCBs

There continues to be vigorous debate in scientific, industrial, and medical
communities regarding the environmental dangers of dioxins, furans, and
PCBs. In one camp are those who feel that the dangers from these chemicals
have been wildly overstated in the media and by some special-interest groups.
They point to the very low concentrations of these substances that exist in
the environment, to the possibility that there is a threshold below which
FIGURE 11-9 Ukranian

president Viktor
Yushchenko before and
after he was poisoned
with dioxin. [Source:
AP Photo/Efrem Lukatsky.]
these compounds have no effect on human health, to the lack of known

human fatalities resulting from them, and to the enormous economic costs
associated with instituting further controls and cleanup measures. At the
other extreme are persons who point to the substantial biomagnification and
high toxicity per molecule of these substances and to their presence in almost
all environments. They consider the detrimental effects such as cancer and
birth deformities caused by these chemicals in wildlife to be “warning
canaries” that signal potential ill effects in humans. Discovering where the
truth lies between these opposing viewpoints presents a challenge even for
environmental science students, to say nothing of the public at large!
Review Questions
1. Using structural diagrams, write the reaction 5. What does PCB stand for? Draw the structural
by which 2,3,7,8-TCDD is produced from diagram of the 3,4
,5
-trichloro PCB molecule.
2,4,5-trichlorophenol.
6. What were the main uses for PCBs? What is
2. Draw the structure of 1,2,7,8-TCDD. What is meant by an open use?
the full name for this dioxin?
7. Draw the structure of a representative
3. What, chemically speaking, was Agent Orange, polychlorinated dibenzofuran congener.
and how was it used?
8. Other than the chlorophenols and PCBs, what
4. Draw the structure of pentachlorophenol. What are some of the other sources of dioxins and furans
is its main use as a compound? What is the main in the environment? What is currently the biggest
dioxin congener that it could produce? anthropogenic source of dioxins?
9. From what medium—air, food, or water—does 12. Are all dioxin congeners equally toxic? If not,
most human exposure to dioxin come about? Why what pattern of chlorine substitution leads to the
is this so? greatest toxicity? Which is the most toxic dioxin?
10. What molecules can be eliminated by a PCB 13. What is meant by a coplanar PCB? What
molecule when it is heated to moderately high structural features give rise to noncoplanarity?
temperatures?
14. What does TEQ stand for? Why is it used?
11. Are PCBs acutely toxic to humans? What is
15. Is dioxin carcinogenic to humans or not?
the basis for health concerns about them? Recount
Discuss the evidence for and against.
recent evidence that shows that PCBs can affect
human development.

See the discussion of focus areas and the principles (b) List at least three of the twelve principles of
of green chemistry in the Introduction before green chemistry that are addressed by the green
attempting these questions. chemistry developed by Collins.
1. The development of TAML catalyst for 2. What environmental advantages does the
hydrogen peroxide oxidation by Terry Collins won a TAML/hydrogen peroxide method of bleaching
Presidential Green Chemistry Challenge Award. pulp have over the use of elemental chlorine?
Additional Problems
1. Deduce which combination(s) of two different photochemical dechlorination of OCDD. What
tetrachlorophenol isomers would produce the potential flaw exists in treating water by UV light,
following hexachlorodibenzo-p-dioxins: given the nature of the products that are formed?
(a) the 1,2,3,7,8,9 isomer, (b) the 1,2,4,6,8,9 4. Using mechanical ball-and-stick or computer-
isomer, and (c) the 1,2,3,6,7,9 isomer. generated molecular models, construct structures
[Hint: See Box 11-1.] for (a) 2,3,7,8-TCDD, (b) dibenzofuran, and
2. Deduce which dioxins would likely result from (c) biphenyl. Place chlorines onto the dibenzofuran
the low-temperature combustion of a commercial and biphenyl models such that the space filled by
sample of PCP. the carbon, oxygen, and chlorine atoms overlaps
that of the dioxin as much as possible without
3. In the purification of wastewater contaminated occupying much of the space associated with
by pentachlorophenol and 2,3,5,6-tetrachlorophe- the alpha positions. Do the resulting congeners
nol using ultraviolet light, it was noticed that represent the most toxic furan and biphenyl
OCDD and 1,2,3,4,6,7,8-heptachlorodibenzo-p- according to TEQ values?
dioxin were formed. Deduce whether the latter
was formed by the coupling of a molecule of each 5. Consider the PCDF on the next page. Deduce
of the phenols or must have been formed by which PCBs could produce this furan if they are
moderately heated in air, given that PCDFs can animals, can you predict whether biomagnification
result from HCl elimination with or without occurs for the latter relative to its diet?
2,3 interchange, or from Cl2 elimination.
7. Predict the order of toxicity of the three tetra-
[Hint: See Box 11-2.]
chlorobiphenyls with the following numbering:
(a) 2,4,3
,4
; (b) 3,4,5,4
; (c) 2,4,2
,6
. [Hint: Will
these PCB molecules be coplanar?]
O 8. In the potential reactions of chlorinated

phenols undergoing incineration in separate
Cl facilities, what dioxins could be formed from
(a) 2,5-dichlorophenol, and (b) 2,4,6-
6. By comparing the average dioxin levels in
trichlorophenol? Name the two dioxins, and
humans to those in our food, decide whether or
predict which would be the more toxic.
not dioxin is biomagnified in the transition. Given
the food typically eaten by domestic animals such 9. The partitioning of PCBs among air, water, and
as cattle and chickens compared to that of the sediments can be estimated by the fugacity model
fresh-water fish we eat, can you explain why dioxin discussed in Chapter 10. The Z values for a typical
TEQ levels in Figure 11-8 for the fish exceed those environmental PCB are 4 104 in air, 0.03 in
for the animals? Why is the TEQ value for butter water, and about 10,000 in sediment (and biota).
so much higher than that for milk, and that for hot Using the model world volumes in Chapter 10,
dogs greater than the general levels for meat? Why calculate the equilibrium concentrations when
is the TEQ value for a vegan diet so very low? Given 1 mole of PCBs is distributed among air, water,
the vegan-diet TEQ and that for the domestic and sediment.
C H A P T E R
12
OTHER TOXIC ORGANIC
COMPOUNDS OF
ENVIRONMENTAL CONCERN
topics are used:
 Elementary organic chemistry (as in the Appendix in
this book)
 Concept of vapor pressure

 Maximum Contaminant Level (MCL) (Chapter 10)
 Structures of dioxins, furans, and PCBs; congeners
(Chapter 11)
 Structures of DDT, DDE, and atrazine (Chapter 10)
 Concepts of bioaccumulation; Kow (Chapter 10)
 Concepts of free-radical and chain reactions (Chapters 1–5)
 LD50 (Chapter 10)
Introduction
In this chapter, we shall look at a series of toxic organic compounds that do
not contain chlorine but that have become common air and water pollutants.
We begin by considering PAHs, pollutants that accompany the combustion
of most natural organic materials, and then consider a wide range of environ-
mental chemicals—most of which have been encountered in other contexts—
that may have disruptive effects on our reproductive systems. We then
consider the surprising mechanism by which persistent substances become
distributed around the world by air currents. Finally, we survey two new classes
507
508 Chapter 12 Other Toxic Organic Compounds of Environmental Concern
of commercial products that are causing environmental concern and are being
transported to remote regions by this mechanism. The topic of pharmaceutical
contamination of drinking water will be discussed in Chapter 16.
Polynuclear Aromatic Hydrocarbons (PAHs)

One of the most common and ancient types of environmental pollutant,
whether in air, water, or soil, is a large series of hydrocarbons known as PAHs.
We first discuss the molecular structure of these compounds, then relate their
occurrence in the environment and their health effects on humans.
The Molecular Structure of PAHs

There is a series of hydrocarbons whose molecules contain several six-
membered benzene-like rings connected by the sharing of a pair of adjacent
carbon atoms between two adjoining fused rings. The simplest example is
naphthalene, C10H8:
H H
C C
H C C C H
or
H C C C H
C C
H H
naphthalene
Notice that there are ten, not twelve, carbon atoms in total and that there are
only eight hydrogen atoms, since the shared carbons have no attached hydro-
gen atoms. As a compound, naphthalene is a volatile solid whose vapor is
toxic to some insects. It has found use as one form of “moth balls,” the other
being 1,4-dichlorobenzene.
Conceptually, there are two ways to fuse a third benzene ring to two
carbons in naphthalene; one results in a linear arrangement for the centers
(the “nuclei”) of the rings while the other is a “branched” arrangement:
anthracene phenanthrene
The resulting molecules, anthracene and phenanthrene, are PAH pollutants

arising from incomplete combustion, especially of wood and coal. They are
also released into the environment from the dumpsites of industrial plants
that convert coal into gaseous fuel and from the refining of petroleum and
shale. In rivers and lakes they are found mainly attached to sediments rather
than dissolved in the water; both are subsequently partially incorporated into
fresh-water mussels.
P R O B L E M 12-1
Draw the full structural diagram for phenanthrene, showing all atoms and
bonds explicitly.
P R O B L E M 12-2
By determining their molecular formulas, show that the molecules below are
not additional isomers of C14H10:
P R O B L E M 12-3
Using a systematic procedure, deduce the structural formulas for the five
unique isomers of C18H12, which contains four fused benzene rings.
In general, hydrocarbons that display benzene-like properties are called

aromatic; those that contain fused benzene rings are called polynuclear (or
polycyclic) aromatic hydrocarbons, or PAHs for short. Like benzene itself,
most PAHs have a planar geometry and contain alternating single and double
bonds producing unusually high stability. A few PAHs also contain one or
more five-membered rings. Other than naphthalene, they are not manufac-
tured commercially. However, some PAHs are extracted from coal tar and
used in commerce.
PAHs as Air Pollutants

PAHs are common air pollutants and are strongly implicated in the degradation
of human health. Typically, the concentration of PAHs in urban outdoor air
amounts to a few nanograms per cubic meter, although it reaches 10 times
this amount in very polluted environments. PAHs are formed when carbon-
containing materials are incompletely burned. Elevated PAH concentrations
in domestic indoor air are typically due to the smoking of tobacco and the
burning of wood and coal.
PAHs containing four or fewer rings usually remain as gases if they are
released into air, since the vapor pressures of their liquid forms are relatively
high. After spending on average less than a day in outside air, such PAHs are
degraded by a sequence of free-radical reactions that begin, as expected from
our previous analysis of air chemistry (Chapters 3 and 5), by the addition of
the OH radical to a double bond.
In contrast to their smaller analogs, PAHs with more than four benzene
rings do not exist for long in air as gaseous molecules. Owing to their low
vapor pressure, they condense and become adsorbed onto the surfaces of sus-
pended soot and ash particles. PAHs are found mainly on particles of submi-
cron, i.e., respirable, size; consequently, the PAHs can be transported into the
lungs by breathing.
Figure 12-1 illustrates the concentrations of the most abundant PAHs in
an air sample taken in Sweden. The leftmost four PAHs in the figure have
three or four fused rings and, as expected, occur mainly as gases. The remain-
ing ones, which in contrast are found mainly associated with fine particulate
40
Gas phase
35 PM2.5
Ambient air concentration (ng/m3)
30
25
20
15
10
FIGURE 12-1 The distri-
bution of individual PAHs 5
attached to fine particles
(PM2.5) and in the gas
phase in an ambient air 0
ne
ne
ne
ne
e
en
en
en
en
en
en
Ba
sample from Sweden.

re
he
re
se
ac
ac
th
th
yl
r
th
Py
py
ry
nt
an
an
er
hr
hr
[Source: C.-E. Bostrom et al.,

an
Ch
ra
d]
i]p
nt
nt
or
or
en
uo
[c
A
]a
flu
flu
gh
“Cancer Risk Assessment for

no
Ph
Fl
[a
b]
k]
o[
de
nz
Polycyclic Aromatic Hydrocar-

o[
o[
nz
In
Be
nz
nz
Be
bons,” Environmental Health

Be
Be
Perspectives 110 (supplement 3)

(2002): 451.]
matter, are larger. Even PAHs with two to four rings are adsorbed onto parti-
cles in the wintertime, since their vapor pressure decreases sharply at lower
temperatures. The role of vapor pressure in determining the long-range air
transport of pollutants such as PAHs is discussed later in this chapter.
By 2001, the concentrations of PAHs in rural air in eastern North America
(Nova Scotia) were found to have declined by an order of magnitude since
reaching their peak in 1985, presumably due to air pollution abatement pro-
grams in Canada and the United States. In contrast, the concentrations of
PAHs in sediments laid down in urban lakes increased substantially over that
period.
Soot itself is mainly graphite-like carbon; it consists of a collection of
tiny crystals (crystallites), each composed of stacks of planar layers of carbon
atoms, all of which occur in fused benzene rings. Graphite is the ultimate
PAH—its parallel planes of fused benzene rings each contain a vast number
of carbon atoms.
graphite
There are no hydrogen atoms in graphite except at the periphery of the layers.
The surfaces of soot particles are excellent adsorbers of gaseous molecules,
especially organic ones.
PAHs are introduced into the environment from a number of sources:
the exhaust of gasoline and especially diesel combustion engines, the “tar” of
cigarette smoke, the surface of charred or burned food, the smoke from burning
wood or coal, and other combustion processes in which the carbon of the fuel
is not completely converted to CO or CO2. Although PAHs constitute only
about 0.1% of airborne particulate matter, their existence as air pollutants is
of concern since many them are carcinogenic, at least in test animals. Vehicle
exhaust, especially from diesel engines, older gasoline-powered cars, and all
vehicles in which the engine has not warmed up, is the major contributor to
PAH levels in cities. Aluminum smelters are a source of PAHs since their
heated graphite anodes deteriorate over time, releasing the hydrocarbons.
A survey of PAH emissions in Taiwan from exhaust stacks found the fol-
lowing trends for different types of restaurants, the differences presumably
arising from the style of cooking employed:
Chinese Western fast-food Japanese
PAH levels in the air were particularly high near the site of World Trade
Center buildings in New York for many days after they had been destroyed in
September 2001. However, the heat generated by the flames carried most of
the smoke aloft. In addition to PAHs, the high temperatures and anaerobic
conditions within the piles of debris resulted in the oxidation by chlorine of
metals and organic substances, producing a wide variety of contaminants.
PAHs as Water Pollutants

Polycyclic aromatic hydrocarbons also are serious water pollutants. PAHs
enter the aquatic environment as a result of spills of oil from tankers, refineries,
and offshore oil-drilling sites. In drinking water, the PAH level typically
amounts to a few parts per trillion and usually is an unimportant source of
these compounds to humans. The larger PAHs bioaccumulate in the fatty
tissues of some marine organisms and have been linked to the production of
liver lesions and tumors in some fish. PAHs, PCBs, and the insecticide mirex
are thought to play a role in the devastation of the populations of beluga
whales in the St. Lawrence River; since discharges of these pollutants to the
river have decreased substantially in recent years, the health of the belugas
may eventually improve.
PAHs are generated in substantial quantity in the production of such
coal-tar derivatives as creosote, a wood preservative used especially on rail-
way ties. Up to 85% of the 200 compounds in creosote are PAHs, including
some carcinogenic ones. In addition to concerns about PAH exposure to
workers installing the ties, gardeners who buy used railway ties for land-
scape design and people burning discarded ties are at risk. The leaching of
PAHs from the creosote used to preserve the immersed lumber of fishing
docks and the like represents a significant source of pollution to crustaceans
such as lobsters.
Formation of PAHs During Incomplete Combustion

The mechanism of PAH formation during combustion of organic materials is
complex but is due primarily to the repolymerization of hydrocarbon frag-
ments that are formed during the cracking (i.e., the splitting into several
parts) of larger fuel molecules in the flame. Fragments containing two carbon
atoms are particularly prevalent after cracking and partial combustion have
occurred. Two C2 fragments can combine to form a C4 free-radical chain,
which could add another C2 to form a six-membered ring. Such reactions
occur quickly if one of the original C2 fragments is itself a free radical.
The repolymerization reaction occurs particularly under oxygen-deficient

conditions. Generally the PAH formation rate increases as the oxygen-to-fuel
ratio decreases. The fragments often lose some hydrogen, which forms water
after combining with oxygen during the reaction steps. The carbon-rich frag-
ments combine to form the polynuclear aromatic hydrocarbons, which are the
most stable molecules that have a high C-to-H ratio.
Since neither methane, the main component of natural gas, nor methanol
molecules contain any C¬C bonds with which to form C2 units, their com-
bustion as fuels produces very little PAH or other soot-based particulates.
Carcinogenic Properties of PAHs

The most notorious and common carcinogenic PAH is benzo[a]pyrene, BaP,
which contains five fused benzene rings:
benzo[a]pyrene pyrene
The molecule is named as a derivative of pyrene, which has the structure

shown at the right. Conceptually, if an additional benzene ring is added at the
pyrene bond labeled a, the benzo[a]pyrene molecule is obtained.
Benzo[a]pyrene is a common by-product of the incomplete combustion of
fossil fuels, of organic matter (including garbage), and of wood. It is a carcinogen
in test animals and a probable human carcinogen. BaP is worrisome since it
bioaccumulates in the food chain—its log Kow value is 6.3, comparable to that
of many organochlorine insecticides (see Table 10-3). It is considered to be one
of the top 15 organic carcinogens in drinking water, as listed in Table 12-1 along
with the other 14 compounds in this category, most of which are pesticides.
A second example of a carcinogenic PAH is the four-ring hydrocarbon
benz[a]anthracene, which is anthracene with an additional benzene ring
fused to the a bond:
benz[a]anthracene
The relative positions in space of the fused rings in PAHs play a major
role in determining their level of carcinogenic behavior in animals. The
Top Organic Carcinogens in

TABLE 12-1 U.S. Drinking Water*
Cancer Risk per

Chemical MCL in ppb 100,000 People
Ethylene dibromide 0.05 12.5

Toxaphene 3 9.6
Vinyl chloride 2 8.4
Heptachlor 0.4 5.2
Heptachlor epoxide 0.2 5.2
Hexachlorobenzene 1 4.6
Benz[a]pyrene 0.2 4.2
Chlordane 2 2.0
Carbon tetrachloride 5 1.9
1,2-Dichloroethane 5 1.3
PCBs 0.5 0.5
Pentachlorophenol 1 0.3
Di(2-ethylhexyl) phthalate 6 0.2
Dichloromethane 5 0.1
(methylene dichloride)
Source: A. H. Smith et al., “Arsenic Epidemiology and Drinking Water Standards,” Science
296 (2002): 2146.
*Chemicals ordered by their cancer risk, were they to be consumed at their MCL (maximum
contaminant level).
PAHs that are the most potent carcinogens each possess a bay region formed
by the branching in the benzene ring sequence: The organization of carbon
atoms as an open bay indirectly imparts a high degree of biochemical reactiv-
ity to the PAH, as explained in Box 12-1.
bay region
P R O B L E M 12-4
Based upon the bay region theory, would you expect naphthalene to be a car-
cinogen? How about anthracene or phenanthrene? What about the PAH
called benzo[ghi]perylene, whose structure is shown on the next page?
BOX 12-1 More on the Mechanism of PAH Carcinogenesis
esearch has established that the PAH mol- The double bond (shown in the structure) that
R ecules themselves are not carcinogenic
agents; rather they must be transformed by
remains in the same ring as the two 9 OH
groups subsequently undergoes epoxidation,
several metabolic reactions in the body before yielding the molecule that is the active
the actual cancer-causing species is produced. carcinogen:
The first chemical transformation that
occurs in the body is the formation of an epoxide
ring across one C " C bond in the PAH. The O
specific epoxide of interest to the carcinogenic
behavior of benzo[a]pyrene is
H
OH
H OH
By adding H, this molecule can form a

O particularly stable cation that can bind to mol-
ecules such as DNA, thereby inducing muta-
A fraction of these epoxide molecules subse- tions and cancer.
quently add H2O, to yield two — OH groups The metabolic reactions of epoxide
on adjacent carbons: formation and H2O addition are part of the
body’s attempt to introduce 9 OH groups
into hydrophobic molecules like PAHs to
make them more easily dissolved in water and
then eliminated. For BaP and other PAHs
that possess a bay region, one of the interme-
H diate products in this multistep process can be
OH diverted instead into the formation of a very
H OH stable cation that induces cancer.
benzo[ghi]perylene
Some PAHs with certain of their hydrogen atoms replaced by methyl groups
are even more potent carcinogens than are the parent hydrocarbons.
Environmental Levels of PAHs and Human Cancer

Has exposure to PAHs been demonstrated to produce cancer in humans? The
answer is both yes and no. For over 200 years, it has been known that pro-
longed exposure in occupational settings to very high levels of coal tar, the
principal toxic ingredient of which is benzo[a]pyrene, leads to cancer in
humans. In 1775 the occurrence of scrotal cancer in chimney sweeps was
associated with the soot lodged in the crevices of the skin of their genitalia.
Modern workers in coke-oven and gas-production plants likewise experience
increased levels of lung and kidney cancer due to this PAH.
The evidence for cancer induction in the general public, whose exposure
to PAHs is at levels that are orders of magnitude lower than in these occupa-
tional environments, is less clear-cut. The main cause of lung cancer is the
inhalation of cigarette smoke, which contains many carcinogenic compounds
in addition to PAHs; the deduction from health statistics of the much smaller
influences of air pollutants such as PAHs from other sources is difficult to
accomplish. Some scientists speculate that the higher death rate from lung
cancer in cities as compared to rural areas found in many countries is due in
part to breathing carcinogenic air pollutants like PAHs, although other fac-
tors such as a higher smoking rate also contribute.
Many cities in developing countries have chronic problems with carbon-
based particulate air pollution. For example, the serious indoor and outdoor
air pollution, which arises primarily from the unvented burning of coal and
biomass for cooking and heating and consists primarily of PAHs, sulfur diox-
ide, and particulate matter, is reputed to be responsible for over 1 million
deaths annually in China. The rate of lung cancer in Chinese women is
higher than that for men, possibly due to higher and longer indoor exposures
to PAHs from coal burning and from cooking-oil fumes.
Diesel-engine exhaust has been labeled a “probable human carcinogen.”
It contains not only PAHs but also some of their derivatives containing the
nitro group, ¬NO2, as a substituent; these nitrated substances are even more
active carcinogens than are the corresponding PAHs. For example, nitropy-
rene and dinitropyrene are responsible for much of the mutagenic character of
diesel exhaust, i.e., its ability to cause mutations that could ultimately pro-
duce cancer. These compounds are formed within the engines by the reaction
of pyrene with NO2 and N2O4. There is also evidence that PAHs are nitrated
by some of the constituents of photochemical smog.
As discussed in Chapter 3, the emission of particulates from heavy-duty
diesel engines can be controlled by means of filter traps in the exhaust stream.
These devices temporarily retain the solids, including soot, in the exhaust and
eventually oxidize them further. Some scientists have worried that, during
their residence in the traps, PAHs could undergo reaction to produce even
greater quantities of nitrated PAHs. While this apparently does occur, tests
indicate that the total mutagenic activity of a given amount of engine exhaust
is actually decreased by the devices, since most of it is oxidized in the trap.
For most nonsmokers in developed countries, by far the greatest exposure

to carcinogenic PAHs arises from their diet, rather than directly from polluted
air, water, or soil. As expected from their mode of preparation, charcoal-
broiled and smoked meat and fish contain some of the highest levels of PAHs
found in food. However, leafy vegetables such as lettuce and spinach can con-
stitute an even greater source of carcinogenic PAHs due to the deposition of
these substances from the air onto the leaves of the vegetables while they are
growing. Unrefined grains also contribute significantly to the total amount of
PAHs ingested from food.
Environmental Estrogens
In the last two decades, a new threat to the health of wildlife, and possibly of
humans, exposed to synthetic organic chemicals in the environment has been
identified. It has been established that certain compounds can affect the repro-
ductive and immune health of higher organisms and may also increase the rate
of cancer in reproductive organs. Much of the public interest in this issue was
stirred by the 1996 publication of the book Our Stolen Future by Theo Colburn
and her associates. However, there remains great uncertainty and debate in
the scientific community about whether or not there are significant risks to
human health from environmental levels of these compounds.
Mechanism of Action of Environmental Estrogens

The chemicals in question interfere with the system in the organism that oper-
ates by transmitting extremely low concentrations, on the parts-per-trillion
level, of chemical messenger molecules called hormones. The hormones flow
through the bloodstream from the point of production and storage to their tar-
get organs, including those involved in sexual reproduction in both females
and males. The arrival of the hormone at a receptor is a signal for the cell to
initiate action of some type. Much of the concern about humans centers upon
interference with estrogens, the female sex hormones (which also are present
in males, but at a smaller concentration.) There also exist environmental
substances that interfere with androgens, the male sex hormones, and with
thyroid hormones. Sex hormones, including estrogens and androgens, contain
the characteristic four-ring steroid structure (see top of Figure 12-2). They are
produced from cholesterol in the ovaries of females and the testes of males in
response to signals from the brain and other organs.
Hormone actions are initiated by the binding of the hormone to a spe-
cific receptor within a cell. The resulting hormone–receptor complex binds
to specific regions of DNA in the cell nucleus, an action that in turn deter-
mines the action of the genes. Certain environmental chemicals can also
bind to the hormone receptor and thereby either mimic or block the action
of the hormone itself. In particular, the “promiscuous” estrogen receptor
will bind to a number of compounds, even ones that bear little structural
FIGURE 12-2 The struc- OH
tures of estradiol and some CH3
environmental estrogens.
HO
estradiol, the main estrogen
CCl3 CCl3
CH3O C OCH3 C Cl
H H
Cl
methoxychlor
o,p
-DDT
Cl
O
Cl
O Cl2
Cl10
Cl
kepone
Cl
dieldrin
O
Clm Cln Clm Cln
O
dioxins PCBs
CH3
HO C9H19 HO C OH
nonylphenol CH3
bisphenol-A
OH O
OH O
C9O9R
HO O C9O9R
genistein
O
phthalate esters (R ethyl,
n-butyl, n-hexyl, n-octyl, isononyl,
isodecyl, benzyl butyl, 2-ethylhexyl)
518
resemblance to estrogen itself. However, most such compounds bind to

the receptor with only a small fraction of the strength of estrogen itself.
Estrogen itself binds to its main receptor by hydrogen bonding from its two
¬OH groups and by attractive van der Waals forces from its ring system to
amino acid side chains. A second estrogen receptor has recently been dis-
covered. In addition to the interfering mechanisms discussed above, some
compounds can accelerate the breakdown of natural hormones, and it has
recently been established that some promote the conversion of male hor-
mones into female ones.
As a class, substances that interfere with the endocrine system of hor-
mone production and transmission are often referred to as environmental
estrogens (or ecoestrogens). More general names for this class of substances
have also been suggested: synthetic hormonally active agents (HAAs), endocrine
disrupting chemicals (EDCs), environmental hormones, and xenoestrogens.
The Chemicals That Operate as Environmental Estrogens

Although most ecoestrogens operate by attaching themselves to, or by
blocking access to, the hormone receptor, there is not a strong resemblance
in overall structure between synthetic substances that have been identified
as hormonally active and the natural sex hormones, nor is there much
structural similarity of the synthetic ones to each other. It is true that many
molecules identified as environmental estrogens contain one or more
hydroxyl groups, as does estrogen. Oxygen-containing organochlorine
insecticides that are known to act hormonally include methoxychlor and
kepone (Figure 12-2). However, other environmental estrogens are
organochlorine molecules, including some PCBs, dioxins, and insecticides
(Figure 12-2) that contain no oxygen atoms. In metabolizing them, how-
ever, the body itself attaches hydroxyl groups to some of the nonchlori-
nated carbon atoms in such molecules. Some of the resulting hydroxylated
organochlorines are more hormonally active agents than the original com-
pounds. The same is true with polycyclic aromatic hydrocarbons when they
are hydroxylated.
Most nonchlorinated environmental estrogens are alcohols, often with
the phenolic ring that is present in the steroidal hormones. Nonylphenol
(Figure 12-2) is one important example. Octylphenol (which has a C8 rather
than a C9 chain attached to the phenol ring) is even more hormonally active.
Both these alkylphenols occur in the environment—including drinking
water—as a result of the breakdown, e.g., in sewage treatment plants, of larger
ethoxylate molecules. The ethoxylates are used in detergents, spermicides,
paints, and some plastics. They are also commonly used as emulsifying
agents in pesticide formulations, and the nonylphenols produced by their
decomposition enter the food chain via sprayed fruits and vegetables. The
European Union is moving toward banning the use of ethoxylates, as Norway

has done already for applications for which alternatives exist.
Another phenolic environmental estrogen of concern is bisphenol-A
(Figure 12-2); the prefix bis means “two” and is used here to signify that two
phenol rings are connected together. It is a widely used substance that is poly-
merized industrially into the polycarbonate plastics employed as linings in
most food and beverage cans and in some epoxy resins. Bisphenol-A is a con-
troversial chemical, with very different views regarding its potential estrogenic
effects in humans being taken by the plastics industry and some of the scientists
whose research they support financially compared to those of some academic
scientists who have performed tests with the compound on animals.
Some bisphenol-A is leached if food containers made using the polymer-
ized resin are heated for sterilization purposes. The plastics industry states that
migration of bisphenol-A from plastic food containers does not occur under
normal cleaning and use conditions, although some consumer groups claim
evidence that some, albeit small, amount of leaching from polycarbonate plastics
such as baby bottles does occur. Although resins containing the compound are
used to line aluminum beer and soda cans, bisphenol-A apparently does not
leach from these containers. Bisphenol-A also could potentially leach from
dental sealants that are made from resins prepared from it, though the initial
evidence that this occurs is now in doubt. Urine testing indicates that the great
majority of Americans have been exposed to bisphenol-A, though most of it
ingested by humans is metabolized.
Another hormonally active diol is genistein, a molecule whose structure
(Figure 12-2) has similarities to that of estrogen. Genistein is produced natu-
rally by plants, rather than being a synthetic product. It is a member of a
group of natural chemicals called flavonoids. Genistein is found in significant
concentrations in wood products and in soybeans and soy-based food prod-
ucts. Researchers have discovered that genistein from pulp-mill effluent may
cause feminizing and other reproductive effects in fish that swim in the effluent-
fed waters. Both nonylphenol and genistein have been found to produce
effects at very low doses in test animals. It is not clear yet whether genistein
overall has a positive or a negative effect on human health. However, some
scientists are worried about the levels of genistein ingested by babies fed with
soy milk.
The PCB congeners commonly found in environmental samples and
identified recently by screening as showing some, albeit weak, estrogenic
activity all have at least one ortho chlorine atom.
Phthalate esters (Figure 12-2) are widely used as plasticizers in common
plastics such as polyvinyl chloride, PVC, from which they can leach into the
environment, since they are not chemically bonded to the polymer. They
have antiandrogenic action. An important example is di-2-ethylhexyl
phthalate, DEHP, which is present in many plastics found around the home,
including some used by children, where phalate plasticizers can constitute up
to 45% of the weight of the object. The presence of DEHP in plastic medical
devices such as intravenous PVC bags is also of concern since leakage of small
amounts the plasticizer into the patient occurs during medical procedures. In
the United States, neither DEHP nor other phthalates are used in food wrap
or food packaging.
The European Commission has banned the use of phthalate softeners in
PVC toys meant for children under three years of age, since such children
tend to suck and chew on these toys, particularly rattles and teethers, and
would thereby extract and ingest some of the phthalate esters. However, a sci-
entific panel convened by the U.S. Consumer Product Safety Commission
concluded that the most common plasticizer used in PVC toys, diisononyl
phthalate, does not pose a risk to humans.
The compounds discussed above are thought to be the most significant
environmental estrogens uncovered to date. However, the estrogenic proper-
ties of many synthetic substances is not yet known. The U.S. EPA in 1999
began an extensive process of screening potential endocrine disruptors.
Effects of Environmental Estrogens on Wildlife

The most devastating consequences of environmental estrogens commonly
are not observed in the mammals that originally ingest them. Rather, they
result from their transfer from the mother to the fetus or egg. Their presence
disrupts the hormone balance in the recipient and causes reproductive abnor-
malities or produces changes that can result in cancer when the offspring
grows to adulthood. During its development, the fetus is particularly sensitive
to fluctuations in hormone levels. For that reason, exposure to low levels of
natural or environmental hormones can result in physiological changes that
do not occur in adults who are exposed at the same levels.
The most famous example of the environmental effects of hormone-like
chemicals upon wildlife involves alligators in Lake Apopka, Florida. In 1980,
massive amounts of DDT and its analogs were spilled into the lake. In the
mid-1980s, Professor Louis Guilette, Jr., of the University of Florida at
Gainesville found that very few alligator eggs were hatching, and few hatch-
lings survived of those that were born, thereby threatening the future popula-
tion of the colony. Furthermore, the eggs that did hatch produced alligators
with abnormal reproductive systems, which therefore were unlikely them-
selves to be able to reproduce. The ratio of natural estrogen to the male sex
hormone testosterone was greatly elevated in the young alligators. Presum-
ably as a consequence, the penises of male alligators were reduced in size com-
pared to the norm. Apparently these effects were caused by DDE, the
metabolite of DDT, which has been found by research to inhibit binding of
male hormones to their receptor.
Another Florida-based example involves the nearly extinct Florida pan-
thers that live in the Everglades. Their reproductive difficulties may result
from the consumption of raccoons whose levels of DDE and other endocrine
disruptors are high as a consequence of their consumption of contaminated
fish. Some researchers have linked reproductive problems of birds in the
Great Lakes area, such as embryo mortality and deformities, to the hormonal
activity of pollutants such as PCBs and dioxins. Abnormalities in the repro-
duction and/or development of frogs, seals, polar bears, mollusks, and several
types of birds have been linked to exposure of the fetuses to endocrine
disrupting chemicals.
Test have revealed that the most estrogenic component of commercial
DDT is not the main (~75%) ingredient, the p,p
-DDT isomer (Chapter 10),
but is rather the minor (15–20%) o,p
-DDT isomer (Figure 12-2), which has
one of the ring chlorines in the ortho position and one in the para. Some sci-
entists have speculated that women who are directly exposed to o,p
-DDT by
spraying may be at much higher risk of subsequently developing breast cancer
than those in the developed world, whose main exposure now is through DDE
in their diets.
Research reported in 2002 and 2003 indicated that environmental con-
centrations, ppb levels, of the herbicide atrazine (Chapter 10) could modify
the balance of hormones in just-hatched frogs and thereby affect their
sexual development. The effect of atrazine was to increase the levels of an
enzyme that converts the male hormone testosterone to the female one,
estrogen. About 20% of the male tadpoles developed into hermaphrodites,
having both testes and ovaries. Because of this, atrazine may be contributing
to the worldwide decline in the amphibian population. This hormonal
action indicates yet another way, in addition to attaching to or blocking
a hormone receptor, that environmental chemicals could upset hormonal
balances. However, research reported from some other groups has failed
to duplicate the findings at very low atrazine concentrations, so the issue
of whether or not this is a significant environmental problem is as yet
unresolved.
Researchers have also found that both natural estrogen, secreted by
women as part of their monthly cycles, and the synthetic derivative used in
birth control pills are present in wastewater and sewage effluent, and can
cause feminization of males in some species of fish. Such feminization was
encountered in the 1990s in some British waterways and was initially blamed
on the presence of nonylphenol discharges in the water. A survey of estrogens
in coastal waters found much higher levels in shallow bays that receive input
from sewage than in the open oceans.
Effects of Environmental Estrogens on Humans

The areas of human health that are considered to be at potential risk from
exposure to environmental hormones are reproduction, neurobehavior,
immune function, and cancer.
Much of the human evidence concerning the possible effects of estro-

gen mimics on developing fetuses was obtained from the experience of
women who took the synthetic estrogen DES (diethylstilbestrol) in the
1948–1971 period to prevent miscarriage. Many of the daughters of these
women are sterile, and a small fraction of them have developed a rare vagi-
nal cancer, as a consequence of their prenatal exposure to DES. The male
offspring have an increased incidence of abnormalities in their sexual
organs, have decreased average sperm counts, and may have an increased
risk of testicular cancer as a consequence of this exposure, but their fertility
is not affected.
Although there is good evidence that high concentrations of environ-
mental estrogens have caused reproductive problems in wildlife and laboratory
animals, it is not certain that comparable effects occur in humans at levels to
which we are exposed. In the early 1990s, a connection between the rise in
environmental contamination by endocrine disruptors and an apparent
increase in certain male disorders of the reproductive system was postulated.
In particular, the decline in male sperm counts and quality, the increase in
the rate of testicular cancer, and the increase in incidence of male reproduc-
tive problems in newborns were cited. However, the changes in the frequency
of these problems found in some locations may not, in fact, be general phe-
nomena. Both sperm counts and testicular cancer rates vary significantly
between geographical regions, and the variations are neither worldwide nor
apparently closely linked to differences in pollution levels. Similarly, no clear
picture has emerged relating trends in exposure to environmental estrogens
to human fertility or the rates of spontaneous abortion, though an association
has been found between delayed conception and exposure to high concentra-
tions of environmental contaminants.
Perhaps the most dramatic effects of an environmental hormone on
human reproduction is the effect of dioxins and furans in influencing the
male:female sex ratio, i.e., the ratio—normally about 0.51—of boys to girls at
birth. Epidemiological evidence from the dioxin-exposed group in Seveso,
Italy, and from the Taiwanese PCB-poisoned-oil group (Chapter 11) indi-
cates that males who were exposed to high concentrations of dioxins, or to
furans, dioxins, and PCBs, respectively, during adolescence are in adulthood
much less likely to father boys than girls. Most studies of men exposed as
adults to high levels of dioxins did not show a similar result, and the same is
largely true for men who were over age 20 and for all females at the time of
the Taiwanese incident. However, research from Austria indicates that work-
ers occupationally exposed to TCDD when under 20 years of age later
fathered many more girls than boys, whereas initial dioxin exposure at a later
age had no effect on the sex ratio.
Thus it appears that exposure during puberty to environmental hor-
mones from the dioxin-furan-PCB family of compounds can have measur-
able lifelong effects on subsequent reproduction characteristics of human
males. Interestingly, higher-than-normal exposure of males to industrial

PCB mixtures through the diet can result in a higher male:female sex ratio,
perhaps because some PCB congeners exhibit estrogenic whereas others
exhibit antiestrogenic or androgenic behavior, the dominant effect
depending upon the ratio of one to the other. In addition to PCB con-
geners, particularly those having one ortho and two para chlorines, other
environmental compounds that have been found to interfere with the
androgen receptor include the common DDT metabolite p,p
-DDE and
the fungicide vinclozolin. Recent research indicates that environmental
estrogens in humans can affect sexual characteristics: Girls who were
exposed prenatally to high levels of DDE reach puberty on average almost
a full year before those with the lowest exposures. Boys were not affected
in this way.
The effects on neurological development of prenatal exposure to PCBs
cited in Chapter 11 may arise from disruption of thyroid hormones, but
further research is required to establish this connection more definitely.
Concern about human health effects from exposure to phthalates has
increased over the past few years. Of particular interest—and controversy—
has been research linking phthalate metabolite levels in new mothers to the
incomplete development of the sex organs in male infants born to them,
possibly due to prenatal exposure to phthalates. An expert panel convened
by the U.S. government found this research to be inconclusive and recom-
mended that it be repeated and expanded. A subsequent report linked
phthalate levels in human breast milk to abnormal levels of reproductive
hormones in infant boys.
Some researchers have postulated a connection between the increasing
exposure of the general population to endocrine disrupting chemicals and
the rising incidence of cancers at hormonally sensitive sites, including the
breast, the uterus, the testes, and the prostate gland. A recent review of the
medical literature concluded that “the overall strength of a causal associa-
tion is weak” between the two, although “there is not enough information
to completely reject the hypothesis” that endocrine disruptors could play
a role.
Some scientists discount any adverse health effects of synthetic chemi-
cals acting as environmental estrogens by pointing out that we all ingest
much greater quantities of plant-based estrogen mimics called phytoestro-
gens, including genistein. Common sources of these natural chemicals
include all soy products, broccoli, wheat, apples, and cherries. Indeed, there
is some evidence that phytoestrogens have a protective effect against some
types of cancers. It is true that phytoestrogens are quickly metabolized by the
body and perhaps do not survive long enough to exert effects on a developing
fetus, for example, whereas many synthetic environmental estrogens are
stored in body fat rather than being metabolized. However, the current aver-
age dioxin level in humans is less than an order of magnitude greater than the
Fractional response
FIGURE 12-3
Dose–response
Dose (logarithmic scale) curve (schematic) for
estrogen and its mimics.
lowest dose found by experiments to cause reproductive problems in the off-

spring of rats.
The greatest difficulty that scientists face in trying to discover whether
environmental estrogens affect human health significantly is the lack of
exposure data from the suspected substances. Thus, the jury is still out
regarding whether environmental estrogens pose a substantial threat to
humans or not.
Another puzzle in the environmental estrogen story relates to their
dose–response behavior. In contrast to most toxic substances for which the
response increases with the dose, eventually leveling off, the response curves
for action by estrogen and estrogen mimics have an inverted-U shape
(see Figure 12-3). The greatest effects are produced at low dosages; large
dosages shut down the responding system to some extent. For example, the
effects of atrazine on frogs are found by some researchers to operate only at
very low concentrations, not at higher levels.
As an added complication, some estrogenic compounds are found to
increase estrogenic activity in some tissues and block it in others! The rele-
vance of the findings discussed above and many other unanswered questions
in the environmental estrogen story will only be sorted out once much more
research is done in this fascinating new chapter concerning the effects of low
environmental levels of toxic organic chemicals upon living organisms.
The Long-Range Transport of

Atmospheric Pollutants
At first glance, it seems amazing to discover that relatively nonvolatile
organochlorines and PAHs can eventually travel thousands of kilometers by
air from their point of release and end up contaminating relatively pristine
areas of the world such as the Arctic. Some quantitative understanding of this
long-range transport of atmospheric pollutants (LRTAP) has been made
using principles of physical chemistry.
By a global fractionation (or distillation) process, pollutants travel at dif-
ferent rates and are deposited in different geographical regions depending upon
their physical properties. Most persistent organic pollutants have sufficient
volatility to evaporate—often rather slowly—at normal environmental tem-
peratures from their temporary locations at the surface of soil or water bodies.
However, because the vapor pressure of any chemical increases exponentially
with temperature, evaporation is favored in tropical and semitropical areas, so
these geographic regions are rarely the final resting places for pollutants. In con-
trast, cold air temperatures favor the condensation and adsorption of gaseous
compounds onto suspended atmospheric particles, most of which are subse-
quently deposited onto the Earth’s surface. Thus the Arctic and Antarctic
regions are the final resting places for relatively mobile pollutants that are not
deposited at lower latitudes because of their high volatility. Unfortunately,
these compounds degrade even more slowly in these regions because tempera-
tures there are so cold.
Example of pollutants that migrate to polar regions are the highly chlo-
rinated benzenes; PAHs having three rings; and PCBs, dioxins, and furans
that have only a few chlorines (see Table 12-2). Substances with even
greater volatility, such as naphthalene and the less chlorinated benzenes,
are not deposited even at the cold temperatures of polar regions; conse-
quently, they continue their worldwide travels more or less indefinitely until
they are chemically destroyed, usually by reaction initiated by the hydroxyl
radical.
As implied in Table 12-2, the mobility of a chemical increases as the
vapor pressure of its condensed form (as measured by that of the supercooled
liquid at 25°C) increases. In addition, mobility increases as the temperature
of condensation of the vapor form of the pollutant gas decreases. Thus, sub-
stances that do not condense until the temperature drops to - 30°C or lower
eventually accumulate in polar regions, where such air temperatures are
common. Substances having condensation temperatures below 50°C
remain airborne indefinitely, since not even polar regions sustain such tem-
peratures for long.
DDT is an intermediate case on these transport scales. It does evaporate
sufficiently rapidly (supercooled liquid vapor pressure is 0.005 pascals), but its
relatively high condensation temperature of 13°C (55°F) means that much of
it becomes permanently deposited at mid-latitudes (especially in the winter)
and only a small fraction of it migrates to the Arctic.
Although PCBs are predicted by the model to deposit mainly in temper-
ate areas rather than migrating en masse to the Arctic, the migration that
does occur is sufficient that animals there are quite contaminated by these
TABLE 12-2 Predicted Mobilities of Persistent Airborne Pollutants
Global Transport Low Relatively Relatively

Behavior Mobility Low Mobility High Mobility High Mobility
Property
Vapor pressure of 104 102 1
liquid at 25°C
in pascals*
Condensation 30°C 10°C 50°C
temperature
Examples
PAHs 4 rings 4 rings 3 rings 1 – 2 rings
Chlorobenzenes — — 5 – 6 Cl 0 – 4 Cl
PCBs 9 – 8 Cl 4 – 8 Cl 1 – 4 Cl 0 – 1 Cl
PCDDs/PCDFs 4 – 8 Cl 2 – 4 Cl 0 – 1 Cl —
Pesticide examples Mirex DDT HCB Moth balls

Toxaphene Dieldrin
Chlordane Hexachloro-
cyclohexane
Source: Adapted mainly from F. Wania and D. Mackay, “Tracking the Distribution of Persistent Organic Pollutants,”
Environmental Science and Technology 30 (1996): 390A – 396A.
*For the supercooled liquid.
chemicals. The world record for PCB contamination, 90 ppm, is held by polar
bears in Spitsbergen, Norway. Even breast milk is higher in PCBs for women
who live in far northern areas than in more temperate ones, a result partially
of their high-fat diet since organochlorines are known to accumulate in such
a medium.
P R O B L E M 12-5
DDE has a 25°C vapor pressure (for its supercooled liquid) of 0.0032 Pa and
a condensation temperature of 2°C. Is DDE more or less volatile than
DDT? Predict whether a larger or smaller fraction of the fraction that does
vaporize will be deposited at polar latitudes compared to DDT itself.
Owing to the variations in air temperature during their transport, most

molecules of mobile pollutants experience several successive cycles of evapo-
ration and condensation as they migrate gradually toward colder climates.
t1 t6
t2
Amount
t3
FIGURE 12-4 Calculated
t5
variation with time in the t4
geographic distribution
of an airborne pollutant
released at the Equator (EQ).
[Source: F. Wania and
D. Mackay, “Tracking the Tropic Subtropic Temperate Subpolar Polar
EQ Latitude
Distribution of an Airborne
Emission pulse
Pollutant,” Environmental
at time t0
Science and Technology 30
(1996): 390A.]
This “grasshopper effect” is illustrated in Figure 12-4 for a pulse of a relatively

mobile pollutant that was emitted near the Equator at time t0. At a later
time t1, the majority of the pollutant mass is still present in tropical regions,
but at a subsequent time t2 it has moved mainly to the subtropics. Whether
it eventually ever moves (“hops”) from temperate and subpolar regions to
polar ones (at a later time t6) depends upon whether or not its mobility is
sufficiently high.
Brominated Fire Retardants

Highly brominated organic compounds are common commercial fire retardants.
Large amounts of these fire retardants are used worldwide, and because of
their persistence, they now are accumulating in the environment and have
even been detected in the Arctic, to which they presumably migrated by the
LRTAP mechanism discussed above. Based upon animal studies, they may
have potential for liver toxicity, thyroid hormone-level disruption, and repro-
duction and development effects.
Many brominated organic compounds function as fire retardants because,
when heated to 200–300°C—the approximate temperature range in which
many polymers begin to decompose—they release free bromine atoms, which
react with the free radicals of combustion and thereby quench any fire. For
example, when a molecule of such a compound has absorbed sufficient energy
from the fire and released Br atoms from one or more of its C¬Br bonds, the
atom may react with one of the free H atoms associated with the free-radical
mechanism of combustion:
H Br 9: HBr
The hydrogen bromide, HBr, molecule so formed may subsequently react

with a free hydroxyl radical, which otherwise would also have continued to
propagate the combustion:
OH HBr 9: H2O Br
The net reaction of these two steps is the formation of a water molecule by
the reaction of H and OH, thereby reducing the concentration of highly
reactive free radicals.
In this way, energy is withdrawn from the propagation mechanism of the
combustion process, and the fire is quenched. The decomposition tempera-
ture of brominated fire retardants lies just below those of the polymers that
they protect.
Iodine organic compounds would be even more effective in withdrawing
energy, but since the C¬I bond is so weak, they decompose at too low a
temperature. Fluorinated compounds are generally unsuitable as fire retar-
dants because most C¬F bonds are so strong that free fluorine atoms would
not be released and because, once formed, HF molecules are so stable that
they would not participate in further reaction.
PBDEs: A New Persistent Pollutant

Brominated diphenyl ethers, especially at levels of 5–30%, are incorporated
into polyurethane foam, textiles, ready-made plastic products, and certain
electronic equipment to prevent them from ever catching on fire. They are
found in common domestic products such as carpet padding, mattresses, cur-
tains, and upholstered couches and chairs.
From a conceptual viewpoint, the molecular structure of diphenyl ether
is analogous to biphenyl, except that an ether oxygen atom joins the two ben-
zene rings. Bromine atoms can occupy any of the 10 other positions on the
rings, analogous to the chlorine atoms in PCBs, again giving 209 possible
congeners. Molecules with fewer than four bromines are generally not present
in commercial mixtures.
Br Br
O O Br
diphenyl ether Br Br
a PBDE
As a class, these compounds are known as polybrominated diphenyl ethers,

PBDEs.
PBDE molecules are of particular environmental concern because some

migration of them has occurred from their commercial products into the
environment, where they now are widely distributed. Like PCBs, they are
persistent and lipophilic, they bioaccumulate, and some of them are toxic.
PBDEs have been detected in U.S. sewage sludge (much of it destined to be
spread on agricultural land), in some fish caught in the wild, and even in
sperm whales, which normally feed only in deep ocean waters. Also like
PCBs, the commercial products are mixtures of congeners, not pure com-
pounds, although the number of congeners present in each product is rela-
tively small. Unlike most PCBs, PBDEs are solids under ambient conditions
rather than liquids.
The acute toxicity of PBDEs decreases as the number of bromines per
molecule increases. Consequently, the least toxic PBDE is the fully bromi-
nated congener decabromodiphenyl ether. It is the almost exclusive ingre-
dient ( 97%) in Deca, the commercial mixture that is the predominant
PBDE product on the market and that is used as the flame retardant in plas-
tic components in computers and TV housings. Some scientists suspect
that the PBDEs in Deca, while not themselves highly toxic, may degrade in
the environment by loss of some bromine, thereby increasing the toxicity
of the mixture, since PBDEs having intermediate bromine content are
more toxic than is decabromodiphenyl ether. Indeed, there is growing evi-
dence that Deca can undergo debromination by photochemical decompo-
sition in sunlight; by reduction with elemental iron; and by metabolic
processes in fish, such as carp and rainbow trout, and in rats. It is also
debrominated anaerobically in sewage sludge if certain other chemicals are
also present.
P R O B L E M 12-6
Deduce the structures of (a) the three unique PBDEs formed by loss of one
bromine atom, and (b) the twelve PBDEs formed by loss of two bromine
atoms, from a molecule of decabromodiphenyl ether. Assume that the two
rings cannot rotate relative to each other around the intermediate
oxygen atom.
The product called Penta is a mixture mainly of PBDEs having four or

five bromine atoms. It was used as a fire retardant in polyurethane foams,
such as those used in furniture upholstery and padding in vehicles. The
Penta mixture constitutes up to 30% by mass of some polyurethane foams,
products that easily deteriorate by outdoor weathering and break into small,
easily transportable fragments that can eventually find their way into natu-
ral waters. From this source, PBDE molecules can enter the aquatic food
chain. Indeed, it is tetra- and pentabromodiphenyl ethers that are most

widely distributed in the environment and that are the most bioaccumula-
tive and the most toxic. The commercial PBDE product called Octa, which
consists mainly of congeners with six or seven bromine atoms, is used in
thermoplastics.
PBDEs with a large amount of bromine (more than six Br atoms per mole-
cule) probably do not bioaccumulate because they are not readily incorpo-
rated by organisms; instead they bind to particles and accumulate in
sediments. However, congeners with four to six bromines are taken up by
organisms and have the potential to biomagnify in the food chain. They may
in the future represent a danger to human health due to our exposure to them
in food, especially fish.
Although some human exposure to PBDEs occurs through the food we
eat, inadvertent digestion of household dust appears to be an even more
important source, especially in North America. The difference in exposure to
this source may account for the higher blood levels of PBDEs found in Amer-
icans and Canadians compared to Europeans. One recent small-scale study
found a definitive link between PBDE levels in human breast milk and their
levels in the dust of the women’s homes.
The concentrations of PBDEs in human blood, milk, and tissues had
risen exponentially for three decades, until at least the early 2000s, with a
doubling time of about five years. Though few data are available, the con-
centration of PBDEs in human breast milk is known to have risen sharply
in the 1990s in both U.S. and Canadian women—by more than a factor of
10 from 1982 to 2002 for the latter—and is approaching that of PCBs,
though the levels in milk samples from European women are much lower.
The main human health concern is that PBDEs having relatively few
bromine atoms may affect hormone and liver systems and interfere with
neurodevelopment.
P R O B L E M 12-7
The concentration of PBDEs in herring gull eggs from the Great Lakes was
about 1100 ppb in 1990 and about 7000 ppm in 2000. What is the doubling
time for the PBDEs in this source? If past trends continue, what will be the
concentration in 2010? [Hint: For exponential growth Aekt, the doubling time is
equal to 0.69/k.]
Because of environmental concerns, the European Union banned the

Penta and Octa products in 2006. The sole North American manufacturer of
Penta and Octa voluntarily ceased production of these products at the end of
2004. However, the Deca product is still available and widely used in Europe
and North America, though there is much controversy within the European
Union concerning whether or not it should be banned. The argument against
banning brominated fire retardants is that they are vital in reducing losses of
human lives and of property in fires.
Other Brominated Fire Retardants

Two non-PBDE brominated organic compounds are also widely used as fire
retardants. Indeed, the retardant of largest usage volume of all is TBBPA,
tetrabromobisphenol-A, a compound composed of molecules in which all
four carbon atoms that stand ortho to the two hydroxyl groups of bisphenol-
A (see Figure 12-2) have been brominated:
Br Br
CH3
HO C OH
CH3
Br Br
TBBPA
Commonly, TBBPA is incorporated chemically into the structure of polymers

by covalent coupling at the two hydroxyl groups; retardants that are cova-
lently bonded to polymers are called reactive ones. Printed circuit boards are a
major reactive use for TBBPA. When incorporated into materials in this man-
ner, retardants are much less likely to leach or volatilize into the environment
compared to those such as PBDEs, which are only physically dissolved in
materials and are called additive substances. In some products, however,
TBBPA is used as an additive rather than a reactive retardant. The compound
itself is not very toxic (its LD50 is several grams per kilogram), and although it
has been found in some biota, it decomposes in air, water, and sediment in
weeks or a few months.
The other important brominated fire retardant is the half-brominated
cyclic hydrocarbon hexabromocyclododecane, HBCD, which is used prima-
rily as an additive in polystyrene foams used in building materials and uphol-
stery, though it is also finding new applications in replacing PBDEs. It is not
used as a reactive retardant, since it contains no reactive groups that can
bond to the polymer chain. Like TBBPA, it is of low acute toxicity. How-
ever, it is now a ubiquitous contaminant in the environment, and it undergoes
biomagnification in top predators such as birds of prey and marine mammals.
To date, it has been detected only in much lower levels in humans. Its envi-
ronmental levels in Europe are higher than those in North America, owing
to its greater use there.
Perfluorinated Sulfonates 533
P R O B L E M 12-8
Draw the structure of HBCD, given that its name is 1,2,5,6,9,10-hexabromo-
cyclododecane. Then, knowing that Br2 molecules will add across C" C
bonds, deduce the structure of the cyclic triene that could be brominated to
produce HBCD. [Hint: Dodeca means “twelve.”]
Polybrominated biphenyls, PBBs, were also used as fire retardants but are
now banned in some countries, including the United States. A 1973 industrial
accident in Michigan resulted in the widespread contamination of the food
supply there with PBBs.
Perfluorinated Sulfonates
All the organic compounds discussed previously in this chapter act either as
hydrophobic (water-repelling) or as oleophobic (oil-repelling) substances, but
not as both. There exists a small class of organic compounds that will dissolve
in neither of these classes. Fluorinated surfactants are compounds that con-
sist of molecules and ions having a long perfluorinated carbon tail; i.e., a
hydrocarbon chain in which each hydrogen atom has been replaced by a flu-
orine atom. The best-known example of such a molecule is perfluorooctane
sulfonate (PFOS):
CF3(CF2)7 9 S 9 OH
O
Notice the similarity in its structure to that of sulfuric acid: One ¬ OH group
in the latter has been replaced by an unbranched, perfluorinated eight-carbon
octane chain. This substance was used to make the 3M product Scotchgard,
a fabric protector that, because of the characteristics of the perfluoro chain,
repelled both water and oily spills and potential stains. Other compounds
based upon PFOS were used in fire-fighting foams, pesticide formulations,
cosmetics, lubricants, grease-resistant coatings for paper products, adhesives,
and paints and polishes.
The 3M company has voluntarily phased out the production of PFOS
because it persists long enough in the environment to eventually be detected
in human blood samples. Although it is not very toxic, its concentration in
some wildlife had reached levels of concern to some scientists. Since 2003,
3M has used the corresponding perfluorosulfonate having a chain of only
four, rather than eight, carbon atoms, since such chains do not seem to either
bioaccumulate or be toxic.
The fully fluorinated eight-carbon carboxylic acid compound perfluorooc-

tanoic acid, PFOA (CF3(CF2)6COOH), and its associated carboxylate salts
have also become of environmental concern since they have no environmental
or metabolic degradation pathways. Indeed, the very lack of reactivity that
makes perfluorinated compounds so appealing in practical uses also results in
their persistence in the environment. Although its lifetime in rats is only
several hours, PFOA is only slowly eliminated in humans, resulting in an
average lifetime of about four years. Due to its slow elimination, the acid is
now found at the parts-per-billion level in the blood of most humans and wild
animals worldwide. It is potentially acutely toxic, potentially carcinogenic,
and may cause developmental problems. Human exposure to PFOA results
from its use in producing polymers used to coat surfaces of nonstick cookware,
including frying pans, as well as for the membranes of breathable outdoor
garments. Fully fluorinated carbon chains are added by covalent bonds to
polymer chains in order to make the materials stain-resistant. PFOA has been
detected in samples of drinking water in several U.S. states; there is no fed-
eral standard for it. In 2006, the U.S. EPA announced a voluntary program,
requesting companies using PFOA in consumer products to stop using the
compound.
PFOA is the most prominent member of the family of perfluoroalkyl
acids, PFAAs. In general, the longer the carbon chain in such molecules, the
more persistent is the acid in the human body. 3M is formulating products that
use PFAAs with relatively short chains in order to overcome the persistence
problems of eight-carbon-chain substances.
PFOA and similar compounds are now found even in remote regions
such as the Arctic, being transported there by LRTAP. Apparently such
PFOA results from the atmospheric reaction of fluorotelomer alcohols,
CF3(CF2)nCH2CH2OH, industrial compounds that are used to make stain
repellants. Unfortunately, a small fraction of the alcohols are released
inadvertently into the atmosphere during the manufacturing process. In addi-
tion, the very small concentration of the reactant that was not converted into
a repellant but was instead weakly incorporated into the material slowly
degasses from it, adding to the atmospheric load of the alcohol.
In air, the fluorotelomer alcohols are converted to the carboxylic acids by
a chain reaction that begins when a hydroxyl radical, OH, in air abstracts a
hydrogen atom from the ¬CH2¬ group bonded to OH. This process initiates
a sequence of free-radical reactions, the net result of which is the oxidation
of the terminal ¬CH2CH2OH group to COOH, producing the final
perfluorocarboxylic acid, CF3(CF2)nCOOH. It is also thought that microbial
action and animal metabolism play a role in converting the alcohols to acids.
Fluorotelomer alcohols have become the main remaining source of PFOA
in the environment. In 2006, the Canadian government proposed to ban
fluorotelomer polymers that can decompose into long-chain perfluorinated
carboxylic acids.
Review Questions
1. What does PAH stand for? Draw the structures 7. What does LRTAP stand for?
of two examples.
8. Which three physical properties are used to
2. In what processes are PAHs commonly formed? predict the ultimate deposition zone of volatile
chemicals?
3. By means of a structural diagram, show what is
meant by the bay region present in certain PAHs. 9. What does PBDE stand for? Draw the structure
How is the presence of this region related to the of any PBDE. What are some of the uses of this
health effects of PAHs? class of compound?
4. Define the term environmental estrogen. Give 10. Draw the structure of a perfluorinated sulfonate.
two chloroorganic and two nonchloroorganic What are such substances used for?
examples.
11. What do PFOA and PFFA stand for? What is
5. Recount some of the evidence that environmen- the molecular structure of PFOA? What is meant
tal estrogens affect the health of wildlife and of by the term fluorotelomer alcohol? What are such
humans. alcohols used for?
6. What is a phytoestrogen?
Additional Problems
1. In an experiment, the level of benzo[a]pyrene in (b) What does 1.52 ng/g translate to on a “parts-per”
hamburgers was found to depend significantly on scale?
the cooking method and cooking time. For oven- (c) How many micrograms of benzo[a]pyrene
broiled hamburgers, levels of 0.01 ng/g were found would be ingested in the consumption of a typical
for both medium and very-well-done burgers. For “quarter pounder” hamburger if it was barbecued to
barbecued burgers, levels of 0.09 and 1.52 ng/g were the very-well-done stage and there was no loss in
found for medium and very-well-done burgers, mass during its cooking?
respectively.
2. Which octabromo diphenylether isomers identi-
(a) Explain the observed difference in
fied in Problem 12-6b would not correspond to iso-
benzo[a]pyrene formation by the two cooking
latable compounds if free rotation were to exist
methods, and explain the difference in medium
about the C¬ O bonds?
versus very-well-done barbecued burgers.
Further Readings
1. C. Maczka et al., “Evaluating Impacts of Implications,” Canadian Medical Association
Hormonally Active Agents in the Environment,” Journal 163 (2000): 1471; S. H. Safe, “Endocrine
Environmental Science and Technology (1 March Disruptors and Human Health: Is There a
2000): 136A; G. M. Solomon and T. Schletter, Problem?” Environmental Health Perspectives 108
“Environment and Health: 6. Endocrine (2000): 487.
Disruption and Potential Human Health
2. P. H. Jongbloet et al., “Where the Boys Aren’t: and Toxicology,” Environmental Health Perspectives
Dioxin and the Sex Ratio,” Environmental Health 109 (supplement 1) (2001): 49.
Perspectives 110 (2002): 1.
5. R. Renner, “The Long and Short of Perfluorinated
3. World Health Organization, “Global Assessment Replacements,” Environmental Science and Technology
of the State-of-the-Science of Endocrine Disruptors” 40 (2006): 12.
(2007): available at www.who.int/ipcs/publications/
6. K. S. Betts, “Perfluoroalkyl Acids: What Is
new_issues/endocrine_disruptors/en/
the Evidence Telling Us?” Environmental Health
4. P. A. Darnreud et al., “Polybrominated Perspectives 115 (2007): A250.
Diphenyl Ethers: Occurrence, Dietary Exposure,
Electron Capture Detection of Pesticides 537
Environmental Electron Capture Detection

Instrumental
Analysis III
of Pesticides
Chlorine-containing organic compounds of the exit the column, they enter the ECD and are
type that have been discussed in the preceding detected.
chapters usually occur in the environment at very The principle upon which the ECD works
small concentrations, but they can be detected and involves the disruption of a detector’s elec-
quantified by techniques such as the one discussed tronic standing current by the arrival in the
in this box. ECD of an analyte containing electron-loving
(electrophilic) atoms such as halogens, which
he widespread occurrence of pesticides in is the basis for the ECD signal. The standing
T the environment makes their detection
an important task, but their often-low con-
current is generated by a piece of radioactive
nickel-63 fixed on the wall of the detection
centration makes this job difficult. One of chamber. This unstable element (half-life
the solutions to detecting very small amounts 92 years) continuously emits beta particles
of environmentally important chemicals is to (␤ particles, high-energy electrons from nuclear
use very sensitive chromatographic detectors. decay, as described in Chapter 9) at a rela-
In the case of methane, this is accomplished tively constant rate. The GC carrier gas used
with the flame ionization detector (see Envi- in this analysis is usually a mixture of helium
ronmental Instrumental Analysis Box II). and a small amount (say, 5%) of another
The most common gas chromatographic volatile compound, such as methane, at a con-
(GC) detector used for halogen-containing stant concentration. Because the carrier gas
pesticides is the electron capture detector mixture is homogeneous, a constant ratio of
(ECD). Since many important pesticides con- helium and CH4 flows into the ECD. The flow
tain chlorine, a detector system that responds of ␤ particles from 63Ni collides with some of
to molecules that contain this element is the the methane molecules in the carrier gas and
key to sensitive biospheric analysis. Examples create a “cloud” of slow (or thermal) electrons
of target chlorinated pesticides are DDT (and in the detection chamber. This cloud creates
its breakdown product DDE), lindane, and an electrical potential between the two
chlordane. The only chlorine-containing com- electrodes placed in the detection chamber;
pounds unsuitable for this technique are those the resultant current is amplified and sent to
whose high boiling points make them unsuit- the computer (or integrator). Since this con-
able for gas chromatographic analysis. stant standing current is present whenever the
The electron capture detector, like all GC detector is on and the carrier gas is flowing,
detectors, is located at the end of the chro- the computer receives a constant detector sig-
matographic column (see Environmental nal. The figure on the top of next page shows
Instrumental Analysis Box II) located in a the major components of the ECD.
temperature-controlled (and programmable) The ECD’s standing current changes when
oven. When analytes (compounds that have an analyte arrives in the ECD from the end
been separated by the chromatographic process) of the GC column after chromatographic
538 Environmental Instrumental Analysis III
Environmental Electron Capture Detection

Instrumental
Analysis III
of Pesticides (continued)
brasiliensis). These animals absorb

63Ni
DDT and DDE from their diet of
source
insects that have been exposed to
Waste/ e e e ee e Analyte DDT in the environment. Although
trap e e e e e e the DDT content of the bats is very
e e e ee e ee
e low, the breakdown product p,p
-DDE
Electrodes
remains detectable. The figure below
GC column shows two (superimposed) chromato-
Computer entrance grams resulting from ECD analysis of
carcasses of female bats collected
from two southwestern U.S. caves,
separation: Target compounds decrease the Carlsbad Caverns, New Mexico, and
standing current because some of the electrons Vickery Cave, Oklahoma (Thies and McBee,
are captured by electrophilic atoms that are 1994). Although no DDT itself was detected in
present in the analyte. The more of the com- either animal, the DDE content of the bat car-
pound that arrives, the larger the decrease in cass (all tissue except brain and intestines) from
current. The computer measures the amount of Vickery Cave was approximately 41.9 mg DDE
this decrease and correlates detector signal with per gram of total fat.
analyte concentration; however, unlike the Seabirds collected in the Barent Sea (in
positive FID signal (in which more analyte the Arctic, above 75°N) have also been ana-
means more signal), the ECD signal is “upside lyzed using this instrument. A number of chlo-
down”—its information is a measure of missing rinated pesticides were determined for two
signal. The result is, however, the same: The bird species whose diets were known to consist
amount of each target analyte can be
sensitively and reproducibly deter-
mined by the ECD. Furthermore, like 2.0
ECD response (current decrease)
DDE
other chromatographic systems, the Vickery Cave,
Oklahoma
time that each compound exits the 1.5 Carlsbad Caverns,
column and generates the detector New Mexico
signal can be used as a means of iden-
tification if other analyses and chemi- 1.0
Solvent
cal standards are used. Internal
Among many other applications, 0.5 standard
the ECD has been used to measure
the presence and amount of DDT 0
and the related substance DDE 0 2 4 6 8 10 12 14 16
(Chapter 10) in the tissue of Time (minutes)
Mexican free-tailed bats (Tadarida
Electron Capture Detection of Pesticides 539
Artic bird species

Black guillemot
Kittiwake
0 20 40 60 80
Mean contribution to total chlorinated pesticides and metabolites
HCB b -HCH oxychlordane cis-chlordane
trans-nonachlor p,p′-DDE Mirex
entirely of polar codfish. DDT’s metabolite with the DDT metabolite DDE. But for two
DDE was again found, along with six or seven other bird species examined, DDE was very
chlorinated pesticides. The mean DDE slowly eliminated and, in fact, is bioaccumulat-
concentrations were 608 (43) ppb for Black ing in relation to the PCB-153 standard in
guillemot and 1168 (231) ppb for Kittiwake, those species. This result means that the bio-
expressed as mass of DDE per mass of bird lipid transformation of chlorinated compounds is
(Borga et al., 2007). The figure above shows highly bird-species-specific.
the mean distribution of seven chlorinated
compounds examined using this method. References: K. Borga, H. Hop, J. U. Skaare, H. Wolkers,
By comparing the ratio of the concentra- and G. W. Gabrielsen, “Selective Bioaccumulation of
tion (in these birds’ fat) of a specific chlorinated Chlorinated Pesticides and Metabolites in Artic
Seabirds,” Environmental Pollution, 145 (2007):
pesticide such as cis-chlordane to that of a 545–553.
highly bioaccumulated polychlorinated biphenyl
(PCB 153), workers have been able to deter- M. L. Thies and K. McBee, “Cross-Placental Transfer
of Organochlorine Pesticides in Mexican Free-Tailed
mine a relative measure of bioaccumulation for Bats from Oklahoma and New Mexico,” Archives
the chlorinated pesticides and metabolites of Environmental Contamination and Toxicology 27
examined. In comparing the bird species Black (1994): 239–242.
guillemot and Kittiwake, cis-chlordane was bet- Chemistry-Based Animations, 2006. http://www.shsu
ter eliminated by both species when compared .edu/~chm_tgc/sounds/sound.html.
540 Environmental Instrumental Analysis IV
Environmental Gas Chromatography/Mass

Instrumental
Analysis IV
Spectrometry (GC/MS)
Analytical identification of volatile compounds example of ionization is the formation of

in samples taken from the environment often CH4 cations from methane molecules. This
relies on this extremely powerful technique. The ion has a charge of 1 and a mass of 16,
heart of this method is mass spectrometry, a giving a mass/charge (m/z) ratio of 16.
method of identifying molecules by their unique After their formation, the ions are sepa-
“fingerprints.” rated from one another according to their m/z
ratio in the mass analyzer and then enter the
s we saw in our discussion concerning mass detector. In the figure on the top of next
A FID identification (page 537), gas chro-
matography (GC) is a very powerful tool for
page, depicting a 70-electron-volt ionization
source, the GC column effluent enters on the
separating the components of a mixture. In right, ionization occurs where the stream of
identifying the structure of individual com- electrons cross its path, and ionized frag-
pounds in a separated mixture, one of the most ments are accelerated by the charged plates
powerful gas chromatography detectors is the and exit from the ionization chamber and
mass spectrometer (MS); it is one the few GC into the mass analyzer on the left. The inten-
detectors whose analytical signals actually sity of the mass detector’s signal versus m/z is
probe the structure and elemental composi- recorded in each mass spectral scan, the mass
tion of the molecules it analyzes. Since the MS spectrum.
can be used as a stand-alone analytical tool, The chromatographic plot for GC/MS is
the combination of GC and MS is called a called the total ion chromatogram; it displays
“hyphenated technique”: gas chromatography/ the total ion current on the y axis versus time
mass spectrometry, GC/MS. on the x axis. The individual peaks correspond
Like the FID and ECD, the mass spectro- to different compounds in the mixture that
metric detector is positioned at the end of the were separated by the GC. This plot is compa-
gas chromatographic column and analyzes com- rable to the FID’s chromatogram, which has
pounds one by one, as they exit the GC column the FID signal on the y axis and time on the
in the gas phase. The MS can be divided into x axis. (In contrast to GC/MS, the FID tech-
three parts: the ionization/fragmentation source, nique requires chemical standards—known
the mass analyzer, and the mass detector. compounds—whose retention-time data can
As the molecules enter the low-pressure be compared to the unknown compounds for
ionization/fragmentation chamber of the mass identification purposes.) In the figure on the
spectrometer, they are bombarded with high- bottom of next page, the ionization source has
energy electrons, which causes many of the been miniaturized and shown above and feed-
molecules to lose an electron, to form free- ing molecular fragments to the quadrupole
radical cations. Only charged molecular frag- mass analyzer. The mass detector is shown
ments are accelerated from there to the mass below the mass analyzer. An example of a
analyzer; all un-ionized particles are sucked GC/MS total ion chromatogram is shown at
out, by the vacuum system, to waste. A simple the right in the figure.
Gas Chromatography/Mass Spectrometry (GC/MS) 541
High-voltage source
To vacuum Heated filament

(electron source)
~10–3 to 10–6 torr H H H
e– e– e–
H C C
C +
H e–
To C H H e–
e–
mass H H H H e–
e–
analyzer H C C + e–
C
H H
e–
e–
Column
H H from GC via
Charged slits/plates accelerate and focus ions transfer line
Anode
(+70-V bias)
Mass analyzer
(quadrupole)
e e–
e –e–
e –e––
e –e
–
– –e
e e
H H
+
–
C
H
H
H
+
C
C
C
H
H
H
H
H
H
H
H
cuum
C
Total ion chromatogram

C
H
H
H
a
torr
To v
–3
~10
Rf
Total ion current
e sl it
Entranc
DC Scannable
quadrupole
Time
slit
To Exit
vacuum s
Mas r
e t e cto
10–6 to 10–8 torr D
542 Environmental Instrumental Analysis IV
Environmental Gas Chromatography/Mass

Instrumental
Analysis IV
Spectrometry (GC/MS) (continued)
The CH4 species that is generated from fragmentation pattern is compared to a library
methane is know as the molecular (M) or par- of GC/MS patterns from known molecules.
ent ion; from its m/z ratio of 16, one can deter- For instance, the mass spectral frag-
mine the molecular weight of the molecule, a mentation patterns of two chlorinated phenol
parameter that would aid in the identification isomers—which, of course, have the same
of this compound if it were an unknown. molecular weight—can be used to differentiate
Because the electrons that impact the mole- between them. For example, although 2,3,4
cules have more than enough energy to cause trichlorophenol and 2,4,5 trichlorophenol have
the formation of the molecular ions, some of vanishingly small differences in boiling point
them generally break down by cleavage of and other physical properties, their electron
bonds to form fragment ions having lower m/z impact mass spectra are significantly different
ratios. In the case of CH4, since there are only since to some extent they fragment differently,
C¬H bonds, the fragmentation pattern is and therefore they can be used to discriminate
very simple, producing CH3 (m/z 15), between these two isomers. Databases containing
CH2 (14), CH (13), and finally C (12). electron impact mass spectra are available free
Such fragmentation patterns yield more infor- online (NIST, 2005) and are for sale from GC/MS
mation about the molecular structure of the instrument manufacturers.
parent compound; its structural formula can The figure below shows the mass spec-
often then be identified, particularly when the trum, reconstructed from data in the NIST
100
C14H6Cl2+
80
C14H8Cl4+
60
Intensity
40
C14H8+
20
0
0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340
m/Z
Gas Chromatography/Mass Spectrometry (GC/MS) 543
database, for p,p

-DDE, the environmental such as o,p
-DDE, would have different rela-
breakdown product of p,p
-DDT. The formu- tive intensities of the ion peaks.
las corresponding to the three most intense
References: Chemistry-Based Animations, 2006. http://
mass spectral peaks in the DDE mass spectrum www.shsu.edu/~chm_tgc/sounds/sound.html.
are shown above their appropriate m/z values.
P. Janos and P. Aczel, “Ion Chromatographic Separa-
The C14H8Cl4 peak corresponds to the par- tion of Selenate and Selenite Using a Polyanionic
ent ion, whereas the other two labeled peaks Eluent,” Journal of Chromatography A 749 (1996):
correspond to fragment ions formed by the loss 115–122.
of two or of all four chlorine atoms. The frag- NIST Chemistry WebBook, 2005. http://webbook.nist
mentation pattern for other DDE isomers, .gov/chemistry.
Tackling Mal
Interventions available today
could lead to decisive gains in
prevention and treatment—if only
the world would apply them
By Claire Panosian Dunavan
Claire Panosian Dunavan, “Tackling Malaria,”
Scientific American, December 2005, 76–83.
Long ago in the Gambia, West Africa, a two-year-old boy named

Ebrahim almost died of malaria. Decades later Dr. Ebrahim Samba
is still reminded of the fact when he looks in a mirror. That is
because his mother—who had already buried several children by
the time he got sick—scored his face in a last-ditch effort to save his
life. The boy not only survived but eventually became one of the
most well-known leaders in Africa: Regional Director of the World
Health Organization.
Needless to say, scarification is not what rescued Ebrahim
Samba. The question is, What did? Was it the particular strain of
parasite in his blood that day, his individual genetic or immuno-
logical makeup, his nutritional state? After centuries of fighting
malaria—and conquering it in much of the world—it is amazing
what we still do not know about the ancient scourge, including
what determines life and death in severely ill children in its clutch-
es. Despite such lingering questions, however, today we stand on
the threshold of hope. Investigators are studying malaria survivors
and tracking many other leads in efforts to develop vaccines. Most
PHOTOGRAPH BY RANDY HARRIS; PHOTOILLUSTRATION BY JEN CHRISTIANSEN
important, proven weapons—principally, insecticide-treated bed

nets, other antimosquito strategies, and new combination drugs
featuring an ancient Chinese herb—are moving to the front lines.
In the coming years the world will need all the malaria weapons it
can muster. After all, malaria not only kills, it holds back human and
economic development. Tackling it is now an international imperative.
A Villain in Africa
aria
FOUR PRINCIPAL SPECIES of the genus Plasmodium, the parasite that caus-
es malaria, can infect humans, and at least one of them still plagues
BITE OF INFECTED MOSQUITO begins the deadly cycle of malaria—a disease that
kills one million to two million people annually, mainly young children in
sub-Saharan Africa.
546 Tackling Malaria
every continent save Antarctica disease’s trademark fever and stream infection. Furthermore,
to a lesser or greater degree. Today, chills are followed by dizzying experts believe that antibodies
however, sub-Saharan Africa is not anemia, seizures and coma, heart and immune cells that build up
only the largest remaining sanctu- and lung failure—and death. over time eventually protect many
ary of P. falciparum—the most Those who survive can suffer Africans from malaria’s overt
lethal species infecting humans— mental or physical handicaps or wrath. Ebrahim Samba is a real-life
but the home of Anopheles gam- chronic debilitation. Then there example of this transformed state
biae, the most aggressive of the are people like Ebrahim Samba, following repeated infection;
more than 60 mosquito species who come through their acute after his early brush with death,
that transmit malaria to peo- illness with no residual effects. In he had no further malaria crises
ple. Every year 500 million 2002, at a major malaria confer- and to this day uses no preventive
falciparum infections befall ence in Tanzania where I met the measures to stave off new attacks.
(As a tropical medicine
doctor, all I can say is:
Don’t try this on safari,
Malaria not only kills, it holds back human folks, unless you, too,
and economic development. grew up immunized by
hundreds of malarial
mosquitoes every year.)
Africans, leaving one million to surgeon-turned-public health Samba’s story also has another
two million dead—mainly chil- leader, this paradox was still puz- lesson in it. It affirms the hope
dren. Moreover, within heavily zling researchers more than half a that certain vaccines might one
hit areas, malaria and its compli- century after Samba’s personal day mimic the protection that
cations may account for 30 to 50 clash with the disease. arises naturally in people like
percent of inpatient admissions That is not to say we have him, thereby lessening malaria-
and up to 50 percent of outpa- learned nothing in the interim related deaths and complications
tient visits. regarding inborn and acquired in endemic regions. A different
The clinical picture of falci- defenses against malaria. We now malaria vaccine might work by
parum malaria, whether in chil- know, for example, that inherited blocking infection altogether
dren or adults, is not pretty. In hemoglobin disorders such as (for a short time, at least) in vis-
the worst-case scenario, the sickle cell anemia can limit blood- itors such as travelers, aid work-
ers or military peacekeepers,
whose need for protection is less
Overview/Where We Stand Today prolonged.
■ Researchers are laboring to create vaccines that would pre-
On the other hand, the
vent malaria or lessen its severity. promise of vaccines should not be
■ But existing interventions could fight the disease now. They
overstated. Because malaria para-
include insecticide-treated bed nets, indoor spraying and new sites are far more complex than
combination drugs based on an ancient Chinese herb. disease-causing viruses and bacte-
■ The question comes down to one of will and resources: In view
ria for which vaccines now exist,
of all the competing scourges—in particular, HIV/AIDS—is the malaria vaccines may never carry
world ready to take on malaria in its principal remaining strong- the same clout as, say, measles or
hold, sub-Saharan Africa? polio shots, which protect more
than 90 percent of recipients who
Tackling Malaria 547
complete all recommended doses. of Asia and South America third of those previously living
And in the absence of a vaccine, reveal as much about its perenni- under malaria’s cloud.
Africa’s malaria woes could con- al ties to poverty as about its Sub-Saharan Africa, however,
tinue to grow like a multi- biology. was always a special case: with
headed Hydra. Leading the list Take, for example, malaria’s the exception of a handful of pilot
of current problems are drug- flight from its last U.S. strong- programs, no sustained eradica-
resistant strains of P. falciparum hold—the poor, rural South. The tion efforts were ever mounted
(which first developed in South showdown began in the wake there. Instead the availability of
America and Asia and then of the Great Depression when chloroquine—a cheap, man-made
spread to the African continent), the U.S. Army, the Rockefeller relative of quinine introduced
followed by insecticide resis- Foundation and the Tennessee after World War II—enabled
tance among mosquitoes, crum- Valley Authority (TVA) started countries with scant resources to
bling public health infrastruc- draining and oiling thousands of replace large, technical spraying
tures, and profound poverty that mosquito breeding sites and dis- operations with solitary health
hobbles efforts to prevent infec- tributing quinine (a plant-based workers. Dispensing tablets to
tions in the first place. Finally, antimalarial first discovered in almost anyone with a fever, the
the exploding HIV/AIDS pan- South America) to purge humans village foot soldiers saved millions
demic in Africa competes for of parasites that might otherwise of lives in the 1960s and 1970s.
precious health dollars and dis- sustain transmission. But the Then chloroquine slowly began to
courages the use of blood trans- efforts did not stop there. The fail against falciparum malaria.
fusions for severe malarial TVA engineers who brought With little remaining infrastruc-
anemia. hydroelectric power to the South ture and expertise to counter
Where does this leave us? also regulated dam flow to Africa’s daunting mosquito vec-
With challenges, to be sure. But maroon mosquito larvae and tors, a rebound in deaths was vir-
challenges should not lead to installed acres of screen in win- tually ordained.
despair that Africa will always be dows and doors. As malaria Along the way, economists
shackled to malaria. Economic receded, the local economies grew. learned their lesson once again.
history, for one, teaches us it sim- Then came the golden days Today in many African house-
ply isn’t so. of DDT (dichlorodiphenyl- holds, malaria not only limits
trichloroethane). After military income and robs funds for basic
Lessons of History forces used the wettable powder necessities such as food and
WHEN I LECTURE about malaria to to aerially bomb mosquitoes in youngsters’ school fees, it fuels
medical students and other doc- the malaria-ridden Pacific the- fertility because victims’ families
tors, I like to show a map of its ater during World War II, pub- assume they will always lose chil-
former geography. Most audi- lic health authorities took the dren to the disease. On the
ences are amazed to learn that lead. Five years later selective regional level, it bleeds countries
malaria was not always confined spraying within houses became of foreign investment, tourism and
to the tropics—until the 20th the centerpiece of global malaria trade. Continentwide, it costs up
century, it also plagued such eradication. By 1970 DDT to $12 billion a year, or 4 percent
unlikely locales as Scandinavia spraying, elimination of mos- of Africa’s gross domestic product.
and the American Midwest. The quito breeding sites and the In short, in many places malaria
events surrounding malaria’s expanded use of antimalarial remains entrenched because of
exit from temperate zones and, drugs freed more than 500 mil- poverty and, at the same time, cre-
more recently, from large swaths lion people, or roughly one ates and perpetuates poverty.
HOW MAL ARIA SPREADS
MALARIA PARASITE needs both humans
and mosquitoes to propagate itself. This
complex life cycle has hindered efforts
5 In the mosquito’s
gut, the gametocytes
develop into gametes Anopheles
to engineer a vaccine that can crush
the parasite. Current vaccine research
gambiae strategies focus on three stages of the
and fuse to eventually
produce an oocyst that parasite’s life cycle (a, b and c), two in
releases sporozoites. the human and one in the mosquito.
These travel to the
mosquitos’ salivary Sporozoite
glands, ready to
Oocyst ITO
be transferred QU
M OS MA
N
into another E HU
victim.
Fertilization I D
NS INSI
D E
1 While feeding,
an infected female
I
Anopheles mosquito passes

Sporozoite
sporozoites of the malaria
parasite Plasmodium into Host’s liver
Male the victim’s bloodstream. a
gamete
Female
c
gamete
The Disease 2 Within 30 to 60
minutes, the
sporozoites enter
The rupture of infected blood cells the victim’s liver
causes malaria’s fever, chills and
progressive anemia. Death may occur cells, where they
from severe anemia as well as clogging reproduce asexually,
of blood vessels in the brain, lungs and forming thousands
other organs by parasitized red blood Liver cell of merozoites, most
cells. In pregnancy, malaria-laden of which are later
placentas rob babies of growth Merozoites
released into the
before they are even born. bloodstream.
4 Eventually some
of the merozoites
develop into male and Female gametocyte b
female gametocytes,
which can be ingested
by a previously
Male gametocyte
Host’s
3 The merozoites
invade red blood
cells and multiply,
uninfected mosquito red causing the cells to
taking a blood meal. blood
cell rupture, releasing yet
more merozoites. The
cycle repeats.
Vaccine Targets
aa SPOROZOITE: The goal of bb MEROZOITE: Vaccines based on merozoite c GAMETOCYTE: So-called altruistic gametocyte-
sporozoite vaccines is to antigens lessen malaria’s severity by based vaccines do not affect human disease
block parasites from entering or hobbling the invasion of new generations of but are designed to evoke human antibodies that
growing within human liver cells. red blood cells or by reducing complications. derail parasite development within the mosquito.
JEN CHRISTIANSEN
Battling the Mosquito humans: nighttime bites of para- highly intelligent residents of
everyone
YEARS AGO I THOUGHT site-laden Anopheles mosqui- malaria-plagued communities
knew how malaria infected toes. Today I know better. Some still believe that an evil spirit or
MALARIA
certain foods cause the illness, a

fact that underscores yet anoth-
er pressing need: better malaria
education. Nevertheless, long
Increasing burden
before Ronald Ross and Giovanni
Batista Grassi learned in the late
of malaria
19th century that mosquitoes
transmit malaria, savvy humans
were devising ways to elude mos-
quito bites. Writing almost five
POVERTY
centuries before the common era,
Herodotus described in The
Histories how Egyptians living in
marshy lowlands protected
themselves with fishing nets:
“Every man has a net which he
Increasing burden
uses in the daytime for fishing,

but at night he finds another use
of poverty
for it: he drapes it over the bed....

Mosquitoes can bite through any
cover or linen blanket... but they
do not even try to bite through
the net at all.” Based on this pas-
MALARIA AND POVERTY cover common ground. Costs levied by the disease go far
sage, some bed-net advocates beyond expenditures on prevention and treatment to include lost income,
view nets steeped in fish oil as the investment and tourism revenue. Annual economic growth in countries
world’s earliest repellent-impreg- with endemic malaria averaged 0.4 percent of per capita GDP between 1965
nated cloth. and 1990, compared with 2.3 percent in the rest of the world.
It was not until World War
II, however, when American later trials, without the drugs, in ilies and communities benefited
forces in the South Pacific dipped Ghana, Kenya and Burkina Faso from the nets—even people who
nets and hammocks in 5 percent confirmed a similar lifesaving did not sleep under them.
DDT, that insecticides and tex- trend, plus substantial health gains But insecticide-treated bed
tiles were formally partnered. in pregnant women. Moreover, nets also have drawbacks. They
After public opinion swung with wide enough use, whole fam- work only if malaria mosqui-
against DDT, treating bed nets
JEN CHRISTIANSEN; SOURCE: ROLL BACK MALARIA
with a biodegradable class of

insecticides—the pyrethroids— CLAIRE PANOSIAN DUNAVAN, a tropical medicine specialist at the David
was the logical next step. It Geffen School of Medicine at the University of California, Los Angeles, is
T H E AU T HOR
proved a breakthrough. The first co-editor of a recently published Institute of Medicine report, Saving
major use of pyrethroid-treated Lives, Buying Time: Economics of Malaria Drugs in an Age of Resistance. A
nets paired with antimalarial graduate of Stanford University, Northwestern University Medical School
drugs, reported in 1991, halved and the London School of Hygiene and Tropical Medicine, she is an avid
mortality in children younger teacher and clinician whose second career as a medical journalist spans
than five in the Gambia, and nearly two decades.
toes bite indoors during sleeping long-lasting pyrethroid-impregnat- out insecticide are simply unaf-
hours—a behavior that is not uni- ed nets—became available, nets had fordable for many people. A
versal. Nets make sleepers hot, to be redipped every six to 12 recent study in Kenya found that
discouraging use. Until recently, months to remain effective. Finally, only 21 percent of households
when PermaNet and Olyset—two at $2 to $6 each, nets with or with- had even one bed net, of which 6
DDT: A Symbol Gone Awry

In the 1950s a worldwide campaign to eradicate malaria had Spraying the interior surfaces of a house, in contrast, would
as its centerpiece the spraying of houses with DDT require roughly half a kilogram, applied once or twice a year.
(dichlorodiphenyltrichloroethane). In less than two
decades, the pesticide enabled many countries to control
the disease. In India, for example, deaths from malaria
plummeted from 800,000 annually to almost zero for a time.
Then, in 1972, the U.S. government banned DDT for
spraying crops—although public health and a few other
minor uses were excepted. Rachel Carson’s eloquent book
Silent Spring, published a decade earlier, is often said to
have sparked the ban. Carson meticulously charted the way
DDT travels up the food chain in increasing concentrations,
killing insects and some animals outright and causing
genetic damage in others. DDT became a symbol of the
dangers of playing God with nature, and the developed 1997 1999 2001 2003 MALARIA CASES DECLINED
countries, having got rid of malaria within their borders, aban- dramatically in KwaZulu-Natal
7,000
Annual maximum
doned the chemical. Most of Europe followed the U.S. in ban-
Malaria Cases in KwaZulu-Natal
when the South African govern-

ning the pesticide for agricultural applications in the 1970s. 6,000 ment sprayed dwellings with
For sub-Saharan Africa, where malaria still rages, these DDT and later also treated
5,000
JEN CHRISTIANSEN; SOURCE: IOM REPORT (graph); KAREN DUTHIE AfricanPictures.net (photography)
decisions have meant the loss of a valuable weapon. Most patients with an artemisinin-
4,000 based combination treatment
countries there go without DDT not because they have
(graph). One of the few African
banned it themselves—in fact, it is allowed for public health 3,000
countries wealthy enough to
uses in most areas of the world where malaria is endemic— 2,000 fund its own program, it did not
but because wealthy donor nations and organizations are have to rely on aid from donors
1,000
resistant to funding projects that would spray DDT even in reluctant to use the chemical.
responsible ways. 0 The eaves of a typical African
Many malaria researchers think DDT should be given house, such as those in the
DDT spraying begins photograph, provide many
another look. In addition to being toxic to mosquitoes, they
New drug treatment begins points of entry for mosquitoes.
note, it drives the insects off sprayed walls and out of doors
before they bite, and it deters their entry in the first place. It
is a toxin, irritant and repellent all rolled into one. Moreover,
it lasts twice as long as alternatives, and it costs a quarter DDT alone will not save the world from malaria; for
as much as the next cheapest insecticide. instance, spraying houses works only against mosquitoes
The chemical’s deadly trajectory through the food chain that bite indoors. Effective drugs for patients already
had its roots in massive agricultural spraying (mainly of infected are essential, as are other measures to control
cotton fields)—not in its much more moderate use inside mosquitoes. But most malaria health professionals support
dwellings to repel mosquitoes. Dusting a 100-hectare cotton the targeted use of DDT as an important part of the
field required some 1,100 kilograms of DDT over four weeks. tool kit. —The Editors
percent were insecticide-treated. A How about harnessing the and killing others that perch on
summary of 34 surveys conducted winged creatures themselves to treated walls after feeding. A
between 1999 and 2004 reached kill malaria parasites? In theory, stunning example of its effec-
an even more depressing conclu- genetic engineering could quell tiveness surfaced in KwaZulu-
sion: a mere 3 percent of African parasite multiplication before the Natal in 1999 and 2000.
youngsters were protected by protozoa ever left the insects’ Pyrethroid-resistant A. funestus
insecticidal nets, although reports salivary glands. If such insects plus failing drugs had led to the
on the ground now suggest that succeeded in displacing their nat- largest number of falciparum
use is quickly rising. ural kin in the wild, they could cases there since the South African
Insecticide resistance could halt the spread of malaria para- province launched its malaria-
also undermine nets as a long- sites to people. Recently native control program years ago.
term solution: mosquitoes geneti- genes hindering malaria multipli- Reintroduction of residual spray-
cally capable of inactivating cation within Anopheles mosqui- ing of DDT along with new, effec-
pyrethroids have now surfaced in toes have been identified, and tive drugs yielded a 91 percent
several locales, including Kenya genetically reengineered strains drop in cases within two years.
and southern Africa, and some of several important species are
anophelines are taking longer to now on the drawing board. Once
succumb to pyrethroids, a worri- they are reared in the laboratory, Treating the Sick
some adaptive behavior known as however, releasing these Trojan ANTIMOSQUITO MEASURES alone
knockdown resistance. Because insects into the real world poses a cannot win the war against malar-
precious few new insecticides whole new set of challenges, ia—better drugs and health ser-
intended for public health use are including ethical ones. vices are also needed for the mil-
in sight (largely because of paltry Bottom line: for the time lions of youngsters and adults
economic incentives to develop being, old-fashioned, indoor resid- who, every year, still walk the
them), one solution is rotating ual spraying with DDT remains a malaria tightrope far from med-
other agricultural
insecticides on nets.
Decoding the olfactory
clues that attract mos- An ancient disease that is both preventable
quitoes to humans in
the first place is anoth- and curable still claims at least one million
er avenue of research lives every year.
that could yield divi-
dends in new repel-
lents. (Ironically, a
change in body odor when P. fal- valuable public health tool in ical care. Some are entrusted to
ciparum parasites are present in many settings in Africa and else- village herbalists and itinerant
the blood may also attract mos- where [see box on facing page]. quacks. Others take pills of
quito bites; according to a recent Applied to surfaces, DDT is unknown manufacture, quality
report, Kenyan schoolchildren retained for six months or more. or efficacy (including counter-
harboring gametocytes—the It reduces human-mosquito con- feits) bought by family members
malaria stage taken up by mosqui- tact by two key mechanisms— or neighbors from unregulated
toes—drew twice as many bites as repelling some mosquitoes sources. In Africa, 70 percent of
their uninfected counterparts.) before they ever enter a dwelling antimalarials come from the
informal private sector—in other tages, combining them with other based artemisinins (a peroxide
words, small roadside vendors as effective antimalarial drugs in an bond embedded in a chemical
opposed to licensed clinics or effort to prevent or delay ring) are on the horizon, possibly
pharmacies. artemisinin resistance makes sense, within five to 10 years. One pro-
Despite plummeting efficacy, not just for Africa’s but for the totype originating from research
chloroquine, at pennies per entire world’s sake. After all, there done in the late 1990s entered
course, remains the top-selling is no guarantee malaria will not human trials in 2004. Another
antimalarial pharmaceutical return someday to its former promising tactic that could
downed by Africans. The next haunts. We know it can victimize bypass botanical extraction or
most affordable drug in Africa is
global travelers. In recent years P. chemical synthesis altogether is
sulfadoxine-pyrimethamine, an
falciparum–infected mosquitoes splicing A. annua’s genes and
antibiotic that interferes with
folic acid synthesis by the para- have even stowed away on interna- yeast genes into Escherichia coli,
site. Unfortunately, P. falciparum tional flights, infecting innocent then coaxing pharmaceuticals out
strains in Africa and elsewhere bystanders within a few miles of of the bacterial brew. The
are also sidestepping this com- airports, far from malaria’s nat- approach was pioneered by
pound as they acquire sequential ural milieu. researchers at the University of
mutations that will ultimately Yet there is a hitch to the California, Berkeley.
render the drug useless. new combination remedies: their Preventing, as opposed to
Given the looming specter of costs—currently 10 to 20 times treating, malaria in highly vulner-
drug resistance, can lessons from higher than Africa’s more famil- able hosts—primarily African
other infectious diseases guide iar but increasingly impotent children and pregnant women—is
future strategies to beef up malaria drugs—are hugely also gaining adherents. In the
malaria drug therapy? In recent daunting to most malaria victims 1960s low-dose antimalarial pro-
decades resistant strains of the and to heavily affected countries. phylaxis given to pregnant
agents responsible for tuberculo- Even if the new cocktails were Nigerians was found, for the first
sis, leprosy and HIV/AIDS trig- more modest in price, the global time, to increase their newborns’
gered a switch to two- and three- supply of artemisinins is well birthweight. Currently this
drug regimens, which then below needed levels and requires approach has been superseded by
helped to forestall further emer- donor dollars to jump-start the a full course of sulfadoxine-
gence of “superbugs.” Now 18-month production cycle to pyrimethamine taken several
most experts believe that multi- grow, harvest and process the times during pregnancy, infancy
drug treatments can also com- plants. Novartis, the first producer and, increasingly, childhood
bat drug resistance in falciparum formally sanctioned by the WHO immunization visits. Right now
malaria, especially if they include to manufacture a co-formulated the recipe works well in reducing
a form of Artemisia annua, a artemisinin combination treat- infections and anemia, but once
medicinal herb once used as a ment (artemether plus lume- resistance truly blankets Africa,
generic fever remedy in ancient fantrine), may not have enough the question is, What preventive
China. Artemisia-derived drugs funding and raw material to ship treatment will replace sulfadoxine-
(collectively termed “artemisinins”) even a portion of the 120 million pyrimethamine? Although single-
beat back malaria parasites more treatments it once hoped to deliv- dose artemisinins might seem the
quickly than any other treatment er in 2006. logical answer at first blush, these
does and also block transmission The good news? Cheaper, agents are not suitable for preven-
from humans to mosquitoes. synthetic drugs that retain the tion, because their levels in blood
Because of these unequaled advan- distinctive chemistry of plant- diminish so quickly. And repeated
genetic makeup: of the 5,300 Three decades later, in 2004,

proteins encoded by P. falci- efforts bore fruit when a sporo-
parum’s genome, fewer than 10 zoite vaccine more than halved
percent trigger protective respons- serious episodes of malaria in
es in naturally exposed individu- 2,000 rural Mozambican chil-
als—the question is, Which ones? dren between the ages of one and
On top of that, several arms of the four, the years when African
human immune system—antibod- children are most susceptible to
ies, lymphocytes and the spleen, dying from the disease. The for-
for starters—must work together mula used in this clinical trial
to achieve an ideal response to (the most promising to date)
malaria vaccination. Even in included multiple copies of a P.
healthy people, much less popula- falciparum sporozoite protein
tions already beset with malaria fragment fused to a hepatitis B
and other diseases, such responses viral protein added for extra
EBRAHIM SAMBA, who recently retired as do not always develop. potency. Even so, subjects
the WHO’s Regional Director for Africa, still So far most experimental P. required three separate immu-
bears delicate hatch marks incised on his
falciparum vaccines have target- nizations, and the period of pro-
cheeks at the age of two, when he was
close to death from severe malaria. ed only one of malaria’s three tection was short (only six
biological stages—sporozoite, months). Realistically, the earli-
merozoite or gametocyte [see est that an improved version of
dosing of artemisinins in asymp-
box on page 548], although mul- the vaccine known as RTS,S (or
tomatic women and children—an
tistage vaccines, which could any of its roughly three dozen
untested practice so far—could
well prove more effective in the vaccine brethren currently in
also yield unsuspected side effects.
end, are also planned. Some of clinical development) might
In an ideal world, prevention
the earliest insights on attacking come to market is in 10 years, at
equals vaccine.
sporozoites (the parasite stage a final price tag that leaves even
usually inoculated into humans Big Pharma gasping for air.
Where We Stand on through the mosquito’s pro- Because of the anticipated costs,
Vaccines boscis) came in the 1970s, when public-private partnerships such
THERE IS NO DOUBT that creating investigators at the University of as the Seattle-based Malaria
malaria vaccines that deliver Maryland found that x-ray-weak- Vaccine Initiative are now help-
long-lasting protection has ened falciparum sporozoites pro- ing to fund ongoing trials.
proved more difficult than scien- tected human volunteers, albeit There is just one more thing to
tists first imagined, although only briefly. Presumably, the vac- keep in mind about malaria vac-
progress has occurred over sev- cine worked by inducing the cines. Even when they do become
eral decades. At the root of the immune system to neutralize nat- available—with any luck, sooner
dilemma is malaria’s intricate urally entering parasites before rather than later—effective treat-
life cycle, which encompasses they escaped an hour later to ments and antimosquito strategies
several stages in mosquitoes and their next way station, the liver. will still be needed. Why? First of
humans; a vaccine effective in The demonstration that anti- all, because rates of protection
©WHO/P. VIROT
killing one stage may not inhibit bodies artificially elicited against will never reach anywhere near
the growth of another. A second sporozoites could help fend off 100 percent in those who actual-
challenge is malaria’s complex malaria prompted further work. ly receive the vaccines. Other
malaria-prone individuals, espe- renewed assault on malaria, and and development funding noted
cially the rural African poor, President George W. Bush that only $323 million was spent
may not have access to the shots announced a $1.2-billion package in 2004. This amount falls far
at all. Therefore, at least for the to fight malaria in Africa over five short of the projected $3.2 billion
foreseeable future, all preventive years, using insecticide-treated a year needed to cut malaria
and salvage measures must nets, indoor spraying of insecti- deaths in half by 2010. Perhaps it
remain in the arsenal. cides and combination drug treat- is time to mobilize not only
ments. More recently, the World experts and field-workers but
Investing in Malaria Bank has begun looking for ways ordinary folk. At roughly $5, the
ONCE AGAIN THE WORLD is coming to subsidize artemisinin combina- price of a lunch in the U.S. could
to terms with the truth about malar- tion treatments. As this issue of go a long way toward purchasing
ia: the ancient enemy still claims at Scientific American went to an insecticide-treated bed net or a
least one million lives every year press, the Bill and Melinda three-day course of artemisinin
while, at the same time, imposing Gates Foundation announced combination treatment for an
tremendous physical, mental and three grants totaling $258.3 mil- African child.
economic hardships. Given our cur- lion to support advanced devel- In considering their potential
rent tools and even more promising opment of a malaria vaccine, new return on investment, readers
weapons on the horizon, the time drugs and improved mosquito- might also recall a small boy with
has come to fight back. control methods. scars on his cheeks who made it
The past decade has already Despite these positive steps, through malaria’s minefield,
witnessed significant milestones. the dollars at hand are simply not then devoted his adult life to bat-
In 1998 the WHO and the World equal to the task. Simultaneously tling disease. Decades from now,
Bank established the Roll Back with the announcement from the how many other children thus
Malaria partnership. In 2000 the Gates Foundation, a major new spared might accomplish equally
G8 named malaria as one of three analysis of global malaria research wondrous feats?
pandemics they hoped to curb, if
not vanquish. The United Nations
subsequently created the Global
MORE TO EXPLORE
Fund to Fight AIDS, Tuberculosis
and Malaria and pledged to halt What the World Needs Now Is DDT. Tina Rosenberg in New York Times Magazine,
pages 38–43; April 11, 2004.
and reverse the rising tide of
malaria within 15 years. In 2005 Medicines for Malaria Venture; www.mmv.org/
the World Bank declared a World Health Organization, Roll Back Malaria Department: www.who.int/malaria
PART IV
WATER CHEMISTRY
AND WATER
POLLUTION
Contents of Part IV
Chapter 13 The Chemistry of Natural Waters
Chapter 14 The Pollution and Purification of Water
Environmental Instrumental Analysis V

 Ion Chromatography of Environmentally Significant Anions
C H A P T E R
13
THE CHEMISTRY OF
NATURAL WATERS
topics are used:
 Concepts of oxidation and reduction as electron
loss/gain; half-reactions; redox reactions; oxidizing and
reducing agents; electrode potentials
 Solubility product and weak acid/weak base calculations;
water constant K w
 Oxidation numbers and the balancing of redox reactions
(reviewed in Box 13-1)

 Equlibria involving gases dissolved in water: Henry’s law
(Chapter 3)
Introduction
All life forms on Earth depend on water. Each human being needs to consume
several liters of fresh water daily to sustain life. Much more water is used for
other domestic activities: Typical daily usages for showering/bathing, washing,
and toilets each amount to about 50 L, in addition to about 20 L for dishwash-
ing and 10 L for cooking. (A hose delivers 10 L or more of water per minute,
so watering gardens and lawns can easily double average domestic consump-
tion.) Vastly larger amounts per capita are used by industry and especially for
irrigation in agriculture. For example, thousands of liters of fresh water are
required to produce one kilogram of beef or cotton or even of rice.
However, fresh water is at a premium. Over 97% of the world’s water is
seawater, unsuitable for drinking and for most agricultural purposes. Three-
quarters of the fresh water is trapped in glaciers and ice caps. Lakes and rivers
are one of the main sources of drinking water, even though taken together
they constitute less than 0.01% of the total water on the planet. About half
557
558 Chapter 13 The Chemistry of Natural Waters
Atmosphere
13,000
Net transport
Precipitation to land
on land 40,000
111,000
FIGURE 13-1 Global Evapotranspiration
pools and fluxes of water Evaporation
from land from oceans
on Earth, showing the size 71,000
of groundwater storage rel- Precipitation 425,000
River flow
ative to other major water to oceans on oceans
Ice 385,000
sources and fluxes. All pool 40,000
33,000,000
volumes (green) are in
cubic kilometers, and all Soil water
fluxes (black) are in cubic 122,000
kilometers per year.
[Source: W. H. Schlesinger,
Biogeochemistry—An Analysis
Groundwater Oceans
15,300,000 1,350,000,000
of Global Change, 2nd ed. (San
Diego: Academic Press, 1997),
Chapter 10.]
of drinking water is obtained from groundwater, the fresh water that lies
underground and that is discussed in detail in Chapter 14. The annual fluxes
of water between its global pools in the oceans, the air, and beneath the
ground are shown in Figure 13-1, along with the sizes of each pool.
Humanity currently consumes, mostly for agriculture, about one-fifth of
the accessible runoff water that travels through rivers to the seas; this fraction
is predicted to rise to about three-quarters by 2025. Runoff water is highly
variable in both location and time in terms of its availability unless storage
and transport are available. Although only 10% of the world’s population in
2000 lived under conditions of water stress or scarcity, this figure is expected
to rise to 38% by 2025 (Figure 13-2).
It is important to understand the types of chemical activities that prevail
in natural waters and how the science and application of chemistry can be
employed to purify water intended for drinking purposes. Although some dis-
cussion of pollution problems is contained in this chapter, the remediation of
contaminated water is considered in detail in Chapter 14.
It will be convenient to divide our considerations of water chemistry in
this chapter into the two common reaction categories: acid–base reactions
and oxidation–reduction (redox) reactions. Acid–base and solubility phe-
nomena control the concentrations of dissolved inorganic ions such as car-
bonate in waters, whereas the organic content of water is dominated by redox
reactions. The pH and concentrations of the principal ions in most natural
water systems are controlled by the dissolution of atmospheric carbon dioxide
2000 2025 (medium projection)

Total population: 6 billion Total population: 7.9 billion
4%
6%
27%
62%
11% FIGURE 13-2 Global
90% water supply in 2000 and
projection for 2025.
[Source: R. Engelman et al.,
People in the Balance
(Washington, DC: Popular
Action International, 2000)
Percentage of world population with
as reproduced in Nature 422
stress scarcity relative sufficiency (2003): 252.]
and soil-bound carbonate ions; such reactions are considered in detail later in
the chapter. Before considering these acid–base processes, we consider some
important redox processes, especially those involving dissolved oxygen. For
clarity, the phase (aq) for ions and molecules dissolved in aqueous solution
will not be shown in equations but simply assumed.
Oxidation–Reduction Chemistry in Natural Waters

Dissolved Oxygen
By far the most important oxidizing agent (i.e., substance that extracts elec-
trons from other species) in natural waters is dissolved molecular oxygen, O2.
Upon reaction, each of the oxygen atoms in O2 is reduced from the zero
oxidation number to 2, in H2O or OH. (The concept and calculation of
oxidation numbers is reviewed in Box 13-1, as is the balancing of redox equa-
tions.) The half-reaction that occurs in acidic solution is
O2 4 H 4e 9: 2 H2O
whereas that which occurs in basic aqueous solution is
O2 2 H2O 4e 9: 4 OH
The concentration of dissolved oxygen in water is small and therefore
precarious from the ecological point of view. As discussed in Chapter 3, for
the dissolution of a gas in water such as the process
O2(g) Δ O2(aq)
BOX 13-1 Redox Equation Balancing Reviewed
Assigning Oxidation Numbers (v) Chlorine, bromine, and iodine have

O.N.’s of 1 (except when overridden by a
A simple way to determine the extent (if any)
rule higher in the sequence, as an example
to which an element is oxidized or reduced in a
below illustrates).
reaction is to deduce the change in its oxidation
number, O.N., in the product as compared to
that in the reactant. The oxidation number of Some examples:
the elements in most compounds and ions can
HF: F is 1 (rule ii) and H is 1 (rule iii); the
be determined by applying, in sequence, the
sum is zero, as required.
following set of rules, keeping in mind that the
sum of all the oxidation numbers in a substance H2O2: H is 1 (rule iii), but O here cannot be
must equal its net charge. The rules are listed in 2 (rule iv) since the sum of charges would be
terms of priority so that, e.g., if for a compound 2 (1) 2 (2) 2; the charges must add
rule (iv) is inconsistent with rule (iii), then up to zero for the molecule as a whole. Since
rule (iii) takes precedence since it is higher in rule (iii) takes precedence, each H must be
the order. 1, so each O here must be 1 in order that
the sum be zero.
(i) Elements appearing in the free, unbonded
form have an O.N. equal to their ionic charge, ClO2: Each O is 2 (rule iv), for a total of 4,
which is zero if the element is uncharged. so Cl here cannot be 1 (rule v) since the sum
of charges would then be 1 2 (2) 5,
(ii) Fluorine has an O.N. of 1 in com- as compared to the actual net charge of 1.
pounds. Group I and II metals have O.N. values Since O.N.Cl 2 (2) 1, it follows
corresponding to their ionic charges 1 and that O.N.Cl 3 here.
2, respectively, and Al is 3.
As an example of the use of oxidation
(iii) Hydrogen has an O.N. of 1, except numbers in reactions, consider the half-reaction
when bonded to a metal, where it is 1. in which nitrate ion is converted into nitrous
(iv) Oxygen has an O.N. of 2 (except oxide:
when overridden by a rule higher in the
sequence, as an example below illustrates). NO3 9: N2O
the appropriate equilibrium constant is the Henry’s law constant KH, which
for oxygen at 25°C has the value 1.3 103 mol L1 atm1:
KH [O2(aq)]/PO2 1.3 103 mol L1 atm1 at 25°C
Since in dry air at sea level the partial pressure, PO2, of oxygen is 0.21 atmo-
spheres (atm), it follows that the solubility of O2 is 8.7 milligrams per liter of
water (see Problem 13-1). This value can also be stated as 8.7 ppm since, as
discussed in Chapter 10, ppm concentrations for condensed phases are based
Since in nitrate ion, each O is 2, the sum of • Next, to balance charge, add sufficient
which is 6, and the charge on the ion is only H ions to the side having excess negative
1, it follows that N here is 5. charge; note that only real charges on ions and
electrons are considered here, not oxidation
In nitrous oxide, the O is 2, and the sum of oxi- numbers.
dation numbers is zero, so each N must be 1.
• Finally, balance the number of oxygen
Keeping in mind that the reaction requires 2 atoms by adding H2O molecules to the side
nitrate ions to supply enough nitrogen for one deficient in oxygen.
nitrous oxide molecule, we see that 2 5 N’s,
total 10, here become 2 1 N’s, total 2.
Consider, for example, the nitrate to nitrous
Thus the half-reaction must be a (10 2 )
oxide example given above:
8-electron reduction:
2 NO3 8 e 9: N2O 2 NO3 8 e 9: N2O
If it is required to know the amounts of water The actual charge on the left-hand side is
molecules and H or OH ions involved, the 2 (1) (8) 10, but that on the
detailed balancing scheme discussed below right side is zero. Thus we should add 10 posi-
must be employed. tive charges, each in the form of H, to the
left side, so that its charge also becomes zero:
Balancing Redox Equations 2 NO3 8 e 10 H 9: N2O
There are many equivalent schemes to com-
pletely balance redox half-reactions and over- Finally, since we now have 2 3 6 O atoms
all reactions, of which the following is one on the left side and only one on the right side,
example. we need to add 5 O each in the form of H2O
molecules to the right side:
• To balance a half-reaction, first deduce
the number of electrons involved in the 2 NO3 8 e 10 H 9: N2O 5 H2O
process, as in the scheme above, by balancing
atoms other than H and O. The half-reaction is now balanced.
on mass rather than moles. (Note that for simplicity, molar concentrations
rather than activities are used in all equilibrium calculations in this book,
since in general we are considering only very dilute solutions.)
Because the solubilities of gases increase with decreasing temperature,
the amount of O2 that dissolves at 0°C (14.7 ppm) is greater than the
amount that dissolves at 35°C (7.0 ppm). The median concentration of
oxygen found in natural, unpolluted surface waters in the United States is
about 10 ppm.
P R O B L E M 13-1
Confirm by calculation the value of 8.7 mg/L for the solubility of oxygen in
water at 25°C.
P R O B L E M 13-2
Given the solubility quoted above for O2 at 0°C, calculate the value of KH for it
at this temperature.
River or lake water that has been artificially warmed can be considered to
have undergone thermal pollution in the sense that, at equilibrium, it will
contain less oxygen than colder water because of the decrease in gas solubil-
ity with increasing temperature. To sustain their lives, most fish species
require water containing at least 5 ppm of dissolved oxygen; consequently,
their survival in warmed water can be problematic. Thermal pollution often
occurs in the region of electric power plants (whether fossil fuel, nuclear, or
solar), since they draw cold water from a river or lake, use it for cooling pur-
poses, and then return the warmed water to its source.
Oxygen Demand
The most common substance oxidized by dissolved oxygen in water is organic
matter having a biological origin, such as dead plant matter and animal
wastes. If, for the sake of simplicity, the organic matter is assumed to be
entirely polymerized carbohydrate (e.g., plant fiber) with an approximate
empirical formula of CH2O, the oxidation reaction would be
CH2O(aq) O2(aq) 9: CO2(g) H2O(aq)
carbohydrate
Dissolved oxygen in water is also consumed by the oxidation of dissolved

ammonia, NH3, and ammonium ion, NH4—substances that, like organic
matter, are present in water as a result of biological activity—eventually to
nitrate ion, NO3 (see Problem 13-4).
P R O B L E M 13-3
Show that 1 L of water saturated with oxygen at 25°C is capable of oxidizing
8.2 mg of polymeric CH2O.
P R O B L E M 13-4
Determine the balanced redox reaction for the oxidation of ammonia to
nitrate ion by O2 in alkaline (basic) solution. Does this reaction make the
water more alkaline or less? [Hint: Recall the redox balancing procedure in
Box 13-1.]
Water that is aerated by flowing in shallow streams and rivers is con-

stantly replenished with oxygen. However, stagnant water or that near the
bottom of a deep lake is usually almost completely depleted of oxygen because
of its reaction with organic matter and the lack of any mechanism to replen-
ish it quickly, diffusion being a slow process and turbulent mixing being
absent.
The capacity of the organic and biological matter in a sample of natural
water to consume oxygen, a process catalyzed by bacteria present, is called its
biochemical oxygen demand, BOD. It is evaluated experimentally by deter-
mining the concentration of dissolved O2 at the beginning and at the end of
a period in which a sealed water sample seeded with bacteria is maintained in
the dark at a constant temperature, usually either 20°C or 25°C. A neutral
pH is maintained by use of a buffer consisting of two ions of phosphoric acid,
namely H2PO4 and HPO42:
H2PO4 Δ HPO42 H
The BOD equals the amount of oxygen consumed as a result of the oxidation
of dissolved organic matter in the sample. The oxidation reactions are catalyzed
in the sample by the action of microorganisms present in the natural water. If
it is suspected that the sample will have a high BOD, it is first diluted with
pure, oxygen-saturated water so that sufficient O2 will be available overall to
oxidize all the organic matter; the results are corrected for this dilution. Usu-
ally the reaction is allowed to proceed for five days before the residual oxygen
is determined. The oxygen demand determined from such a test, often desig-
nated BOD5, corresponds to about 80% of that which would be determined if
the experiment were allowed to proceed for a very long time—which of
course is not very practical. The median BOD for unpolluted surface water in
the United States is about 0.7 mg O2 per liter, which is considerably less than
the maximum solubility of O2 in water (of 8.7 mg/L at 25°C). In contrast, the
BOD values for sewage are typically several hundreds of milligrams of oxygen
per liter.
A faster determination of oxygen demand of a water sample can be made
by evaluating its chemical oxygen demand, COD. Dichromate ion, Cr2O72,
can be dissolved as one of its salts, such as K2Cr2O7, in sulfuric acid: The
result is a powerful oxidizing agent. It is this solution, rather than O2, that is
used to ascertain COD values. The reduction half-reaction for dichromate
when it oxidizes the organic matter is
Cr2O72 14 H 6 e 9: 2 Cr3 7 H2O
(In practice, excess dichromate is added to the sample and the resulting solu-
tion is back-titrated with Fe2 to the end point.) The number of moles of O2
that the sample would have consumed in accomplishing the oxidation of the
same material equals 6兾4 ( 1.5) times the number of moles of dichromate,
since the latter accepts six electrons per ion whereas O2 accepts only four:
O2 4 H 4e 9: 2 H2O
Thus the moles of O2 required for the oxidation is 1.5 times the number of
moles of dichromate actually used. (See Problems 13-5 and 13-6.)
P R O B L E M 13-5
A 25-mL sample of river water was titrated with 0.0010 M K2Cr2O7 and
required 8.3 mL to reach the end point. What is the chemical oxygen
demand, in milligrams of O2 per liter, of the sample?
P R O B L E M 13-6
The COD of a water sample is found to be 30 mg of O2 per liter. What vol-
ume of 0.0020 M K2Cr2O7 will be required to titrate a 50-mL sample of the
water?
The difficulty with the COD index as a measure of oxygen demand is that
acidified dichromate is such a strong oxidant that it oxidizes substances that
are very slow to consume oxygen in natural waters and that therefore pose no
real threat to their dissolved oxygen content. In other words, dichromate oxi-
dizes substances that would not be oxidized by O2 in the determination of the
BOD. Because of this excess oxidation, namely of stable organic matter such
as cellulose to CO2, and of Cl to Cl2, the COD value for a water sample as a
rule is slightly greater than its BOD value. Neither method of analysis oxidizes
aromatic hydrocarbons or many alkanes, which, in any event, resist degrada-
tion, and therefore oxygen consumption, in natural waters.
It is not uncommon for water polluted by organic substances associated
with animal or food waste or sewage to have an oxygen demand that exceeds
the maximum equilibrium solubility of dissolved oxygen. Under such circum-
stances, unless the water is continuously aerated, it will soon be depleted of
its oxygen, and fish living in the water will die. The treatment of wastewater
to reduce its BOD is discussed in Chapter 14.
Finally, we note that there are two other measures used for the amount of
organic substances present in natural waters. The total organic carbon, TOC,
is used to characterize the dissolved and suspended organic matter in raw
water. For example, the TOC usually has a value of approximately 1 mil-
ligram per liter, i.e., 1 ppm carbon, for groundwater. The parameter dissolved
organic carbon, DOC, is used to characterize only organic material that is
actually dissolved, not suspended. For surface waters, the DOC averages
about 5 ppm, although bogs and swamps can have DOC values that are ten
times this amount, and untreated sewage typically has a DOC value of hun-
dreds of ppm. The largest component of organic carbon in natural waters is
usually carbohydrates, but many other types including proteins and low-
molecular-weight aldehydes, ketones, and carboxylic acids are also present.
The humic materials in water are discussed in Chapter 16.
Green Chemistry: Enzymatic Preparation

of Cotton Textiles
Globally over 40 billion pounds (20 million kilograms) of cotton are pro-
duced each year. Even with the invasion of synthetic fibers such as nylon,
polyester, and acrylics, cotton still holds over 50% of the market share for
apparel and home furnishings that are sold in the United States. In preparing
raw cotton for use as a fiber, several steps—including desizing, scouring, and
bleaching—are required, leaving a fiber that is 99% cellulose. These steps use
copious amounts of chemicals, water, and energy, and they produce millions
of pounds of aqueous waste that is high in BOD and COD.
Raw cotton is composed of several concentric layers. The outermost layer
is composed of fats, waxes, and pectin, while the inner layers consist prima-
rily of cellulose. The fats and waxes make the raw cotton fiber waterproof,
and the pectin acts as a powerful glue to hold the layers together. In order to
prepare cotton for use as a fiber for bleaching and dyeing, the outer layer must
be removed. This process, which is known as scouring, has traditionally been
done by immersing the cotton in 18–25% aqueous sodium hydroxide solu-
tion at elevated temperatures. This results in hydrolysis of the fats (saponifi-
cation) and waxes, which solubilizes the components of the outer layer so
that they can simply be rinsed away. Scouring results in fibers of even and high
wettability. In addition to sodium hydroxide, chelating agents (Chapter 14)
and emulsifiers are added during the scouring process. To end the process, the
mixture is neutralized with acetic acid and rinsed several times.
The scouring process is estimated by the U.S. EPA to account for about
half of the total BOD produced in the preparation of cotton fibers. The BOD
in wastewater from cotton production generally exceeds 1100 mg/L, which is
several times that of raw sewage. In addition to the large amounts of chemi-
cals, energy, and water that are used, and the concomitant pollution that is
produced, another disadvantage of this process is the unintended weakening
and loss of some of the cellulose fibers.
An alternative to the traditional scouring process, known as Bio-
Preparation, was developed by Novozymes-North America Inc. and won a
Presidential Green Chemistry Challenge Award in 2001. BioPreparation
employs an enzyme (a pectin lyase) that selectively degrades pectin at ambi-
ent temperatures. Since pectin acts as a glue to hold the outer layer of
the cotton fiber together, destruction of the pectin results in disintegration of

this layer. Because the lyase is selective for only pectin, its use is much less
aggressive than the typical scouring process and removes much less organic
material (including cellulose) from the cotton. Since the dissolved organic
materials are what contribute to the high BOD and COD of the wastewater,
this enzymatic treatment lowers the BOD by 20% and the COD by 50%.
In addition to these environmental advantages, BioPreparation elimi-
nates the use of sodium hydroxide solutions at elevated temperatures, which
in turn
• lowers the pH of the wastewater,
• eliminates the need for neutralization with acetic acid and the concomi-
tant wastes,
• lowers energy requirements, and
• lowers rinsing requirements, reducing water consumption by 30–50%.
Elimination of the use of sodium hydroxide also reduces the risk to workers,
and the reduced degradation of cellulose provides for more robust fibers and
higher yield.
Decomposition of Organic Matter in Water

Dissolved organic matter will decompose in water under anaerobic (oxygen-
free) conditions if appropriate bacteria are present. Anaerobic conditions occur
naturally in stagnant water such as swamps and at the bottom of deep lakes. The
bacteria operate on carbon to disproportionate it; that is, some carbon is oxi-
dized to carbon dioxide, CO2, and the rest is reduced to methane, CH4:
bacteria
2 CH2O 9: CH4 CO2
organic matter
C oxidation number 0 4 4
This is an example of a fermentation reaction, which in chemistry is defined
as one in which both the oxidizing and the reducing agents are organic mate-
rials. Since methane is almost insoluble in water, it forms bubbles that can be
seen rising to the surface in swamps and sometimes catches fire; indeed,
methane was originally called marsh or swamp gas. The same chemical reac-
tion shown above occurs in digestor units used by rural inhabitants in semi-
tropical developing countries (India, for instance) to convert animal wastes
into methane gas that can be used as a fuel. The reaction also occurs in land-
fills, as discussed in Chapter 16.
Since anaerobic conditions are reducing conditions in the chemical
sense, insoluble Fe3 compounds that are present in sediments at the bottom
of lakes are converted into soluble Fe2

compounds, which then dissolve into the
Aerobic conditions CO2 H2CO3 HCO3–
lake water: (warm water)
Fe3 e 9: Fe2 SO42– NO3– Fe(OH)3
insoluble Fe(III) soluble Fe(II)

Anaerobic conditions CH4 H2S NH3
It is not uncommon to find aerobic and (cold water)
anaerobic conditions in different parts of NH4+ Fe2+(aq)
the same lake at the same time, particularly
in the summertime when a stable stratifica-
tion of distinct layers often occurs (see Fig-
FIGURE 13-3 The stratifi-
ure 13-3). Water at the top of the lake is warmed by the absorption of
cation of a lake in the
sunshine by biological materials, while that below the level of penetration of summer, showing the
sunlight remains cold. Since warm water is less dense than cold (at tempera- typical forms of the major
tures above 4°C), the warm upper layer “floats” on the cold layer below, and elements it contains at
little transfer between them occurs. The top layer, called the epilimnium, usu- different levels.
ally contains near-saturation levels of dissolved oxygen, due both to its con-
tact with air and to the O2 produced in photosynthesis by algae. Since
conditions in the top layer are aerobic, elements exist there in their most
oxidized forms:
• carbon, with an oxidation number (O.N.) of 4, as CO2 or H2CO3
or HCO3;
• sulfur, O.N. of 6, as SO42;
• nitrogen, O.N. of 5, as NO3; and
• iron, as Fe(III), in the form of insoluble Fe(OH)3.
Near the bottom, in the hypolimnium, the water is oxygen-depleted since it
has no contact with air and since O2 is consumed when biological material,
such as the dead algae that have sunk to these depths, decomposes. Under
such anaerobic conditions, elements exist in their most reduced forms:
• carbon, with an O.N. of 4, as CH4;
• sulfur, O.N. of 2, as H2S;
• nitrogen, O.N. of 3, as NH3 and NH4; and
• iron, as Fe(II), in the form of soluble Fe2.
Anaerobic conditions usually do not last indefinitely. In the fall and win-
ter, the top layer of water is cooled by cold air passing over it, so that even-
tually the oxygen-rich water at the top becomes more dense than that
below it and gravity induces mixing between the layers. Thus in the win-
ter and early spring the environment near the bottom of a lake usually is
aerobic.
TABLE 13-1 Common Oxidation Numbers for Sulfur
Increasing Levels of Sulfur Oxidation
Oxidation Number of S ⫺2 ⫺1 0 ⫹4 ⫹6
Aqueous solution and salts H2S H2SO3 H2SO4

HS HSO3 HSO4
S2 S22 SO32 SO42
Gas phase H2S SO2 SO3
Molecular solids S8
Sulfur Compounds in Natural Waters

The common inorganic oxidation numbers in which sulfur is encountered in
the environment are illustrated in Table 13-1; they range from the highly
reduced 2 form that is found in hydrogen sulfide gas, H2S, and insoluble
minerals containing the sulfide ion, S2, to the highly oxidized 6 form that
is encountered in sulfuric acid, H2SO4, and in salts containing the sulfate
ion, SO42. In organic and bioorganic molecules such as amino acids, inter-
mediate levels of sulfur oxidation are present. When such molecules decom-
pose anaerobically, hydrogen sulfide and other gases such as CH3SH and
CH3SSCH3 containing sulfur in highly reduced forms are released, thereby
giving swamps their unpleasant odor. The occurrence of such gases as air pol-
lutants was mentioned in Chapter 3.
As discussed in Chapter 3, hydrogen sulfide is oxidized in air first to
sulfur dioxide, SO2, and then fully to sulfuric acid or a salt containing the
sulfate ion. Similarly, hydrogen sulfide dissolved in water can be oxidized by
certain bacteria to elemental sulfur or more completely to sulfate. Overall
the complete oxidation reactions correspond to
H2S 2 O2 9: H2SO4
Some anaerobic bacteria are able to use sulfate ion as the oxidizing agent
to convert organic matter, such as polymeric CH2O, to carbon dioxide when
the concentration of oxygen in the water is very low; the SO42 ions are
reduced in the process to elemental sulfur or even to hydrogen sulfide:
2 SO42 3 CH2O 4 H 9: 2 S 3 CO2 5 H2O

Such reactions are especially important in seawater, for which the sulfate
ion concentration is much higher than the average for fresh-water systems.
Acid Mine Drainage

One characteristic reaction of groundwater, which by definition is not well-
aerated since it has spent much time not exposed to air, is that when it
reaches the surface and O2 has an opportunity to dissolve in it, its rather high
level of soluble Fe2 is converted to insoluble Fe3, and an orange-brown
deposit of Fe(OH)3 is formed.
4 Fe2 O2 2 H2O 9: 4 Fe3 4 OH
4 [Fe3 3 OH 9: Fe(OH)3(s)]
The overall reaction is
4 Fe2 O2 2 H2O 8 OH 9: 4 Fe(OH)3(s)
An analogous reaction occurs in some underground coal and metal
(especially copper) mines, especially abandoned ones, and in piles of mined
coal left open to the environment. Normally FeS2, called iron pyrites, or
fool’s gold, is a stable, insoluble component of underground rocks as long as it
does not come into contact with air. However, as a result of the mining of
coal and certain ores—and especially after underground mines have been
abandoned and spontaneously fill with groundwater—some of it is exposed to
water, oxygen, and certain bacteria and becomes partially solubilized as a
result of its oxidation. The disulfide ion, S22, in which sulfur has an average
oxidation number of 1, is oxidized to sulfate ion, SO42, which contains
sulfur in the 6 form:
S22 8 H2O 9: 2 SO42 16 H 14 e

The main oxidizing agent acting on the sulfur is atmospheric O2:
7 [O2 4 H 4 e 9: 2 H2O]
When this (28 e) half-reaction is added to twice the (14 e) oxidation half-
reaction, the net redox reaction is obtained:
2 S22 7 O2 2 H2O 9: 4 SO42 4 H
Since the sulfate salt of the ferrous ion, Fe2, is soluble in water, the iron
pyrites are effectively solubilized by the reaction. More importantly, the reac-
tion produces a large amount of concentrated acid (note the H product),
only a portion of which is consumed by the air oxidation of Fe2 to Fe3 that
accompanies the process:
4 Fe2 O2 4 H 9: 4 Fe3 2 H2O
In acidic environments, this reaction is catalyzed by bacteria (Thiobacillus
ferrooxidans); the resulting Fe3 can oxidize various metal sulfides, liberating
the metal ions.
Combining the last two reactions in the correct ratio, i.e., 2:1, we obtain
the overall reaction for the oxidation of both the iron and the sulfur:
4 FeS2 15 O2 2 H2O 9: 4 Fe3 8 SO42 4 H
i.e., 2 Fe2(SO4)3 2 H2SO4
In other words, the oxidation of the fool’s gold produces soluble iron(III)
sulfate (also called ferrous sulfate), Fe2(SO4)3, and sulfuric acid. The Fe3
ion is soluble in the highly acidic water that is first produced, the pH of which
can be less than zero, with the usual range being 0 to 2. However, once the
drainage from the highly acidic mine water becomes diluted and its pH con-
sequently rises, a yellowish-brown precipitate of Fe(OH)3 forms from Fe3,
discoloring the water and waterway and smothering plant and animal life
(including fish) in it (see Problem 13-7). Thus the pollution associated with
acid mine drainage is characterized in the first instance by the seeping from
the mine of copious amounts of both acidified water and a rust-colored solid.
Unfortunately, the concentrated acid can liberate toxic heavy metals—
especially zinc, copper, and nickel, but also lead, arsenic, manganese, and
aluminum—from their ores in the rock of the mine, further adding to the
pollution of the waterway.
Interestingly, the oxidation of disulfide ion to sulfate ion in the above
process is accomplished to some extent by the action of Fe3 as the oxidizing
agent, rather than by O2:
S22 14 Fe3 8 H2O 9: 2 SO42 14 Fe2 16 H
The phenomenon of acid drainage is currently of particular importance
in the many abandoned mines in the mountains of Colorado. However, the
most acidic water in the world comes from the Richmond Mine at Iron
Mountain, California. There the pH reaches as low as 3.6 because the high
temperatures (up to 47°C) of the mine water cause much of it to evaporate,
thus concentrating the acid. By comparison, the most acidic natural waters
occur near the Ebeko volcano in Russia, with a pH as low as 1.7; the acid-
ity is due to hydrochloric and sulfuric acids in the hot springs water.
The acid produced by acid mine drainage is spontaneously neutralized if
the soil contains limestone, in the same way we encountered for acid rain in
Chapter 4. For example, some of the coal mines in Pennsylvania discharge
water that is acidic (pH 5), whereas others discharge alkaline water result-
ing from dissolution of limestone. Powdered or chipped limestone can also be
added to water exiting the mine, although the insoluble calcium sulfate that
forms on the surface of the limestone particles prevents full reaction. Calcium
oxide or hydroxide can also be used to neutralize the acid. Raising the pH pre-
cipitates most of the liberated heavy metals as their insoluble hydroxides in a
sludge that can be removed from the water. An alternative method of remedi-
ation is the introduction into the waters of anaerobic bacteria that reverse the
oxidation of sulfate ion back to sulfide, thereby precipitating the heavy metals
as insoluble sulfides as well as raising the pH. In some instances, the sulfides are
rich enough in metals to be used as ores. Some abandoned mines have been
sealed to prevent further intrusions of water and oxygen, but this means of
preventing further production of acid is sometimes unsuccessful.
P R O B L E M 13-7
The Ksp values for Fe(OH)2 and Fe(OH)3 are 7.9 1015 and 6.3 1038,
respectively. Calculate the solubilities of Fe2 and Fe3 at a pH of 8, assum-
ing they are controlled by their hydroxides. Also calculate the pH value at
which the ion solubilities reach 100 ppm.
The pE Scale
Environmental scientists sometimes use the concept of pE to characterize the
extent to which natural waters are chemically reducing in nature, by analogy
to the way in which pH is used to characterize their acidity. In particular, pE
is defined as the negative base-10 logarithm of the effective concentration—
i.e., of the activity—of electrons in water, notwithstanding the fact that free
electrons do not exist in solution (any more than do bare protons, H ions).
pE values are dimensionless numbers; like pH, they have no units.
• Low pE values signify that electrons are readily available from substances
dissolved in the water, so the medium is very reducing in nature.
• High pE values signify that the dominant dissolved substances are oxidiz-
ing agents, so that few electrons are available for reduction purposes.
When several acids or bases are present in a water sample, one of them
usually makes a dominant contribution to the hydrogen or hydroxide ion
concentration. In such situations, the position of equilibrium for the other,
less dominant weak acids or bases is determined by the H or OH level set
by the dominant process. In a similar way, in natural waters one or another
redox equilibrium reaction is dominant, and it determines the electron avail-
ability for the other redox reactions that occur simultaneously. If we know the
position of equilibrium for the dominant process, we can calculate the pE and
from it the position of equilibrium—and hence the dominant species—in the
other reactions.
When a significant amount of O2 is dissolved in water, the reduction of
the oxygen to water is the dominant reaction determining overall electron
availability:
1
4 O2 H e Δ 12 H2O
In such circumstances, the pE of the water is related to the acidity and to the
partial pressure of oxygen and its acidity by the following equation, the origin
of which is discussed subsequently:
pE 20.75 log ([H] PO2 1/4)
20.75 pH 14 log (PO2)
For a neutral sample of water that is saturated by oxygen from air, i.e., when
PO2 0.21 atm and is free of carbon dioxide so that its pH 7, the pE value
is calculated from this equation to be 13.9. If the concentration of dissolved
oxygen is less than the equilibrium amount, then the equivalent partial pres-
sure of atmospheric oxygen is less than 0.21 atm, so the pE value is smaller
than 13.9 and in some cases even negative.
The pE expression given above looks very much like the Nernst equa-
tions encountered in the study of electrochemistry. Indeed the pE value for a
water sample is simply the electrode potential, E, for whatever process deter-
mines electron availability, but divided by RT兾F (where R is the gas constant,
T the absolute temperature, and F the Faraday constant), which at 25°C has
the value 0.0591:
pE E兾0.0591
Thus the pE expression for any half-reaction in water can be obtained from
its standard electrode potential E0, corrected by the usual concentration
and/or pressure terms and evaluated for a one-electron reduction. For example,
for the half-reaction linking the reduction of nitrate ion to ammonium ion,
we first write the process as a (balanced) one-electron reduction:
1
8 NO3 54 H e Δ 81 NH4 83 H2O
For this reaction, E0 0.836 volts (from standard tables), so pE0

E0兾0.0591 14.15. The equation for pE involves the subtraction from
the standard pE0 of the logarithm of the ratio of concentrations of prod-
ucts to reactants, each raised to its coefficient in the one-electron half-
reaction:
pE pE0 log ([NH4]1/8兾[NO3]1/8 [H]5/4)
14.15 54 pH 18 log ([NH4]兾[NO3])
(Here we have used the properties of logarithms that log ax x log a, and that
log (1兾b) log b.) As usual, the concentration of water does not appear in
the expression as its effect is already included in pE0.
P R O B L E M 13-8
Deduce the equilibrium ratio of NH4 to NO3 at a pH of 6.0 (a) for aerobic
water having a pE value of 11, and (b) for anaerobic water for which the
pE value is 3.
Returning to the subject of the dominant reaction that determines pE in

natural waters, we note that low values of dissolved oxygen usually are caused
by the operation of microorganism-catalyzed organic decomposition reactions,
and their dissolved products, rather than O2, can determine electron availabil-
ity. For example, in cases of low oxygen availability, the pE of water may be
determined by ions such as nitrate or sulfate. In the extreme case of the anaer-
obic conditions found at the bottoms of lakes in the summer and in swamps and
rice paddies, the electron availability is determined by the ratio of dissolved
methane, a reducing agent, to dissolved carbon dioxide, an oxidizing agent,
both of which are produced by the fermentation of organic matter, discussed
above. They are connected in the redox sense by the half-reaction
1
8 CO2 H e Δ 18 CH4 H2O
The pE value for water controlled by this half-reaction is
pE 2.87 pH 18 log (PCO2/PCH4)
For example, if the partial pressures of the two gases are equal and the water
is neutral, the pE value is 4.1. Thus the lower levels of a stratified lake are
characterized by negative pE values, whereas the oxygenated top layer has a
substantially positive pE.
The pE concept is useful in predicting the ratio of oxidized to reduced
forms of an element in a water body when we know how the electron
availability is controlled by another species. Consider, for example, the equi-
librium between the two common ions of iron:
Fe3 e Δ Fe2
For this reaction,
pE 13.2 log ([Fe3]兾[Fe2])
If the pE is determined by another redox process and its value is known, the
ratio of Fe3 to Fe2 can be deduced. Thus for the oxygen-depleted water dis-
cussed above that has a pE value of 4.1,
4.1 13.2 log ([Fe3]兾[Fe2])

so
log ([Fe3]兾[Fe2]) 17.3
and hence
[Fe3]兾[Fe2] 5 1018
In contrast, for a sample of aerobic water that has a pE of 13.9, the calculated
ratio is 5:1 in favor of the Fe3 ion. The transition between dominance of the
two forms occurs when their concentrations are equal:
pE 13.2 log (1) 13.2 0 13.2
P R O B L E M 13-9
Find the pE value for acidic water at which the ratio of concentrations of
Fe3 to Fe2 is 100:1.
P R O B L E M 13-10
Assuming that dissolved oxygen determines the electron availability in an
aqueous solution and that the partial pressure equivalent to the amount dis-
solved is 0.10 atm, deduce the ratio of dissolved CO2 to dissolved CH4 at a
pH of 4.
pE–pH Diagrams
A visual representation of the zones of dominance for the various oxidation
states in water of an element can be displayed in a pE–pH diagram, as shown
in Figure 13-4 for iron. It is clear from the diagram that the situation is more
complicated than that included in our example above, since, in moderately
acidic or alkaline environments, the solid hydroxides Fe(OH)2 and Fe(OH)3
also come into play in the equilibria. The solid lines in the diagrams indicate
combinations of pE and pH values where the concentrations of the two
species listed on either side of the line are equal. Thus we see from the top
left side of Figure 13-4 that equilibrium between dissolved Fe2 and Fe3
is important only for pH 3. Equality in the concentrations of these two
dissolved forms corresponds to the short horizontal line in the figure. As
expected from our calculations above, the transition occurs at pE 13.2
regardless of pH; hence the line is horizontal.
If iron is in the 3 state at higher pH, it exists predominantly as the solid
Fe(OH)3, whereas solutions containing iron in the 2 state are not mainly
precipitated until the solution becomes basic (Figure 13-4).
20
18
16 Fe3+ H2O O2
14
12
10
8
6
4
pE
Fe2+ Fe(OH)3
2
0
–2
–4
–6
–8
H2O H2 Fe(OH)2 FIGURE 13-4 The pE–pH
–10 diagram for the iron system
–12 at 105 M concentration.
[Source: Adapted from S. E.
–14 Manahan, Environmental
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Chemistry, 4th ed. (Boston, MA:
pH Willard Grant Press/PWS
Publishers, 1984).]
The shaded regions at the top right and bottom left side of the pE–pH
diagram represent extreme conditions, under which water itself is unstable to
decomposition, being oxidized or reduced to yield O2 or H2, respectively:
2 H2O 9: O2 4 H 4 e
and
2 H2O 2 e 9: H2 2 OH
Nitrogen Compounds in Natural Waters

In some natural waters, nitrogen occurs in inorganic and organic forms that
are of concern with respect to human health. As discussed in Chapter 6,
there are several environmentally important forms of nitrogen that differ in
the extent of oxidation of the nitrogen atom.
TABLE 13-2 Common Oxidation Numbers for Nitrogen
Increasing Levels of Nitrogen Oxidation

Oxidation Number of N ⫺3 0 ⫹1 ⫹2 ⫹3 ⫹4 ⫹5
Aqueous solution NH4 NO2 NO3

and salts NH3
Gas phase NH3 N2 N2O NO NO2
The common oxidation numbers of nitrogen, along with the most impor-
tant examples for each, are illustrated in Table 13-2. The most reduced forms
all have the 3 oxidation number, as occurs in ammonia, NH3, and its con-
jugate acid, the ammonium ion, NH4. The most oxidized form, having an
oxidation number of 5, occurs as the nitrate ion, NO3, which exists in
salts, aqueous solutions, and nitric acid, HNO3. In solution, the most impor-
tant intermediates between these extremes are the nitrite ion, NO2, and
molecular nitrogen, N2.
The pE–pH diagram for the existence of these forms in aqueous solution
is shown in Figure 13-5. Notice the relatively small field of dominance (the
small triangle on the right side of the diagram) for the nitrite ion, NO2, in
which nitrogen’s oxidation number has the intermediate value of 3. In par-
ticular, it is the predominant species only under alkaline conditions that are
intermediate in oxygen content (small positive pE values).
The equilibrium between the most highly reduced and the most highly
oxidized forms of nitrogen is given by the half-reaction
NH4 3 H2O Δ NO3 10 H 8 e

Previously we derived the equation relating pE to pH for this reaction written
as a reduction; this equation defines the diagonal line in Figure 13-4 that sep-
arates these two ions when their concentrations are equal, so that
pE 14.15 54 pH 81 log (1) 14.15 54 pH
We might conclude from this equation, and from the slope of the diagonal
line in Figure 13-5 separating NH4 and NO3, that since the oxidation of
ammonium ion is highly pH dependent, it would not occur under highly
acidic conditions. However, electron availability from the reduction of dis-
solved oxygen also decreases as the pH is lowered, so the pE value in such
16
H2O O2
12
NO3–
8
pE
4
NH4+
0 NO2–
–4 FIGURE 13-5 pE–pH

NH3 diagram for inorganic nitro-
H2O H2 gen in an aqueous system.
–8 [Source: Adapted from C. N.
Sawyer, P. L. McCarty, and G. F.
Parkin, Chemistry for Environ-
0 2 4 6 8 10 12 14 mental Engineering, 4th ed.
pH (New York: McGraw-Hill,
1994).]
water is quite high, and nitrate still predominates. For example, the pE
value calculated for oxygen in water at pH of 1 is about 20, so nitrate still
predominates.
Recall from Chapter 6 that in the microorganism-catalyzed process of
nitrification, ammonia and ammonium ion are oxidized to nitrate, whereas
in the corresponding denitrification process, nitrate and nitrite are reduced
to molecular nitrogen. Both processes are important in soils and in natural
waters. In aerobic environments such as the surface of lakes, nitrogen exists
as the fully oxidized nitrate, whereas in anaerobic environments such as the
bottom of stratified lakes, nitrogen exists as the fully reduced forms ammo-
nia and ammonium ion (Figure 13-3). Nitrite ion occurs in anaerobic envi-
ronments such as waterlogged soils that are not sufficiently reducing to
convert the nitrogen all the way to ammonia. Most plants can absorb nitro-
gen only in the form of nitrate ion, so any ammonia or ammonium ion used
as fertilizer must first be oxidized via microorganisms before it is useful to
such plant life.
P R O B L E M 13-11
Consider the reduction of nitrate ion to nitrite ion in a natural water system.
(a) Write the balanced one-electron half-reaction for the process if it
occurs in acidic media.
(b) Given that for this reaction, E0 0.881 volts, calculate pE0.
(c) From your answer to (a), deduce the expression relating pE to pE0 and
ion concentrations.
(d) From your result in part (c), obtain an equation relating the pE and pH
conditions under which the ratio of nitrate to nitrite is 100:1.
(e) From your result in part (c), deduce the ratio of nitrite to nitrate under
conditions of pE 12, pH 5.
Acid–Base Chemistry in Natural Waters:

The Carbonate System
Natural waters, even when “pure,” contain significant quantities of dissolved
carbon dioxide and of the anions it produces, as well as cations of calcium and
magnesium. In addition, the pH of such natural water is rarely equal to
exactly 7.0, the value expected for pure water. In this section, the natural
processes that involve these substances in natural waters are analyzed.
The CO2–Carbonate System

The acid–base chemistry of many natural water systems, including both rivers
and lakes, is dominated by the interaction of the carbonate ion, CO32, a
moderately strong base, with the weak acid H2CO3, carbonic acid. Loss of
one hydrogen ion from the acid produces the bicarbonate ion, HCO3 (also
called hydrogen carbonate ion):
H2CO3 Δ H HCO3 (1)
The acid dissociation constant for this process, K1, is numerically much
greater than K2, the constant for the second stage of ionization, which pro-
duces carbonate ion:
HCO3 Δ H CO32 (2)
In order to discover the dominant form at any given pH, it is instruc-
tive to consider a species diagram for the CO2–bicarbonate–carbonate
system in water, such as that shown in Figure 13-6. In it, the fraction of
the total inorganic carbon that is present in each of the three forms is
shown as a function of the master variable, the pH of the solution. Clearly,
carbonic acid is the dominant species at low pH ( 5), carbonate is
dominant at high pH ( 12), and bicarbonate is the predominant—but
not the only—species present in the pH

1.0
range of most natural waters, i.e., from 7 H2CO3 HCO3– CO32–
to 10. At the pH of natural rainwater,
5.6, most of the dissolved carbon dioxide 0.8
exists as carbonic acid, but a measurable
Fraction of carbon as
fraction is bicarbonate ion (Figure 13-6).
specified species
The curves in Figure 13-6 were con- 0.6
structed by solving for the three unknowns
[H2CO3], [HCO3], and [CO32], relative
0.4
to their total concentration, C, from indi-
vidual equilibrium constant expressions, as
detailed in Box 13-2. 0.2
2
[H2CO3]兾C [H ] 兾D
[HCO3]兾C K1 [H]兾D 0
4 5 6 7 8 9 10 11 12
pH
and
[CO32]兾C K1 K2兾D
FIGURE 13-6 Species
where the common denominator D [H]2 K1[H] K1 K2. diagram for the aqueous
carbon dioxide–bicarbonate
These expressions clearly show that H2CO3 is the dominant species
ion–carbonate system.
under conditions of high acidity and determine the other conditions as dis- [Source: S. E. Manahan,
cussed above. Environmental Chemistry,
The carbonic acid in natural waters results from the dissolution of carbon 6th ed. (Boca Raton, FL: Lewis
dioxide gas in water, the gas originating either in the air or from the decom- Publishers, 2000), Figure 3.3,
p. 54.]
position of organic matter in the water. The gas in the air and the acid in
water in contact with the surface usually are at equilibrium:
CO2(g) H2O(aq) Δ H2CO3(aq) (3)
The relevant equilibrium constant for this reaction is the Henry’s law con-
stant, KH, for CO2. [In fact, much of the dissolved carbon dioxide exists as
CO2 (aq) rather than as H2CO3 (aq), but following conventional practice we
collect the two forms together and represent it all as the latter.] The pH of
pure water in equilibrium with the current level of atmospheric CO2 is 5.6,
according to the methods discussed in Chapter 3 (see Problem 3-10).
The sequestration of carbon dioxide, as such, into oceans would result in
an increase in the acidity of the surrounding waters since the resulting increase
in H2CO3 concentration [reaction (3)] would give rise to further ionization
[reaction (1)], which is called ocean acidic for that reason (Chapter 7). The
resulting decrease in pH could affect biological life in the vicinity. Indeed, the
increase in the atmospheric concentration of CO2 that has already occurred has
resulted in a drop of about 0.1 pH unit in surface ocean water worldwide.
The predominant source of the carbonate ion in natural waters is
limestone rocks, which are largely made up of calcium carbonate, CaCO3.
BOX 13-2 Derivation of the Equations for Species Diagram Curves
he final equations relating the concentra- [CO32] in terms of [HCO3] and [H], and
T tions of carbonic acid, bicarbonate ion,
and carbonate ion to the pH, the equilibrium
substitute these relationships solutions into
the mass balance equation:
constants, and their total concentration C
were obtained by algebraic manipulation of [H2CO3] [HCO3] [H]兾K1
the three simultaneous equations.
[CO32] K2 [HCO3]兾[H]
Mass balance:
[H2CO3] [HCO3] [CO32] C Thus
Acid dissociation constants: ([HCO3] [H]兾K1) ([HCO3])
K1 [HCO3] [H]兾[H2CO3] (K2 [HCO3]兾[H]) C
and Solving this equation for bicarbonate and sub-
2 stituting the solution into the preceding pair
K2 [CO3 ] [H ]兾[HCO3 ]
of equations yields the expressions given in
From the second and third equations, respec- the main text for the fraction of each species
tively, we can express both [H2CO3] and present at any pH.
Although this salt is almost insoluble, a small amount of it dissolves when

water passes over it:
CaCO3(s) Δ Ca2 CO32 (4)
Natural waters that are exposed to limestone are called calcareous waters.
The dissolved carbonate ion acts as a base, producing its conjugate weak acid,
the bicarbonate ion, as well as hydroxide ion in the water:
CO32 H2O Δ HCO3 OH (5)
These reactions that occur in the natural three-phase (air, water, rock) system
are summarized pictorially in Figure 13-7; the reactions of the carbon
dioxide–carbonate system are summarized for convenience in Table 13-3.
In the discussions that follow, we analyze the effects on the composition
of a body of water of the simultaneous presence of both carbonic acid and cal-
cium carbonate. We shall see that the presence of each of these substances
increases the solubility of the other, and that the hydrogen ion and hydroxide
ion produced indirectly from their dissolution largely neutralize each other,
yielding water with almost neutral pH.
To obtain a qualitative understanding

of this rather complicated system, the Air CO2(g)
effect of the carbonate ion alone is first
considered. Water
H2CO3 H+ + HCO3–
Water in Equilibrium with Solid H2O
Calcium Carbonate CO32– + H2O OH– + HCO3 –

+
For simplicity, we first consider a (hypo- Ca2+
thetical) body of water that is in equilib-
rium with excess solid calcium carbonate
Rock, soil,
and in which all other reactions are of or sediments CaCO3(s)
negligible importance. The only process
of interest in this case is reaction (4)
(see Table 13-3). Recall from introductory
chemistry that the appropriate equilibrium FIGURE 13-7 Reactions
among the three phases (air,
constant for processes that involve the dissolution of slightly soluble salts in water, rocks) of the carbon
water is the solubility product, Ksp, which equals the concentrations of the dioxide–carbonate system.
product ions, each raised to its coefficient of the balanced equation. Thus,
for reaction (4), Ksp is related to the equilibrium concentration of the ions
by the equation
Ksp [Ca2] [CO32]
TABLE 13-3 Reactions in the CO2–Bicarbonate–Carbonate System
Reaction Equilibrium K Value

Number Reaction Constant at 25°C
1 H2CO3 Δ H HCO3 Ka1 (H2CO3) 4.5 107

2 HCO3 Δ H CO32 Ka2 (H2CO3) 4.7 1011
3 CO2(g) H2O(aq) Δ H2CO3(aq) KH 3.4 102
4 CaCO3(s) Δ Ca2 CO32 Ksp 4.6 109
5 CO32 H2O Δ HCO3 OH Kb (CO32) 2.1 104
6 CaCO3(s) H2O(aq)
Δ Ca2 HCO3 OH
7 H OH Δ H2O(aq) 1兾Kw 1.0 1014
8 CaCO3(s) CO2(g) H2O(aq)
Δ Ca2 2 HCO3
It follows from the stoichiometry of reaction (4) that as many calcium ions
are produced as carbonate ions, and that in this simplified system both ion
concentrations are equal to S, the solubility of the salt:
S solubility of CaCO3 [Ca2] [CO32]

After substituting S for the ion concentrations in the Ksp equation and insert-
ing the Ksp value from Table 13-3, we obtain
S2 4.6 109
Taking the square root of each side of this equation, a value for S can be
extracted:
S 6.8 105 M
Thus the solubility in water of calcium carbonate is estimated to be 6.8
105 mol/L, assuming that all other reactions are negligible.
P R O B L E M 13-12
Consider a body of water in equilibrium with solid calcium sulfate, CaSO4,
for which Ksp 3.0 105 at 25°C. Calculate the solubility, in g/L, of cal-
cium sulfate in water, assuming that other reactions are negligible.
According to reaction (5), dissolved carbonate ion acts as a base in water.

The relevant equilibrium constant for this process is the base ionization con-
stant, Kb, where
Kb(CO32) [HCO3] [OH]兾[CO32]
Since the equilibrium in this reaction lies to the right in solutions that are
not very alkaline, an approximation of the overall effect resulting from
the simultaneous occurrence of reactions (4) and (5) can be obtained by
adding together the equations for the two individual reactions. The overall
reaction is
CaCO3(s) H2O(aq) Δ Ca2 HCO3 OH (6)
Thus the dissolution of calcium carbonate in neutral water results essentially

in the production of calcium ion, bicarbonate ion, and hydroxide ion.
It is a principle of equilibrium that if several reactions are added together,
the equilibrium constant K for the combined reaction is the product of the
equilibrium constants for the individual processes. Thus, since reaction (6) is
the sum of reactions (4) and (5), its equilibrium constant K6 must equal
KspKb, the product of the equilibrium constants for reactions (4) and (5).
Since the acid and base ionization constants for any acid–base conjugate pair
such as HCO3 and CO32 are simply related by the equation
Ka Kb Kw 1.0 1014 at 25°C
it follows that for the conjugate base CO32
K5 Kb(CO32) Kw兾Ka (HCO3)
Since Ka for HCO3 is the Ka2 value for the carbonic acid system, then from
Table 13-3,
Kb 1.0 1014兾4.7 1011

2.1 104
Thus, since K6 for the overall reaction (6) is KspKb, its value is (4.6 109)
(2.1 104) 9.7 1013.
The equilibrium constant for reaction (6) is related to the ion concentra-
tions by the equation
K6 [Ca2] [HCO3] [OH]
If we make the approximation that reaction (6) is the only process of rele-
vance in the system, then from its stoichiometry we have a new expression for
the solubility of CaCO3, namely
S [Ca2] [HCO3] [OH]
Upon substitution of S for the concentrations, we obtain
S 3 9.7 1013
Taking the cube root of both sides of this equation, we find
S 9.9 105 M
Thus the estimated solubility for CaCO3 is 9.9 105 M, in contrast to the
lesser value of 6.8 105 M that we obtained when the reaction of carbon-
ate ion was ignored. The CaCO3 solubility here is greater than estimated
from reaction (4) alone, since much of the carbonate ion it produces subse-
quently disappears by reacting with water molecules. In other words, the
equilibrium in reaction (4) is shifted to the right since a large fraction of its
product reacts further [reaction (5)].
From these results, it is clear that the saturated aqueous solution of cal-
cium carbonate is moderately alkaline; its pH can be obtained from the
hydroxide ion concentration of 9.9 105 M:
pH 14 pOH 14 log10[OH] 14 log10(9.9 105) 10.0
That the solution is alkaline is not surprising, given that the carbonate ion,
as weak bases go, is a moderately strong one.
P R O B L E M 13-13
Repeat the calculation of the solubility of calcium carbonate by the approxi-
mate single equilibrium method using a realistic wintertime water temperature
of 5°C; at that temperature, Ksp 8.1 109 for CaCO3, Ka 2.8 1011
for HCO3, and Kw 0.2 1014. By comparing the result with that in the
foregoing text for 25°C, decide whether the solubility of calcium carbonate
increases or decreases with increasing temperature.
P R O B L E M 13-14
What is the net reaction when reactions (1) and (3) are added together?
How is the equilibrium constant for this combined process related to K1 and
K3? Show that the pH of the aqueous solution resulting from a CO2 partial
pressure of 0.00037 atm in the combined process has the same value of 5.6 as
is determined by considering the individual reactions consecutively, as in
Problem 3-10.
In the analysis above, it has been assumed that calcium carbonate is dis-
solving in pure water and that the reaction of carbonate with water deter-
mines the pH. In some real-world situations, the pH of the aqueous solution
is predetermined by the presence of some dominant source of H or OH, so
the contribution from calcium carbonate is negligible. In such cases, the ratio
of bicarbonate to carbonate ion can be determined from Kb and the known,
fixed [OH]:
[HCO3]兾[CO32] Kb 兾[OH]
and thus
[HCO3] Kb [CO32]兾[OH]
The solubility S of calcium carbonate, and the resulting dissolved calcium ion
concentration, here equal the sum of the carbonate and bicarbonate ion con-
centrations, so
S [Ca2] [CO32] [HCO3]
[CO32] Kb [CO32]兾[OH]
[CO32] (1 Kb 兾[OH])
If, for convenience, we temporarily define f (1 Kb 兾[OH]), then
S f [CO32]
Substituting this equation for [Ca2] into

the Ksp expression gives 3.5
Ksp f [CO32]2
3.0
Solving for the carbonate concentration,
we obtain 2.5
2 1/2
[CO3 ] (Ksp 兾f) 2.0
Log S
and hence
1.5
S f [CO32] (f Ksp)1/2
{Ksp (1 Kb 兾[OH])}1/2 1.0
Thus, as expected by application of Le 0.5

Châtelier’s principle to the reactions, the
solubility of calcium carbonate decreases 0
4 5 6 7 8 9 10 11 12
as the (fixed) hydroxide concentration pH
increases, the limit at high levels of
OH being (Ksp)1/2, the value we obtained
assuming no reaction of carbonate ion with water. In contrast, for water that FIGURE 13-8 Molar
is neutral or acidic and therefore low in hydroxide ion, the CaCO3 solubility solubility,
0.5
S, in units of
is much larger than this value, as illustrated in Figure 13-8, where the loga- Ksp , of CaCO3 in CO2-
free water versus pH.
rithm of S is plotted against the pH of the water body.
Water in Equilibrium with Both CaCO3

and Atmospheric CO2
The systems discussed above are somewhat unrealistic since they fail to con-
sider the other important carbon species in water—namely, carbon dioxide
and carbonic acid—and the reactions that involve them. These reactions
will now be considered in the context of a body of water that is also in equi-
librium with solid calcium carbonate, i.e., the three-phase system illustrated
in Figure 13-7.
At first sight, it might seem that since reaction (1) provides another
source of bicarbonate ion, then by Le Châtelier’s principle the production of
bicarbonate from the reaction (5) of carbonate with water should be sup-
pressed. However, a more important consideration is that reaction (1) pro-
duces hydrogen ion, which combines with the hydroxide ion that is produced
in reaction (4) by the interaction of carbonate ion with water:
H OH Δ H2O(aq) (7)
Consequently, the equilibrium positions of both reactions that produce bicar-
bonate ion are shifted to the right due to the disappearance of one of their
products by the above reaction.
If reactions (1), (3), (4), (5), and (7) are all added together to deduce the
net process, then after canceling common terms the net result is
CaCO3(s) CO2(g) H2O(aq) Δ Ca2 2 HCO3 (8)
In other words, combining equimolar amounts of solid calcium carbonate and
atmospheric carbon dioxide yields aqueous calcium bicarbonate, Ca(HCO3)2,
without any apparent production or consumption of acidity or alkalinity:
calcium carbonate (rock) carbon dioxide (air) calcium bicarbonate
(in solution)
Natural waters in which this overall process occurs can be viewed as the site
of a giant titration of an acid that originates with CO2 from air with a base
that originates with carbonate ion from rocks. [Note that we need not con-
sider reaction (2) in this analysis, since reaction (5) of the conjugate base of
bicarbonate with water was included.] In the ocean neutral scheme of seques-
tration (Chapter 7), bulk carbon dioxide is reacted with solid calcium car-
bonate or with some other calcium-containing salt; the resulting slurry of
calcium bicarbonate (or other salt) is then transported to and deposited in
the ocean. This technique avoids the pH-lowering side effect of the ocean
acidic scheme in which CO2 is directly dissolved in the ocean water.
It should be noted that each of the individual reactions added together is
itself an equilibrium that does not lie entirely to the right. Since the reactions
differ in their extent of completion, it is an approximation to state that the
overall reaction shown above is the only resulting reaction. Nevertheless, it
is the dominant process, and it is mathematically convenient to first consider
this process alone in estimating the extent to which CaCO3 and CO2 dis-
solve in water when both are present.
Since reaction (8) equals the sum of reactions (1), (3), (4), (5), and (7),
its equilibrium constant K8 is the product of their equilibrium constants:
K8 KspKbKHKa1兾Kw
Here Ka1 is the first acid dissociation constant for carbonic acid. KH is the
Henry’s law constant (see Chapter 3) for reaction (3). Since Kw is the ion
product for water, the equilibrium constant for reaction (7) is 1兾Kw. The
other constants in the equation for K8 have been defined previously (see
Table 13-3). Thus at 25°C for the overall reaction (8), it follows that
K8 1.5 106
From the balanced equation for the reaction, it follows that the expression for
K8 is
K8 [Ca2] [HCO3]2兾PCO2
If the calcium concentration again is called S, then from the stoichiom-
etry of reaction (8) the bicarbonate concentration must be twice as large,
equal to 2S; after substitution for the concentrations in the equation for K8
and rearrangement, we obtain
S (2S)2 K8 PCO2
or
4 S3 K8 PCO2
Thus the solubility of calcium carbonate increases as the cube root of the par-
tial pressure of carbon dioxide to which the water is exposed:
S (K8 PCO2/4)1/3
Substituting the current partial pressure of CO2 in the atmosphere,
0.00036 atm, corresponding to an atmospheric concentration of CO2 of
365 ppm (Chapter 6), and the numerical value of K8 into this equation yields
S 5.1 104 mol/L1 [Ca2]
and thus
[HCO3] 2S 1.0 103 M
The amount of CO2 dissolved is also equal to S and is 35 times that which
dissolves without the presence of calcium carbonate (see results of Problem
3-10). Furthermore, the calculated calcium concentration is four times that
calculated without the involvement of carbon dioxide. Thus the acid reac-
tion of dissolved CO2 and the base reaction of dissolved carbonate have a
synergistic effect on each other that increases the solubilities of both the gas
and the solid (see Table 13-4). In other words, water that contains carbon
dioxide more readily dissolves calcium carbonate. In fact, groundwater may
Calculated Ion Concentrations for Aqueous

TABLE 13-4 Equilibrium Systems
Ion CaCO3 CO2 and CaCO3
[HCO3] 9.9 105 M 1.0 103 M

[CO32] — 8.8 106 M
[Ca2] 9.9 105 M 5.2 104 M
[OH] 9.9 105 M 1.8 106 M
[H] 1.0 1010 M 5.6 109 M
pH 10.0 8.3
become supersaturated with carbon dioxide as a result of biological decom-

position processes; and in that case, the calcium carbonate solubility
increases even more—at least until the water reaches the surface, when
degassing of the excess CO2 would occur.
P R O B L E M 13-15
Repeat the above calculation for the solubility of CaCO3 in water that is also
in equilibrium with atmospheric CO2 for a water temperature of 5°C. At this
temperature, KH 0.065 for CO2 and K1 for H2CO3 is 3.0 107; see Prob-
lem 13-13 for other necessary data.
Finally, the residual concentrations of CO32, of H, and of OH in the

system can be deduced from equilibrium constants for reactions (4), (5), and
(7), since equilibria in these processes are in effect, notwithstanding the over-
all reaction (8). Thus from reaction (4),
[CO32] Ksp兾[Ca2] 4.6 109兾5.1 104 9.0 106 M
From reaction (5),
[OH] Kb [CO32]兾[HCO3]
(2.1 104) (9.0 106)兾1.0 103 1.9 106
and finally from reaction (7)
[H] Kw兾[OH] 1.0 1014兾1.9 106 5.3 109
From this value for the hydrogen ion concentration, we conclude that
according to this calculation, river and lake water at 25°C whose pH is deter-
mined by saturation with CO2 and CaCO3 should be slightly alkaline, with a
pH of about 8.3.
Typically, the pH values of calcareous waters lie in the range from 7 to 9,
in reasonable agreement with our calculations. Due to the smaller amount of
bicarbonate in noncalcareous waters, their pH values are usually close to 7.
Of course, if natural waters are subject to acid rain, the pHs can become sub-
stantially lower since there is little HCO3 or CO32 readily available with
which to neutralize the acid.
About 80% of natural surface waters in the United States have pH val-
ues between 6.0 and 8.4. Lakes and rivers into which acid rain falls will have
elevated levels of sulfate ion and perhaps of nitrate ion since the principal
acids in the precipitation are H2SO4 and HNO3 (see Chapter 4).
P R O B L E M 13-16
In waters subject to acid rain, the pH is determined not by the CO2–carbonate
system but rather by the strong acid from the precipitation. Assuming that
equilibrium with atmospheric carbon dioxide is in effect, calculate the con-
centration of HCO3 in natural waters with pH 6, 5, and 4 at 25°C. (See
Table 13-3 for data.)
P R O B L E M 13-17
Using algebraic expressions and numerical values for Ka1 and Ka2 of H2CO3
(Table 13-3), calculate the pH values for which [H2CO3] [HCO3] and for
which [HCO3] [CO32].
Ion Concentrations in Natural Waters

and Drinking Water
The Abundant Ions in Fresh Water
As is evident from Table 13-5, the most abundant ions found in samples of
unpolluted fresh calcareous water usually are calcium and bicarbonate, as
expected from our previous analysis. Commonly, such water also contains
magnesium ion, Mg2, principally from the dissolution of MgCO3; plus
some sulfate ion, SO42; smaller amounts of chloride ion, Cl, and sodium
ion, Na; and even smaller levels of fluoride ion, F, and potassium ion,
K. The overall reaction (8) of carbon dioxide and calcium carbonate
implies that the ratio of bicarbonate ion to calcium ion should be 2:1, and
this is indeed a rule that is closely obeyed on average in river water in North
America and Europe. The calculated calcium ion concentration, 5.1
104 M, agrees well with the North American river-water average value
of 5.3 104 M, and similarly for the bicarbonate ion data. The close
agreement between the calculated and the experimental results is some-
what fortuitous because river-water temperatures on average lie below
25°C—which results in a higher CO2 solubility than has been assumed—
and because several minor factors have been oversimplified in the calcula-
tion. In fact, even calcareous river water is usually unsaturated with respect
to CaCO3.
Water in rivers and lakes that is not in contact with carbonate salts con-
tains substantially fewer dissolved ions than are present in calcareous waters.
The concentration of sodium and potassium ions may be as high as those of
calcium, magnesium, and bicarbonate ions in these fresh waters. Even in
areas with no limestone in the soil, the waters contain some bicarbonate ion
due to the weathering of aluminosilicates in submerged soil and rock in the
River Water Concentrations and Drinking Water

TABLE 13-5
Standards for Ions
River Water Molar Drinking Water

Concentration Concentration in ppm
Maximum Recommended
Concentration
Average Average Average
Ion for World for U.S. U.S. U.S. Canada
*HCO3 9.2 104 9.6 104 60

Ca2 3.8 104 3.8 104 15
Mg2 1.6 104 3.4 104 8
Na 3.0 104 2.7 104 6 200
Cl 2.3 104 2.2 104 8 250 250
SO42 1.1 104 1.2 104 12 250 500
K 5.4 105 5.9 105 2
F — 5.3 106 0.1 0.8 – 2.4 1.5
NO3 1.4 105 —
Fe3 7.3 106 —
*Note: The value for bicarbonate is actually the total alkalinity.
Sources: World data from R. A. Larson and E. J. Weber, Reaction Mechanisms in Environmental Organic Chemistry
(Boca Raton, FL: Lewis Publishers).
presence of atmospheric carbon dioxide. The weathering reaction can be

written in general terms as
M(Al-silicate)(s) CO2(g) H2O 9: M HCO3 H4SiO4

Here M is a metal such as potassium, and the anion is one of the many alumi-
nosilicate ions found in rocks (see Chapter 16). The weathering of potassium
feldspar is an example of one of the most important sources of potassium ion
in natural waters:
3 KAlSi3O8(s) 2 CO2(g) 14 H2O 9:

2 K 2 HCO3 6 H4SiO4 KAl3Si3O10(OH)2(s)
Thus bicarbonate normally is the predominant anion in both calcareous and
noncalcareous waters since it is produced by the dissolution of limestone and
aluminosilicates, respectively.
The average compositions of river water in the United States and in the
world as a whole are given in Table 13-5. As discussed, the values for the
calcium and magnesium ion concentrations vary significantly from place to

place, depending upon whether or not the underlying soil is calcareous.
Fresh water in which the concentration of ions is abnormally high is
called saline water and is usually unsuitable for drinking. Most saline water is
the result of irrigation, in which water is transported into land where little
rainfall occurs. The water largely evaporates if the climate is hot and dry,
leaving behind salts of the ions that were present in the irrigation water. The
runoff water from rainfall and irrigation into water supplies consequently is
saline. If the irrigation water is recycled, it becomes more and more saline as
time goes on. The wintertime de-icing of roads in northern climates also con-
tributes salinity to water bodies.
Fluoride Ion in Water

The level of fluoride ion, F, in water also displays substantial variations, from
less than 0.01 ppm to more than 20 ppm, in different regions of the world. The
source of most F is weathering of the mineral fluorapatite, Ca5(PO4)3F.
In Mexico and some European countries, sodium fluoride, NaF, is added
to table salt. In many communities of English-speaking countries—including
the United States (about half the population), Canada, Australia, and New
Zealand in which the F concentration in the drinking-water source is low—
a soluble fluoride compound such as fluorosilicic acid, H2SiF6, or its sodium
salt, both of which react with water to release fluoride ion, is often added in
order to bring the fluoride level up to about 1 ppm, i.e., 5 105 M. This
value was considered at least in the past to be optimum in strengthening
children’s teeth against decay while providing a margin of safety. If the fluoride
level is in excess of this value, as it is in some natural waters, deleterious effects
on teeth such as mottling can occur. The maximum contaminant level (MCL)
of fluoride in U.S. drinking water is 4 ppm. Almost all brands of toothpaste
available in developed countries contain added fluoride in the form of sodium
fluoride, stannous fluoride, SnF2, or sodium monofluorophosphate. Most
children in North America also receive topical fluoride not only from their
toothpaste, but in some cases by application from their dentists.
The addition of fluoride ion to public supplies of drinking water contin-
ues to be a controversial subject because at high concentrations fluoride is
known to be poisonous and perhaps carcinogenic, and because some people
feel that it is immoral to force everyone to drink water to which a substance
has been added. In fact, for many people, the total amount of fluoride ion
ingested from food and beverages (especially tea) exceeds that from water.
Bottled Drinking Waters

The maximum concentration of ions recommended for drinking water in the
United States and in Canada is also listed in Table 13-5. The concentration of
sodium ion, Na, in water is of interest since high consumption of it from water
and salted food is believed to increase blood pressure, which may lead to cardio-
vascular disease. Excessive sulfate, beyond 500 mg/L, causes a laxative effect in
some people. It is interesting to note that some varieties of bottled drinking
water, which people presumably drink in preference to tap water due to health
concerns about the latter, exceed the recommended values for some ions. Sev-
eral well-known bottled waters exceeded the drinking water standards for
arsenic and/or fluoride in a 1999 survey by the U.S. National Resources
Defense Council. However, they were remarkably free of chloroform, a sub-
stance that plagues municipal water supplies, as discussed in Chapter 14. A
more recent survey found that most brands would meet the new 10-ppm stan-
dard for arsenic (Chapter 15) but that bisphenol-A (Chapter 12) is leached
from the plastic into the water contained in most large polycarbonate jugs.
Suppliers of bottled water sometimes advertise their products as having
“zero” concentrations of fluoride and/or sodium ions or as being sodium-free or
fluoride-free. These are misleading statements since in reality the actual con-
centrations are not zero but below the level of detection in the analytical
method used by the bottler or below a threshold specified by government.
“Zero” is not a meaningful chemical concept to answer the question of “how
much” of a substance is present in a sample.
Seawater
The total concentration of ions in seawater is much higher than that in fresh
water since it contains large quantities of dissolved salts. The predominant
species in seawater are sodium and chloride ions, which occur at about 1000
times their average concentration in fresh water. Seawater also contains
some Mg2 and SO42 and lesser amounts of many other ions. If seawater
is gradually evaporated, the first salt to precipitate is CaCO3 (present to
the extent of 0.12 g/L), followed by CaSO4 H2O (1.75 g/L), then NaCl
(29.7 g/L), MgSO4 (2.48 g/L), MgCl2 (3.32 g/L), NaBr (0.55 g/L), and finally
KCl (0.53 g/L). Thus “sea salt” is a mixture of all these salts, which together
constitute about 3.5% of the mass of seawater. Due primarily to the operation
of the CO2–bicarbonate–carbonate equilibrium system discussed previously
for fresh water, the average pH of surface ocean water is about 8.1. Seawater
has a low organic content, its DOC value being about 1 mg/L.
Alkalinity Indices for Natural Waters

The actual concentrations of the cations and anions in a real water sample
cannot simply be assumed to be the theoretical values calculated above for
calcium, carbonate, and bicarbonate for two reasons:
• the water may not be in equilibrium with either solid calcium carbonate
or with atmospheric CO2; and
• other acids or bases may also be present.
The index devised by analytical chemists to represent the actual concen-

tration in water of the anions that are basic is provided by the alkalinity value
for the sample. Alkalinity is a measure of the ability of a water sample to act as a
base by reacting with hydrogen ions. In practical use, the alkalinity of a body of
water is a handy measure of the capacity of the water body to neutralize acids
and hence to resist acidification when acid rain falls into it. (Alkalinity dif-
fers from [OH], or pOH, in that the latter equals only the hydroxide con-
centration a water sample has at a particular moment and does not include its
ability to generate additional OH if acid is added to it.) From an operational
viewpoint, alkalinity, more properly termed total alkalinity, is the number of
moles of H required to titrate 1 liter of a water sample to the end point. For
a solution containing carbonate and bicarbonate ions, as well as OH and
H, by definition
(total) alkalinity 2 [CO32] [HCO3] [OH] [H]
The factor of 2 appears in front of carbonate ion concentration since in the
presence of H it is first converted by the ion to bicarbonate ion, which is
then converted by a second hydrogen ion to carbonic acid:
CO32 H Δ HCO3
HCO3 H Δ H2CO3
Minor contributors to the alkalinity of fresh-water systems can include dis-
solved ammonia and the anions of phosphoric, boric, and silicic acids, and H2S,
as well as natural organic matter.
The alkalinities of natural waters range from less than 5 105 M
(50 mM) to more than 2 103 M (2000 mM), compared to the value of
about 3 104 M that corresponds to our estimate for water in contact with
atmospheric CO2 (see Problem 13-19). Lakes having alkalinities less than
about 200 mM are considered “high” in sensitivity to acid rain, those from
200 to 400 mM are classified as “moderate” in sensitivity, and those with alka-
linity greater than 400 mM are considered to have “low” sensitivity. Alkalin-
ity values are sometimes reported as milligrams of CaCO3 equivalent, rather
than moles of H, per liter in a manner similar to that explained below for
the hardness concept.
By convention in analytical chemistry, methyl orange is used as the indi-
cator in titrations by which total alkalinity is determined. Methyl orange is
chosen because it does not change color until the solution is slightly acidic
(pH 4); under such conditions, not only has all the carbonate ion in the
sample been transformed to bicarbonate, but virtually all the bicarbonate ion
has been transformed to carbonic acid (see Problem 13-18 and Figure 13-6).
Another index encountered in the analysis of natural waters is the phe-
nolphthalein alkalinity (also called carbonate alkalinity), which is a measure
of the concentration of the carbonate ion and of other similarly basic anions.
In order to titrate only CO32 and not HCO3 as well, the indicator phe-
nolphthalein or one with similar characteristics is used. Phenolphthalein
changes color in the pH range 8 to 9, so it provides a fairly alkaline end point.
At such pH values, only a negligible amount of the bicarbonate ion has been
converted to carbonic acid, but the majority of CO32 has been converted to
HCO3 (Figure 13-6). Thus,
phenolphthalein alkalinity [CO32]
P R O B L E M 13-18
Calculate the value of the ratios [HCO3]兾[CO32] and [H2CO3]兾[HCO3]
at pH values of 4 and 8.5 to confirm the statements made above concerning
the nature of the species present at the methyl orange and phenolphthalein
end points of the titrations. [Hint: Use the equilibrium constant expressions and
K values for reactions (1) and (2).]
P R O B L E M 13-19
Calculate the value expected for the total alkalinity and for the phenolph-
thalein alkalinity of a 25°C saturated solution of calcium carbonate in water
that is also in equilibrium with atmospheric carbon dioxide. Use the con-
centrations quoted in the last column of Table 13-4.
P R O B L E M 13-20
Calculate the total alkalinity for a sample of river water whose phenolph-
thalein alkalinity is known to be 3.0 105 M, whose pH is 10.0, and whose
bicarbonate ion concentration is 1.0 104 M.
The alkalinity value for a lake is sometimes used by biologists as a mea-

sure of its ability to support aquatic plant life, a high value indicating a high
potential fertility. The reasons for such a situation are often the following
ones. Algae extract the carbon dioxide they need for photosynthesis from
bicarbonate ion, which is plentiful in calcareous waters, by a reversal of the
CO2–CaCO3 reaction discussed previously:
Ca2 2 HCO3(aq) 9: CO2 CaCO3(s) H2O
Indeed, small crystals of calcium carbonate are sometimes observed in lakes
where there is active photosynthesis.
CO2 H2O sunlight 9: CH2O polymer 12 O2

(as algae)
In noncalcareous waters, which have low alkalinity and low calcium content,
dissociation of the bicarbonate ion in the water forms not only carbon diox-
ide but also hydroxide ion:
HCO3 Δ CO2 OH
The algae readily exploit this CO2 for their photosynthetic needs, at the cost
of allowing a buildup of hydroxide ion to such an extent that the lake water
becomes quite basic—with a pH as high as 12.3 in some cases.
The Hardness Index for Natural Waters

As a measure of certain important cations present in samples of natural
waters, analytical chemists often use the hardness index, which measures the
total concentration of the ions Ca2 and Mg2, the two species that are prin-
cipally responsible for hardness in water supplies. Chemically, the hardness
index is defined in this way:
hardness [Ca2] [Mg2]
Experimentally, hardness can be determined by titrating a water sample with
ethylenediaminetetraacetic acid (EDTA), a substance that forms very strong
complexes with metal ions other than those of the alkali metals (see Chapter 15
for details). Traditionally, hardness is expressed not as a molar concentration
of ions but as the mass in milligrams (per liter) of calcium carbonate that contains
the same total number of dipositive (2) ions. For example, a water sample that
contains a total of 0.0010 mole of Ca2 Mg2 per liter would possess a
hardness value of 100 mg of CaCO3, since the molar mass of CaCO3 is 100 g
and 0.0010 mole of it weighs 0.1 g, or 100 mg.
Most calcium enters water from either CaCO3 in the form of limestone
or from mineral deposits of CaSO4. The source of much of the magnesium is
dolmitic limestone, CaMg(CO3)2. Hardness is an important characteristic of
natural waters, since calcium and magnesium ions form insoluble salts with
the anions present in soaps, thereby forming a scum in wash water. Water is
termed “hard” if it contains substantial concentrations of calcium and/or
magnesium ions; thus calcareous water is “hard.” Some scientists define water
as being hard if its hardness index exceeds 150 mg/L.
Many areas possess soils that contain little or no carbonate ion, and thus
its dissolution and reaction with CO2 to produce bicarbonate do not occur.
Such “soft” water typically has a pH much closer to 7 than does hard water,
since it contains few basic anions. However, there are lakes with little dis-
solved calcium or magnesium but relatively high concentrations of dissolved
sodium carbonate, Na2CO3; such lakes have a very low degree of hardness
but are high in alkalinity.
Interestingly, people who live in hard-water areas are found to have a
lower average death rate from ischemic heart disease than do people living in
areas with very soft water. Recent research in rural Finland found the risk of
heart attacks decreased continuously as the magnesium concentration in the
local water supply increased.
P R O B L E M 13-21
What is the value of the hardness index in milligrams CaCO3/L for a 500-mL
sample of water that contains 0.0040 g of calcium ion and 0.0012 g of magne-
sium ion?
P R O B L E M 13-22
Calculate the hardness, in milligrams CaCO3/L, of water that is in equilib-
rium at 25°C with carbon dioxide and calcium carbonate, using results in
the last column of Table 13-4. Assume the water is free of magnesium. Is the
calculated value greater or less than the median hardness value found for
surface waters of 37 mg/L?
Aluminum in Natural Waters

The concentration of aluminum ion, Al3, in natural waters normally is
quite small, typically about 106 M. This low value is the consequence of the
fact that in the typical pH range for natural waters (6 to 9), the solubility of
the aluminum contained in rocks and soils to which the water is exposed is
very small. The solubility of aluminum in water is controlled by the insolubil-
ity of aluminum hydroxide, Al(OH)3. Given that the Ksp of the hydroxide is
about 1033 at usual water temperatures, then for the reaction
Al(OH)3 Δ Al3 3 OH
it follows that
[Al3] [OH]3 1033
Take, for instance, a sample of water whose pH is 6. Since the hydroxide con-
centration in such water is 108 M, it follows that
[Al3] 1033兾(108)3 109 M
Although this value is very small, for every one-unit decrease of the pH, the
concentration of aluminum ion increases by a factor of 1000, so it reaches
106 M at pH 5 and 103 M at a pH of 4. Thus aluminum is much more
soluble in highly acidified rivers and lakes than in those where pH values do
not fall below 6 or 7. Indeed, Al3 is usually the principal cation in waters
whose pH is less than 4.5, exceeding even the concentrations of Ca2 and
Mg2, which are the dominant cations at pH values greater than 4.5.
In the recent past, fears arose that human ingestion of aluminum from
drinking water and from the use of aluminum cooking pots was a major cause
of Alzheimer’s disease; however, the research upon which this conclusion was
reached could not be reproduced. Today many neuroscientists do not believe
that there is a strong connection between the disease and intake of the metal,
since past epidemiological studies on this matter have not been definitive
or consistent. However, Canadian and Australian research reported in the
mid-1990s indicates that consumption of drinking water with greater than
100 ppb aluminum—not an uncommon level in drinking water purified by
aluminum sulfate (see Chapter 14)—can lead to neurological damage such as
memory loss and perhaps to a small increase in the incidence of Alzheimer’s
disease.
It is thought that the principal deleterious effect of acid waters upon fish
arises from the solubilization of aluminum from soil and its subsequent exis-
tence as a free ion in the acidic water, as discussed in Chapter 4. Unfortu-
nately, the Al(OH)3 then precipitates as a gel on contact with the less acidic
gills of the fish, and the gel prevents the normal intake of oxygen from water,
thus suffocating the fish.
It is also believed that aluminum mobilization in soils is one of the
stresses that acid rain places on trees, which in turn results in the dieback of
forests. Soils that contain limestone are usually considered to be buffered
against much change in pH, due to the ability of carbonate and bicarbonate
ion to neutralize H, but over a period of decades, surface soil may gradually
lose its carbonate content due to a continual bombardment by acid rain.
Thus soils receiving acid rain eventually become acidified. When the pH of
the soil drops below about 4.2, aluminum leaching from soil and rocks
becomes particularly appreciable. Such acidification has occurred in some
regions of central Europe, including Poland, the former Czechoslovakia, and
eastern Germany, and the resulting solubilization of aluminum may have
contributed to the forest diebacks observed there in the 1980s.
P R O B L E M 13-23
What is the concentration, in grams per liter, of dissolved aluminum in water
having a pH of 5.5?
P R O B L E M 13-24
Calculate the pH value at which the aluminum ion concentration dissolved
in water is 0.020 M, assuming that it is controlled by the equilibrium with
solid aluminum hydroxide.
Review Questions
1. Write the balanced half-reaction involving O2 11. What are the acid and the base that dominate
when it oxidizes organic matter in acidic waters. the chemistry of most natural water systems and
whose interaction produces bicarbonate ion?
2. How does temperature affect the solubility of
O2 in water? Explain what is meant by thermal 12. What is the source of most of the carbonate
pollution. ion in natural waters? What name is given to
waters that are exposed to this source?’’
3. Define BOD and COD, and explain why their
values for the same water sample can differ slightly. 13. Write the approximate net reaction between
Explain why natural waters can have a high BOD. carbonate ion and water in a system that is not also
exposed to atmospheric carbon dioxide. Is the
4. What do the acronyms TOC and DOC stand
resulting water acidic, alkaline, or neutral?
for, and how do they differ in terms of what they
measure? 14. Write the approximate net reaction between
carbonate ion and water in a system that is exposed
5. Write the half-reaction, used in the COD titra-
to atmospheric carbon dioxide. Is the resulting
tion, which converts dichromate ion to Cr3 ion,
water mildly acidic or mildly alkaline? Explain why
and balance it.
the production of bicarbonate ion from carbonate
6. Write the balanced chemical reaction by which ion does not inhibit its production from carbon
organic carbon, represented as CH2O, is dispropor- dioxide, and vice versa.
tionated by bacteria under anaerobic conditions.
15. If two equilibrium reactions are added
7. Draw a labeled diagram classifying the top and together, what is the relationship between the
bottom layers of a lake in summer as either oxidiz- equilibrium constants for the individual reactions
ing or reducing in character, and show the stable and that for the overall reaction?
forms of carbon, sulfur, nitrogen, and iron in the
16. What is the natural source of fluoride ion in
two layers.
water? How and why is the fluoride level in drink-
8. What are some examples of highly reduced and ing water artificially increased to about 1 ppm in
highly oxidized sulfur in environmentally impor- many municipalities?
tant compounds? Write the balanced reaction by
17. Define the total alkalinity index and the
which sulfate can oxidize organic matter.
phenolphthalein alkalinity index for water.
9. Explain the phenomenon of acid mine drainage,
18. Define the hardness index for water.
writing balanced chemical equations as appropri-
ate. How does Fe3 also act as an oxidizing agent 19. Which are the most abundant ions in clean,
here? fresh water?
10. What is meant by the pE of an aqueous solu- 20. Explain why aluminum ion concentrations in
tion? What does a low (negative) pE value imply acidified waters are much greater than those in
about the solution? What species determines the neutral water. How does the increased aluminum
pE value in aerated water? ion level affect fish and trees?

See the discussion of focus areas and the princi- (b) Would these same environmental problems
ples of green chemistry in the Introduction before or worker hazards be eliminated by the use of
attempting these questions. BioPreparation?
1. What takes place during the scouring of cotton, 3. The development of BioPreparation by
and why is this process necessary for the production Novozymes won a Presidential Green Chemistry
of finished cotton fibers? Challenge Award.
2. BioPreparation (an enzymatic process) replaced (a) Into which of the three focus areas for these
the use of large amounts of sodium hydroxide in the awards does this award best fit?
scouring of cotton. (b) List at least three of the twelve principles of
(a) Describe any environmental problems or worker green chemistry that are addressed by the green
hazards that would be associated with the use of chemistry developed by Novozymes.
sodium hydroxide solutions in the scouring of cotton.
Additional Problems
See Table 13-3 for data.
1. Over a period of several days, estimate your 3. (a) Balance the reduction half-reaction that
approximate daily water usage in the categories of converts SO42 to H2S under acidic conditions.
showering/bathing, clothes washing, toilets, dish- (b) Deduce the expressions relating pE to pH, the
washing, and cooking. (Many flush toilets display concentration of sulfate ion, and the partial pres-
volume-per-flush data. Washing machine water sure of hydrogen sulfide gas, given that for the half-
volume capacity can be estimated from the dimen- reaction, pE0 3.50 V when the pH is 7.0.
sions of the washer cavity: 1 L 10 cm 10 cm
(c) Deduce the partial pressure of hydrogen sulfide
10 cm. Using a measuring cup, discover how
when the sulfate ion concentration is 105 M and
long it takes your shower to deliver 1 liter of water,
the pH is 6.0 for water that is in equilibrium with
and adjust the data accordingly for the length of
atmospheric oxygen.
your average shower.)
4. Calculate the solubility of lead(II) carbonate,
2. The TOC parameter for water samples is mea-
PbCO3 (Ksp 1.5 1013) in water, given that
sured by oxidizing the organic material to carbon
most of the carbonate ion it produces subse-
dioxide and then measuring the amount of this gas
quently reacts with water to form bicarbonate
evolved from the solution. If a 5.0-L sample of
ion. Recalculate the solubility assuming that none
wastewater produced 0.25 mL of carbon dioxide
of the carbonate ion reacts to form bicarbonate.
gas, measured at a pressure of 0.96 atm and a tem-
Is your result significantly different from that
perature of 22°C, calculate the TOC for the sam-
calculated assuming complete reaction of carbonate
ple. Assuming the average composition of the
with water?
organic matter to be CH2O, calculate what the
chemical oxygen demand for the water sample 5. The bicarbonate ion, HCO3, can potentially
would be due to its organic content. [The gas con- act as an acid or as a base in water. Write the
stant R 0.082 L atm mol1 K1.] chemical equations for these two processes, and
from the information given in this chapter, deter- 7. The O2 concentration of a water sample can be
mine the corresponding acid and base dissociation determined using the so-called Winkler titration
constants. Given the relative magnitudes of the method. In it, the oxygen in a small sample of the
dissociation constants, decide whether the domi- water is reacted with MnSO4 in a basic solution.
nant reaction of bicarbonate in water will be as an The reaction precipitates the manganese as MnO2,
acid or as a base. Calculate the pH of an aqueous which converts added I to I2. Molecular iodine is
0.010 M solution of sodium bicarbonate in water then quantitatively determined by titrating it in
using the dominant reaction alone and assuming acidic solution with a standardized solution of
that the amounts of carbonate ion and carbonic sodium thiosulfate, Na2S2O3. The set of equations
acid from other sources are negligible in this case. for the reactions is:
6. A sample of lake water at 25°C is analyzed and 2 Mn2 4 OH O2(aq) 9:
the following parameters are found: 2 MnO2(s) 2 H2O
total alkalinity 6.2 104 M
MnO2(s) 4 H 2 I 9: Mn2 I2 2 H2O
phenolphthalein alkalinity 1.0 105 M
pH 7.6 I2(aq) 2 S2O32 9: S4O62 2 I
hardness 30.0 mg/L
In determining the BOD of a sample of water, a
[Mg2] 1.0 104 M
chemist tested two 10.00-mL samples of the water,
Extract all possible single-ion concentrations that one before and one after the five-day incubation
you can by combining one or more of these data. period. They required 10.15 and 2.40 mL of a
Also determine whether or not the water is at equi- 0.00100 M standard solution of K2S2O3. Calculate
librium with respect to the carbonate–bicarbonate the BOD, in units of milligrams per liter, of this
system and whether or not it is saturated with water sample. On the basis of these results, would
calcium carbonate. you consider this water to be polluted?
Further Readings
1. T. Oki and S. Kanae, “Global Hydrological 4. “What’s in That Bottle?” Consumer Reports
Cycles and World Water Resources,” Science (January 2003): 38.
313(2006): 1968.
5. B. Hileman, “Fluoridation of Water,” Chemical
2. W. Stumm and J. J. Morgan, Aquatic Chemistry: and Engineering News (August 1, 1998): 26.
Chemical Equilibria and Rates in Natural Waters,
6. F. M. M. Morel and J. G. Hering, Principles and
3rd ed. (New York: Wiley-Interscience, 1996).
Applications of Aquatic Chemistry (New York:
3. A. Kousa et al., “Calcium: Magnesium Ratio Wiley, 1993).
in Local Groundwater and Incidence of Acute
7. G. Sposito, ed., The Environmental Chemistry
Myocardial Infarction Among Males in Rural
of Aluminum, 2nd ed. (Boca Raton, FL: Lewis
Finland,” Environmental Health Perspectives 114
Publishers, 1996).
(2006): 730.
C H A P T E R
14
THE POLLUTION AND
PURIFICATION OF WATER
topics are used:
 Acid–base and equilibrium concepts and calculations; pH
 Basic structural organic chemistry (as in the Appendix)
 Oxidation numbers; redox half-reactions
 Catalysis
 Distillation

 Maximum contaminant levels (Chapter 10)
 BOD (Chapter 13)
 VOCs (Chapter 3)
 Photochemical reactions; UV light (Chapters 1–5)
 Free radicals (Chapter 1)
 BTX hydrocarbons (Chapter 7)
 ppm concentration scale in water (Chapter 10)
 No effects level, NOEL (Chapter 11)
Introduction
The pollution of natural waters by both biological and chemical contaminants
is a worldwide problem. There are few populated areas, whether in developed
or undeveloped countries, that do not suffer from one form of water pollution
or another. In this chapter, we shall survey the various methods—both tradi-
tional and innovative—by which water can be purified. We begin by dis-
cussing techniques that are used to purify drinking water from relatively
uncontaminated sources, and then consider the pollution and remediation of
601
602 Chapter 14 The Pollution and Purification of Water
groundwater and of sewage and wastewater. Lastly, we investigate modern

advanced techniques whereby polluted air and water can be cleansed.
Water Disinfection
The quality of “raw” (untreated) water, whether drawn from surface water or
groundwater, that is intended eventually for drinking varies widely, from
almost pristine to highly polluted. Because both the type and quantity of pol-
lutants in raw water vary, the processes used in purification also vary from
place to place. The most commonly used procedures are shown in schematic
form in Figure 14-1. Before discussing the major topic of disinfection, we shall
discuss the various nondisinfection steps that are often taken in the overall
purification process.
Aeration of Water
Aeration is commonly used in the improvement of water quality. Municipal-
ities aerate drinking water that is drawn from underground aquifers in order
to remove dissolved gases such as the foul-smelling hydrogen sulfide, H2S,
and organosulfur compounds, as well as volatile organic compounds, some of
which may have a detectable odor. Aeration of drinking water also results in
reactions that produce CO2 from the most easily oxidized organic material. If
necessary for reasons of odor, taste, or health, most of the remaining organics
can be removed by subsequently passing the water over activated carbon,
although this process is relatively expensive, so rather few communities use it
(see Box 14-1). Another advantage to aeration is that the increased oxygen
content of water oxidizes water-soluble Fe2 to Fe3, which then forms insol-
uble hydroxides (and related species) that can be removed as solids.
Fe3 3 OH 9: Fe(OH)3(s)
(Recall that ions listed in equations without a state specified are assumed to
be in aqueous solution.)
After aeration, colloidal particles in the water are removed. If the water
is excessively hard, calcium and magnesium are removed from it before the
final stages of disinfection and the addition of fluoride. All these procedures
are described below (see Figure 14-1).
Removal of Calcium and Magnesium

If the water comes from wells in areas having limestone bedrock, it will con-
tain significant levels of Ca2 and Mg2 ions, which are usually removed dur-
ing processing since these ions can interfere with soaps and detergents used
by consumers for washing. Calcium can be removed from water by addition of
phosphate ion in a process analogous to that discussed later for phosphate
removal; here, however, phosphate is added in order to precipitate the
BOX 14-1 Activated Carbon
ctivated carbon (activated charcoal) is a increases nor decreases the area. The internal
A very useful solid for purifying water of
small organic molecules present in low con-
structure of the solid involves series of chan-
nels (pores) of progressively decreasing size
centrations. The ability of this material to that are produced by the charring and partial
remove contaminants from water and to oxidation processes. The internal sites where
improve its taste, color, and odor has been adsorption occurs are large enough only for
known for a long time; indeed, the ancient small molecules, including chlorinated sol-
Egyptians used charcoal-lined vessels to store vents. At the typical ppm concentrations
water for drinking purposes. found for organic contaminants in water, each
Activated carbon is produced by anaerobi- gram of activated carbon can adsorb a few
cally charring a high-carbon-content material percent of its mass in contaminants such as
such as peat, wood, or lignite (a soft brown chloroform and the dichloroethenes as well as
coal) at temperatures below 600°C, followed by much higher masses of TCE, PCE, and pesti-
a partial oxidation process using carbon dioxide cides such as dieldrin, heptachlor, and DDT.
or steam at a slightly higher temperature. Once a sample of activated carbon has
The removal of contaminants by activated reached near-saturation in terms of adsorbed
carbon is a physical adsorption process and organics, three alternatives are available. It
therefore is reversible if sufficient energy is can be simply disposed of in a landfill, it can be
applied. The characteristic that makes acti- incinerated to destroy it and the adsorbed con-
vated carbon such an excellent adsorber is its taminants, or it can be heated to rejuvenate the
huge surface area, about 1400 m2/g. This sur- surface by driving off the organic pollutants,
face is internal to the individual carbon parti- which can then be incinerated or catalytically
cles, so that crushing the material neither oxidized.
Aeration Settling and Hardness Disinfection

precipitation removal
Al or Fe salt to Phosphate Ammonia
precipitate colloids and fluoride
Consumer
Water
Suspended
Air Ca2+ pptd. as phosphate Cl2 or ozone or ClO2 particles
FIGURE 14-1 The common stages of purification of drinking water.

calcium ion. More commonly, calcium ion is removed by precipitation and

filtering of the insoluble salt calcium carbonate, CaCO3. The carbonate
ion is either added as sodium carbonate, Na2CO3, or if sufficient HCO3 is
naturally present in the water, hydroxide ion, OH, is added in order to
convert dissolved bicarbonate ion to carbonate:
OH HCO3 9: CO32 H2O
Ca2 CO32 Δ CaCO3(s)

Magnesium ion precipitates as magnesium hydroxide, Mg(OH)2, when the
water is made sufficiently alkaline, i.e., when the OH ion content is increased.
After removal by filtration of the solid CaCO3 and Mg(OH)2, the pH of the
water is readjusted to near-neutrality by bubbling carbon dioxide into it.
P R O B L E M 14-1
Ironically, calcium ion is often removed from water by adding hydroxide ion
in the form of Ca(OH)2. Deduce a balanced chemical equation for the reac-
tion of calcium hydroxide with dissolved calcium bicarbonate, Ca(HCO3)2,
to produce insoluble calcium carbonate. What molar ratio of Ca(OH)2 to
dissolved calcium should be added to ensure that almost all the calcium is
precipitated?
Disinfection to Prevent Illness

In terms of causing immediate sickness and even death, biological contami-
nants of water are almost always much more important than chemical ones.
For that reason, we begin our discussion of the purification of water by exten-
sively discussing its disinfection, i.e., the elimination of microorganisms that
can cause illness.
Many of the microorganisms in raw water are present as a result of contam-
ination by human and animal feces. The microorganisms are principally
• bacteria, including those of the Salmonella genus, one species of which
causes typhoid. In this category is also Escherichia coli O157:H7, whose trans-
mission in water has caused a number of deaths in recent years, including
those from an outbreak in Walkerton, Ontario, in 2000;
• viruses, including polio viruses, the hepatitus-A virus, and the Norwalk
virus; and
• protozoans (single-celled animals), including Cryptosporidium and Giardia
lamblia.
Because many microorganisms of these three types are pathogenic, causing
mild to serious and sometimes fatal illnesses, they must be largely removed
from water before it is suitable for drinking.
Notwithstanding well-known techniques for water disinfection, many of

which have been used extensively for more than a century in developed
countries, there are still about 1 billion people in the world who do not yet
have access to safe drinking water. According to the World Health Organiza-
tion, about 4500 children die daily from the consequences of polluted water
and inadequate sanitation.
Filtering of Water
In addition to dissolved chemicals, the raw water that is obtained from
rivers, lakes, or streams contains a multitude of tiny particles, some of which
consist of or contain microorganisms. Many of the small, suspended particles
consist of clay, resulting from the erosion of soil and rock, whether by natu-
ral forces or due to plowing of land for agriculture, mining, or commercial or
housing development. The suspended particles increase water’s turbidity and
thereby reduce the ability of light to penetrate deeply enough to support
photosynthesis.
The larger of the particles suspended in water are often removed by sim-
ply filtering it. Indeed, the filtration of water by passing it through a bed of
sand is the oldest form of water purification known, dating back to ancient
times. The sand retains suspended solids of all types, including microorgan-
isms, down to about 10 mm in size.
Recently it was realized that forcing raw water through filters having
especially small openings can be used instead of chemicals or light to disinfect
water of some viruses and bacteria, and even some dissolved chemicals, by
just removing them.
Removal of Colloidal Particles by Precipitation

Most municipalities allow raw water to settle, since this permits large particles
to settle out or to be readily separated. However, much of the insoluble matter
originating from rocks and soil, and from the disintegration and decomposi-
tion of water-based plants and animals, will not precipitate spontaneously
since it is suspended in water in the form of colloidal particles. These are par-
ticles that have diameters ranging from 0.001 to 1 mm and consist of groups of
molecules or ions that are weakly bound together. These groups dissolve as a
unit, rather than breaking up and dissolving as individual ions or molecules. In
many cases, the individual units within a colloidal particle are spatially organ-
ized such that the surface of the particles contains ionic groups. The ionic
charges on the surface of one particle repel those of like charge on neighbor-
ing particles, preventing their aggregation and subsequent precipitation.
Colloidal particles must be removed from drinking water for both aes-
thetic and health and safety reasons. To capture the colloidal particles, a
small amount of either iron(III) sulfate, Fe2(SO4)3, or aluminum sulfate,
Al2(SO4)3 (“alum”), is deliberately dissolved in the water. By then making

the water neutral or alkaline in pH (7 and up), both the Fe3 and Al3 ions
produced from the salts form gelatinous hydroxides that physically incorpo-
rate the colloidal particles and form a removable precipitate. The water is
greatly clarified once this precipitate has been removed. Commonly, after the
removal of the colloidal particles, the water is filtered through sand and/or
some other granular material.
Although the idealized formulas of the precipitates are Fe(OH)3 and
Al(OH)3, the actual situation is much more complex. For example, alu-
minum actually forms a polymeric cation, Al13O4(OH)247, which produces
a loose network structure that is held together by hydrogen bonds. This net-
work entraps the colloidal particles and forms the precipitate. Only if the pH
rises to quite a high value does the aluminum in solution form the expected
hydroxide Al(OH)3. Since the concentration of aluminum sulfate added to
the water is only about 10 mm/L, very little residual aluminum ion is left in
the treated water.
P R O B L E M 14-2
Calculate the approximate number of atoms contained in colloidal particles
of (a) 1-mm and (b) 0.01-mm diameters, assuming that their densities are sim-
ilar to that of water and that the atomic mass of the atoms averages 10 g/mol.
Disinfection of Water by Membrane Technology

Water can be purified of most contaminant ions, molecules, and small parti-
cles, including viruses and bacteria, by passing it through a membrane in
which the individual holes, called pores, are of uniform and microscopic size.
The range of sizes of the various contaminants in raw water are summarized in
Figure 14-2. Clearly, for a technique to be effective in providing a barrier, the
pore size of the membrane must be smaller than the contaminant size.
In the processes of microfiltration and ultrafiltration, a membrane or
some other analogous barrier containing pores of 0.002- to 10-mm diameter
(2–10,000 nm) is employed to remove larger constituents from water. The
water can be forced through the barrier by pressure or can be drawn through it
by suction, leaving behind the larger impurities. In one modern version of this
technology, the barrier is composed of thousands of strands of plastic tubing
having walls that are pierced with thousands of tiny pores of similar size.
Some bacteria and colloid particles are as small as 0.1 mm and so can pass
through conventional filters and even some microfilters (Figure 14-2).
Viruses can be as small as 0.01 mm and therefore require at least the ultrafil-
tration level to eliminate them. However, filtration using membranes can be
Microfiltration
Ultrafiltration
Nanofiltration
Reverse osmosis
H2O
Pressure Bacteria Ca2+
Na+
and Viruses Mg2+
K+
colloids M2+
10 1 0.1 0.01 0.001 0.0001

FIGURE 14-2 Filtration of
Size of contaminant ( μm)
contaminants by various
methods.
used to disinfect water if a sufficiently small pore size is used and if the water
is later irradiated with ultraviolet light to eliminate any microbes that have
passed through the filtration stage.
Neither microfiltering nor ultrafiltering removes dissolved ions or small
organic molecules. Generally speaking, before water is treated using mem-
branes with even smaller pores (see below), it must be pretreated to remove
the larger particles—especially colloids—which would otherwise foul the
finer membrane by leaving deposits.
Membrane systems have been developed recently that purify water of vir-
tually all contaminants by nanofiltration. Water is pumped under pressure
through fine membranes that have pores only about 1 nm wide, which there-
fore remove not only most bacteria and viruses, but also any larger organic
molecules that would nourish the regrowth of bacteria. These nanofilters still
allow water molecules to pass through the filter, since the molecules are only
a few tenths of a nanometer in size. Unlike ultrafiltration, nanofiltration can
be used to soften water, since hydrated divalent ions such as Ca2 and Mg2
are larger than the pores and so do not pass through. Hydrated monovalent
ions such as sodium and chloride also pass through some nanofilters, but not
through ones with subnanometer pore sizes. As a consequence, some nanofil-
ter membrane systems can be used to desalinate seawater and to help purify
wastewater, as discussed later in this chapter.
Reverse Osmosis
The ultimate in membrane filtration occurs in the widely used technique
called reverse osmosis, sometimes called hyperfiltration. Here, water is forced
under high pressure to pass through the pores in a semipermeable membrane,
composed of an organic polymeric material such as cellulose acetate or triac-
etate or a polyamide. Since only water (and other molecules of its small size)
can pass efficiently through the pores, the liquid on the other side of the
membrane is purified water. The solution on the impact side of the membrane
becomes more and more concentrated in contaminants as time goes on and is
discarded. The procedure is called reverse osmosis because, by use of pressure,
the natural phenomenon of osmosis—by which pure water would sponta-
neously migrate through the membrane into solution, thereby diluting it—is
reversed.
Particles, molecules (including small organic molecules), and ions down
to less than 1 nm (0.001 mm) in size, or about 150 g/mol in mass, are removed
by reverse osmosis. It is particularly useful for removing alkali and alkaline
earth metal ions, as well as salts of heavy metals. Thus it is employed in hos-
pitals and renal units to produce water that is particularly free of ions. Reverse
osmosis is used on large scale for the desalination, i.e., the removal of salts,
from seawater and brackish water, a topic considered in Box 14-2.
BOX 14-2 The Desalination of Salty Water
esalination is the production of fresh Gulf. The evaporation method is even more
D water from salty water, often seawater, by
the removal of its ions. There are more than
energy-intensive than is reverse osmosis.
Modern, large-scale thermal distillation plants
15,000 large-scale desalination plants in oper- use energy to raise salty water to the boiling
ation, located in more than 125 countries. point, then reduce the air pressure above the
Reverse osmosis is widely used in some areas of liquid to create a partial vacuum into which
the world, such as the Middle East, to generate the liquid readily “flash” evaporates, leaving
drinking water from salt water. the salt behind in the remaining liquid. The
The other main commercial desalination vapor is removed and condensed as desalted
process is the thermal distillation—evaporation— water. Thermal distillation plants are often
of seawater or brackish water. Desalination of incorporated within electricity-generating
seawater by evaporation is a technique that plants to use the low-grade waste steam from
goes back to ancient times; it is especially the latter as their energy source.
suited even today for seawater that contains Desalination of water is also sometimes
particularly high levels of dissolved salts and accomplished using the technique of electro-
suspended solids in areas such as the Persian dialysis, which is described later in this chapter.
Water destined for drinking purposes is commonly pretreated, e.g., by

filtering it through sand and gravel, and passing it over activated carbon to
remove the larger particles such as bacteria, etc., and treating it with chlo-
rine, before subjecting it to reverse osmosis in order to minimize fouling and
degradation of the membrane.
Because of the high pressures needed to force water through the small
pores in the membrane, reverse osmosis is an energy-intensive process. A
pressure of about 2 atm is sufficient for portable and domestic units, but a
greater force must be applied to brackish or salty water. However, advances in
the engineering of large-scale desalination plants have markedly reduced
energy consumption by redirecting pressure from waste brine to low-pressure
incoming water.
Reverse osmosis tends to be wasteful of water, since so much of it—a
third to a half—is discarded. Also, the accumulated discharges of brine—
sometimes called concentrate—from desalination processes of any kind can
cause cumulative environmental problems, such as harming fish populations,
in the immediate area of the seacoast into which it is deposited if it is not first
treated. In some locations, the brine is injected into an underground saltwa-
ter aquifer. In others, the brine is left to evaporate in large outdoor pools, and
the salts disposed of later.
Some domestic consumers of drinking water have installed small under-
the-sink reverse osmosis units to further purify their water by removing
unwanted contaminants such as heavy metal cations (e.g., lead), hard water
cations (calcium and magnesium), anions (e.g., nitrate and fluoride), and
organic molecules from water obtained from domestic supplies. Small reverse
osmosis units are also used in medical facilities for producing water that is
particularly ion-free.
Some bottled water has been purified and deionized by reverse osmosis,
but small amounts of salts are reintroduced into it before it is sold to con-
sumers. Drinking large amounts of deionized water is not healthy, since the
ion balance in the body can be upset as a consequence.
Disinfection by Ultraviolet Irradiation

Ultraviolet light can also be used to disinfect and purify water. Powerful
lamps containing mercury vapor whose excited atoms emit UV-C light (see
Chapter 1) centered at a wavelength of 254 nm are immersed in the water
flow. About 10 seconds of irradiation are usually sufficient to eliminate the
toxic microorganisms, including Cryptosporidium, which is resistant to treat-
ment by some other methods. The germicidal action of the light disrupts the
DNA in microorganisms, preventing their subsequent replication and
thereby inactivating the cells. At the molecular level, absorption of UV-C
light results in the formation of new covalent bonds between nearby thymine
units on the same strand of DNA. If sufficient such thymine dimers are
formed, the DNA molecule becomes so distorted that subsequent replication

of the organism is prevented.
The use of ultraviolet light to purify water is complicated by the presence
of dissolved iron and humic substances, both of which absorb the UV light
and thus reduce the amount available for disinfection. Small solid particles
suspended in the water also inhibit the action of the UV light since they can
shade or absorb bacteria and also scatter or absorb the light. An advantage of
UV disinfection technology is that small units can be employed to serve small
population bases, whether in the developed or developing world, so the con-
tinuous monitoring activity of chemical systems is avoided. As discussed
later, UV light can also be used to purify water of dissolved organic com-
pounds, but by a different mechanism.
Disinfection by Chemical Methods:

Ozone and Chlorine Dioxide
To rid drinking water of harmful bacteria and viruses, especially those arising
from human and animal fecal matter, by use of a chemical agent requires an
oxidizing agent more powerful than O2. In some localities, particularly in
France and other parts of western Europe but also in some North American
cities—Montreal and Los Angeles are examples—ozone is used for this pur-
pose. Since O3 cannot be stored or shipped because of its very short lifetime,
it must be generated on-site by a relatively expensive process involving elec-
trical discharge (20,000 V) in dry air. The resulting ozone-laden air is bubbled
through the raw water; about 10 minutes of contact is usually sufficient for
disinfection. Since the lifetime of ozone molecules is short, there is no resid-
ual protection in the purified water to ensure that it will not be subject to
future contamination. Some pollutants in water react with the ozone itself
and others with free radicals such as hydroxyl and hydroperoxy (Chap-
ters 1–5) that are produced when ozone reacts with water.
Unfortunately, the reaction of ozone with bromine in water leads to the
formation of oxygen-containing organic compounds, particularly those con-
taining the carbonyl group, C " O , such as formaldehyde and other low-
molecular-weight aldehydes and various other compounds, some of which are
toxic. In addition, ozone reacts with bromide ion, Br, present in the water
to produce the bromate ion, BrO3, a carcinogen in test animals and proba-
bly also in humans. The reaction of ozone with bromide, a natural con-
stituent of water that is often present at ppm concentrations, occurs in several
steps; the overall reaction is
Br 3 O3 9: BrO3 3 O2
The bromate ion produced by ozonation may subsequently react with
organic matter in the water to produce toxic organobromine compounds,
though experiments have shown that the only brominated product under
water treatment conditions is dibromoacetonitrile, CHBr2CN, produced by

the reaction of bromate ion with acetonitrile. The MCL (maximum contam-
inant level) of bromate ion in drinking water is set at 10 ppb (0.010 ppm) by
the U.S. EPA. Substances such as bromate ion that are produced during water
purification are called disinfection by-products, or DBPs. All known chemi-
cal methods of disinfecting water produce DBPs of one type or another.
Similarly, chlorine dioxide gas, ClO2, is used in more than 300 North
American and several thousand European communities to disinfect water.
The ClO2 molecules, themselves free radicals, operate to oxidize organic
molecules by extracting electrons from them:
ClO2 4 H 5 e 9: Cl 2 H2O
The organic cations created in the accompanying oxidation half-reaction
subsequently react with oxygen and eventually become more fully oxidized.
Since chlorine dioxide is not a chlorinating agent—it does not generally
introduce chlorine atoms into the substances with which it reacts—and since
it oxidizes the dissolved organic matter, much smaller amounts of toxic
organic chemical by-products are formed than if molecular chlorine were
used (see below).
As is the case with ozone, ClO2 cannot be stored since it is explosive in
the high concentrations that its practical use calls for, so it must be generated
on-site. This is accomplished by oxidizing its reduced form, the chlorite ion,
ClO2, from the salt sodium chlorite, NaClO2:
ClO2 9: ClO2 e
Some of the chlorine dioxide in these processes is converted to chlorate ions,
ClO3. The presence of chlorite and chlorate ions as residuals in the final
water has raised health concerns due to their potential toxicity. The U.S.
EPA has set an MCL of 1.0 ppm for chlorite ion, and a MRDL (maximum
residual disinfectant level) of 0.8 ppm for chlorine dioxide, in drinking water.
Disinfection by Chlorination: History

The most common water purification agent used in North America is
hypochlorous acid, HOCl. About half the U.S. population uses surface
water, and one-quarter of the population uses groundwater, that is disinfected
by HOCl. This neutral, covalent compound kills microorganisms, as it read-
ily passes through their cell membranes. In addition to being effective, disin-
fection by chlorination is relatively inexpensive. Incorporating a small excess
of the chemical in the treated water provides it with residual disinfection
power during its subsequent storage and transmission to the consumer. Chlo-
rination is more common than ozonation in North America because gener-
ally the raw water is less polluted. Chlorination of public water supplies in the
United States, Canada, and Great Britain began in the early years of the
twentieth century. For the previous 50 years, chlorination had been practiced
on an emergency basis during epidemics caused by water-borne pathogens.
Disinfection by Chlorination: Production

of Hypochlorous Acid
Like ozone, HOCl is not stable in concentrated form and so cannot be stored.
For large-scale installations, e.g., municipal water treatment plants, it is gen-
erated by dissolving molecular chlorine gas, Cl2, in water. At moderate pH
values, the equilibrium in the reaction of chlorine with water lies far to the
right and is achieved in a few seconds:
Cl2(g) H2O(aq) Δ HOCl(aq) H Cl
Thus a dilute aqueous solution of chlorine in water contains very little aque-
ous Cl2 itself. If the pH of the reaction water were allowed to become too
high, the result would be the ionization of the weak acid HOCl to the
hypochlorite ion, OCl, which is less able to penetrate bacteria on account
of its electrical charge. Once chlorination is complete, the pH of the water is
adjusted upward, if necessary, by the addition of lime, CaO.
In small-scale applications of chlorination, as in swimming pools, the
handling of cylinders of Cl2 is inconvenient and dangerous. The chlorine gas
can be produced as needed on the spot by the electrolysis of salty water. More
commonly, hypochlorous acid instead is generated from the salt calcium
hypochlorite, Ca(OCl)2, or is supplied as an aqueous solution of sodium
hypochlorite, NaOCl. In water, an acid–base reaction occurs to convert most
of the OCl in these substances to HOCl:
OCl H2O Δ HOCl OH
Close control of the pH in an environment like a swimming pool is necessary
to avoid the shift to the left side in the position of equilibrium for this reac-
tion that occurs if a very alkaline condition is permitted to prevail. On the
other hand, corrosion of pool construction materials can occur in acidic
water, so the pH is usually maintained above 7 to prevent such deterioration.
Maintenance of an alkaline pH also prevents the conversion of dissolved
ammonia, NH3, to the chloramines NH2Cl, NHCl2, and especially NCl3,
which is a powerful eye irritant:
NH3 3 HOCl 9: NCl3 3 H2O
Significant respiratory and eye irritation problems from exposure to chlo-
ramines in the air around indoor swimming pools has been reported when
appropriate ventilation is unavailable.
It is desirable to adjust the equilibrium point in the OCl 9: HOCl
reaction to favor the predominance of the disinfectant molecular species,
HOCl. Since the equilibrium between HOCl and OCl shifts rapidly in
favor of the ion between pH values of 7 and 9, however, the acidity level must
be meticulously controlled. Swimming pool acidity can be adjusted by the

addition of acid (in the form of sodium bisulfate, NaHSO4, which contains the
acid HSO4) or a base (sodium carbonate, Na2CO3) or a buffer (sodium
bicarbonate, NaHCO3, which contains the amphoteric anion HCO3).
Chlorine must be constantly replenished in outdoor pools since UV-B and
the short-wavelength components of UV-A light in sunshine are absorbed
by and decompose the hypochlorite ion, thereby affecting the equilibrium in
the OCl 9: HOCl process toward the ion:
UV
2 ClO 9: 2 Cl O2
Hypochlorous acid can also be generated by the reaction with water of

the chlorine-containing compound isocyanuric acid, C3N3O3H3:
O
H H
N N
O N O
H
Either the trichloro derivative, in which each hydrogen is replaced by Cl to

give C3N3O3Cl3, or the sodium dichloro derivative, C3N3O3Cl2Na, is used.
In either case, the OH group from water combines with the chlorine to
produce HOCl and the hydrogen of H2O becomes bonded to the nitrogen,
giving isocyanuric acid, C3N3O3H3:
C3N3O3Cl3 3 H2O Δ C3N3O3H3 3 HOCl
Since this process is an equilibrium, not all the compound is immediately
converted to hypochlorous acid. As HOCl is used up, both by its use as a dis-
infectant and through dissociation in sunlight of its ionic form, the equilib-
rium shifts to the right and more HOCl is produced. None of the various
forms of isocyanuric acid absorb UV light, so its chlorine is “protected”
against decomposition by sunlight. Since the bulk chlorinated forms of iso-
cyanuric acid are expensive, it is common to supply hypochlorite from a
cheaper source and to add isocyanuric acid as a stabilizer, temporarily revers-
ing the above reaction to “store” the chlorine until it is needed.
Disinfection by Chlorine: By-Products and

Their Health Effects
An important drawback to the use of chlorination in disinfecting water is the
concomitant production of chlorinated organic substances, some of which
are toxic, since HOCl is not only an oxidizing agent but also a chlorinating
agent. Examples of these important by-products are the group of halogenated
acetic acids (haloacetic acids), such as CH2Cl9COOH, which the U.S. EPA
restricts to 60 ppb as an MCL annual average for drinking water, and halo-
acetonitriles, such as CH2Cl9CN. Dichloroacetic acid, CHCl29COOH, is
a more potent carcinogen than is chloroform.
If the water to be disinfected contains phenol, C6H5OH, or a derivative
thereof, chlorine readily substitutes for the hydrogen atoms on the ring to
give rise to chlorinated phenols: These compounds have an offensive odor
and taste and are toxic. Some communities switch from chlorine to chlorine
dioxide when their supply of raw water is temporarily contaminated with
phenols to avoid the formation of chlorinated phenols.
A more general problem with chlorination of water lies in the produc-
tion of trihalomethanes, THMs. Their general formula is CHX3, where the
three X atoms can be chlorine or bromine or a combination of the two. The
THM of principal concern is chloroform, CHCl3, which is produced when
hypochlorous acid reacts with organic matter dissolved in the water (see
Box 14-3). Chloroform is a suspected liver carcinogen in humans, and it
may also give rise to negative reproductive and developmental effects. Its
BOX 14-3 The Mechanism of Chloroform Production in Drinking Water
umic acids, with which HOCl reacts In the presence of the HOCl, the terminal car-
H to form chloroform, are water-soluble,
nonbiodegradable components of decayed
bon becomes trichlorinated, and the 9CCl3
group is readily displaced by the OH in water
plant matter. Of particular importance are to yield chloroform:
humic acids that contain 1,3-dihydroxybenzene
HOCl
rings. The carbon atom (#2) located between R 9 C 9 CHCl2 R 9 C 9 CCl3
those carrying the 9 OH groups is readily
chlorinated by HOCl, as in this elementary O O
case: OH
H
R 9 C 9 OH CHCl3
OH O
O
1 Cl
HOCl 2
Cl Analogous sequences of reactions produce
3 bromoform, CHBr3, and mixed chlorine–
OH OH bromine trihalomethanes from the action on
humic materials of hypobromous acid, HOBr,
Subsequently the ring cleaves between C-2 which is formed when bromide ion in water
and C-3 to yield a chain: displaces chlorine from HOCl:
R 9 C 9 CHCl2 HOCl Br EF HOBr Cl
O
presence, even at very low levels of approximately 30 ppb, raises the specter
that chlorinated drinking water may pose a health hazard, though one that
pales by comparison with the benefits that it confers in the elimination of
fatal waterborne diseases. The annual average limit of total THMs in drink-
ing water in the United States and the European Union (EU) has been
reduced to 80 ppb. The previous limit of 100 ppb is still used in Canada. In
fact, these 80–100-ppb limits are set not only to regulate the THM chemicals
themselves but also as an indicator that the production of other chlorinated
organic DBPs (see below) is not excessive.
The U.S. EPA has set a maximum contaminant level goal, MCLG, of
70 ppb for THMs in drinking water. An MCLG is the maximum level at which
the contaminant is believed to be safe, allowing for adequate margins of safety, but
unlike the MCL (Chapter 10), it is not an enforceable standard. A nonzero
goal is considered by some scientists and policymakers to be appropriate to
substances, like chloroform, that are believed to operate indirectly as carcino-
gens. They do not damage DNA directly but cause tissue damage that leads to
rapid cell proliferation, which in turn increases the likelihood that cancer will
form in the damaged tissue. A threshold below which no effects are likely to
be observed is expected for carcinogens that operate in this manner.
The level of trihalomethanes formed in water depends sharply on the
organic content of the raw water since the THMs are formed from the reac-
tion of organics with HOCl (see Box 14-3). THM levels can reach 250 ppb
in areas of Scotland and Northern Ireland that have peat moorlands. Water
exposed to bogs in Newfoundland, Canada, has generated THM levels in
excess of 400 ppb. As of the early 1990s, about 1% of the larger U.S. drinking
water utilities that used surface waters, but none that used groundwater, had
average THM levels exceeding 100 ppb. The THM content of chlorinated
water could be decreased by using activated carbon either to remove dis-
solved organic compounds before the water is chlorinated or to remove
THMs and other chlorinated organics after the process, although THMs are
not very efficiently adsorbed by the carbon and it is an expensive process.
An analysis of epidemiological studies relating the chlorination of water
to cancer rates in various communities in the United States led to the con-
clusion that the risk of bladder cancer in humans increased by 21%, and that
of rectal cancer by 38%, for Americans who drank chlorinated surface water
in the past. A similar study in Ontario found even higher bladder cancer risk
factors for people who drank water for 35 years or more that had THM levels
greater than 50 ppb, and for colon cancer when the concentration exceeded
75 ppb, but found no correlations of THMs with rectal cancer rates. A recent
study found no increased risk for pancreatic cancer from lifetime exposure to
the by-products of chlorinated water.
Given that slightly more than half the population of the United States
drinks surface water, one effect of chlorination is to have increased bladder
cancer incidence by about 4200 cases per year and rectal cancer incidence by
about 6500 cases annually. Because of these risks, some communities are con-
sidering a switch, or have already switched, to water disinfection by ozone or
chlorine dioxide, since these agents produce little or no chloroform. The
extent of chlorination has already been reduced in most American communi-
ties relative to the levels that led to these statistics.
Several other mutagenic chlorinated organic DBPs formed during chlori-
nation have been detected in water, in addition to chloroform. It is not clear
whether the main carcinogens in the chlorinated drinking water are the
THMs themselves or some nonvolatile, higher-molecular-weight mutagenic
by-product present at still lower concentrations but whose concentration
would presumably be proportional to THM. The same risks do not usually
apply to chlorinated well water, since its organochlorine content is much less
(only 0.8 ppb on average, versus 51 ppb for surface water) because it contains
much smaller amounts of organic matter that could become chlorinated.
Exposure to chloroform by dermal contact and inhalation of the gases deab-
sorbed from the hot water during showers, baths, and hand-washing of dishes
contribute more to one’s intake of THMs, as measured by the blood levels of
these compounds, than does drinking the water itself. Swimming in pools in
which the water is chlorinated for disinfection also contributes significantly
to dermal exposure. Recently it has been found that use of the disinfectant
triclosan, a phenol-based compound present in some hand soaps, in chlori-
nated water can produce additional chloroform and chlorinated phenols, to
which the user is then exposed.
Recently, public health officials have expressed concern about the possi-
ble link between THMs and adverse human reproductive outcomes, includ-
ing first-term miscarriages, stillbirths, impaired fetal growth, and certain birth
defects. Even though the existing research in this area is not yet definitive,
some officials suggest that women drink bottled water rather than chlorinated
tap water during their first three months of pregnancy.
Disinfection by Chlorine: Advantages over Other Methods

Notwithstanding the preceding discussion of chlorination by-products, it is
important to point out that the disinfection of water by chlorine is extremely
important in protecting public health and saves many more lives—by a very
wide margin—than are affected negatively. For example, both typhoid and
cholera were widespread in both Europe and North America a century ago
but have been almost completely eradicated in the developed world, thanks
to chlorination and the other disinfection methods for drinking water and to
improved sanitation in general. The same is not true in many developing
countries; e.g., there were more than half a million cases of cholera in Peru in
the early 1990s. Overall, about 20 million people, most of them infants, die
from waterborne diseases annually worldwide in underdeveloped countries,
where water purification is often erratic or even nonexistent. Under no
circumstances should effective disinfection of water be abandoned because of

concern for the by-products of chlorination!
An advantage chlorination has over disinfection by chlorine dioxide or
ozone or by UV is that some chlorine remains dissolved in water once it has
left the purification plant, so that the water is protected from subsequent bac-
terial contamination before it is consumed. Indeed, some chlorine is usually
added to water purified by the other methods to provide this protection.
There is very little danger of significant chloroform production in the purified
water since its organic content has been virtually eliminated before the chlo-
rine is introduced. If the chlorine level in water purified by chlorination is too
high, it can be lowered by the addition of sulfur dioxide.
The residual chlorine in water often exists in the form of the chloramines
NH2Cl, NHCl2, and NCl3, which are produced from reaction with dissolved
ammonia gas, NH3. Although not as fast as HOCl in disinfecting water, the
mono- and dichloroamines especially are good disinfectants. The mixture of
chloramines, called combined chlorine, is longer-lived in water than is
hypochlorous acid and thus provides longer residual protection. Indeed,
ammonia is often added to purified drinking water in order to convert the
residual chlorine to the combined form (Figure 14-1). Chloramines are some-
times used, rather than chlorine or ozone or chlorine dioxide, as the main dis-
infectant in the purification of drinking water. They have the advantage over
chlorine of producing little (though not zero) amounts of THMs and
haloacetic acids. The U.S. EPA has set MRDLs of 4.0 ppm for both chlorine
and chloramine in drinking water.
Bromine rather than chlorine is sometimes used as the disinfectant in
swimming pools. The main disinfecting agent in bromination is hypobro-
mous acid, HOBr, in analogy with the role of hypochlorous acid in chlorina-
tion. HOBr reacts more rapidly with dissolved ammonia than does HOCl,
producing mainly NH2Br, which is also a good disinfectant.
To disinfect water for drinking purposes, hikers either boil raw water or
treat it chemically with either chlorine, in the form of bleach, which provides
HOCl, or iodine, as elemental I2 or hypoiodous acid, HIO. Concerns have
been expressed about chronic health problems such as thyroid dysfunction
associated with long-term usage of iodine, however. Treating the water with
elemental iodine tends to make it unpalatable as well.
P R O B L E M 14-3
Assuming that the nitrogen atom in monochloramine, NH2Cl, has an oxida-
tion number of 3, calculate that of the chlorine atom. Using the principle
that unlike charges attract, predict whether it will be the hydrogen ion or the
hydroxide ion from dissociated water molecules that will extract the Cl from
NH2Cl; from your result, predict the products of the decomposition reaction
of chloramine in water.
A drinking-water quality issue of current concern involves the patho-

genic protozoa called Cryptosporidium, which was responsible for the death of
100 people and for about 400,000 cases of watery diarrhea in Milwaukee in
1993. Less serious Cryptosporidium outbreaks occurred in Oxford, England, in
1989, and in Saskatchewan, Canada, in 2001. This deadly parasite is resistant
to standard methods of disinfection, such as chlorination at normal levels,
and is so small (about 5-mm diameter) that it easily passes through the stan-
dard filters used to separate sediments. Several possible solutions have been
advanced, including ozonation or the use of ultrafiltration or UV irradiation
or the application of monochloramine following chlorination. A longer-
than-usual exposure of water containing Cryptosporidium is necessary with
ozonation, since the activation energy for inactivation of protozoa by ozone
is about twice as large as that for bacteria (80 vs. about 40 kJ/mol).
Another protozoa, Giardia lamblia, also causes many instances of water-
borne disease. Like Cryptosporidium, it is also somewhat resistant to chlorina-
tion, but since it is larger (about 10-mm diameter), it is more easily removed
by filtration through sand.
Groundwater: Its Supply, Chemical

Contamination, and Remediation
The Nature and Supply of Groundwater
The great majority of the available fresh water on Earth lies underground,
half of it at depths exceeding a kilometer. As one digs into the ground below
the initial belt of soil moisture, the aeration or unsaturated zone, where the
particles of soil are covered with a film of water but in
which air is present between the particles, is next
Precipitation
encountered. At lower depths is the saturated zone, in
which water has displaced all the air from these pore
Surface
spaces. Groundwater is the name given to the fresh
Soil moisture
water in the saturated zone (see Figure 14-3); it makes
Aeration zone up 0.6% of the world’s total water supply. The ultimate
(unsaturated) source of groundwater is precipitation that falls onto
the surface; a small fraction of it eventually filters
Water table down to the saturated zone. Underground water ranges
Groundwater in in “age” from a few years to millions of years. For
saturated zone
(aquifer) example, in zones that are now arid, much of the
groundwater currently being accessed has been present
Clay or impervious rock since the wetter conditions of the last ice age and will
not be quickly replaced.
The top of the groundwater (saturated) region is
FIGURE 14-3 Ground- called the water table. In some places it occurs right at
water location in relation the surface of the soil, a phenomenon that gives rise to swamps. Where the
to regions in the soil. water table lies above the soil, we encounter lakes and streams.
If groundwater is contained in soil that is composed of porous rocks such

as sandstone, or in highly fractured rock such as gravel or sand, and if the
water is bounded at its lower depths by a layer of clay or impervious rocks,
then it constitutes a permanent reservoir—a sort of underground lake—
called an aquifer. Some aquifers lie below several layers of impermeable rock
or soil; these are called confined or artesian aquifers.
Groundwater in aquifers can be extracted by wells, and it is the main sup-
ply of drinking water for almost half the population of North America and
over 1.5 billion people worldwide. In the United States in 1990, groundwater
supplied 39% of the water used for public supplies and 96% of that withdrawn
for individual domestic systems, the latter being very common in rural homes.
In Europe the proportion of public drinking water extracted from aquifers
ranges from nearly 100% for Denmark, Austria, and Italy, to about two-thirds
in Germany, Switzerland, and the Netherlands, to less than one-third in
Great Britain and Spain.
In the United States, the majority of groundwater usage is for irrigation
purposes, almost all of it in the western states. The massive extraction of
water from American aquifers has given rise to fears about future supplies of
fresh water (and about the sinking of land above the aquifers), since such
aquifers are replenished only very slowly. In the High Plains of the central
United States, more than half the groundwater in storage has been depleted
in some areas. In northern China, the depletion of shallow aquifers is forc-
ing the sinking of wells more than 1 km deep in order to reach a new sup-
ply of groundwater. Indeed, groundwater depletion—along with the buildup
of salts in the soil—is now the dominant threat to irrigated agriculture. In
addition, the contamination of groundwater by chemicals is becoming a
serious concern in many areas. A side effect of the rise in sea levels that will
accompany global warming is the intrusion of salt water into aquifers near
coasts.
The Contamination of Groundwater

Groundwater has been traditionally considered to be a pure form of water.
Because of its filtration through soil and its long residence time underground,
it contains much less natural organic matter and many fewer disease-causing
microorganisms than water from lakes or rivers, although the latter point may
be a misconception, according to recent evidence. Some groundwater is nat-
urally too salty or too acidic for either drinking or irrigation purposes and
may contain too much sodium, sulfide, or iron for many uses.
Humans have been concerned about the pollution of surface water in
rivers and lakes for a long time. Indeed, a recent survey indicated that stream
water in both agricultural and urban areas of the United States contains pes-
ticide concentrations that exceed human-health benchmark standards. In
contrast, the contamination by chemicals of groundwater was not recognized
as a serious environmental problem until the 1980s, notwithstanding the fact
that it had been occurring for half a century. To a large extent, groundwater
contamination was neglected because it was not immediately visible—it was
“out of sight, out of mind”—even though groundwater is a major source of
drinking water. We were ignorant of the long-range consequences of our
waste disposal practices. Ironically, surface water can be cleaned up relatively
easily and quickly, whereas groundwater pollution is a much harder, much
more expensive, long-range problem to solve.
Because we are now aware of the consequences—including high remedi-
ation costs—of the uncontrolled disposal of organic chemical wastes, most
large corporations in developed countries have become much more responsi-
ble in their disposal of chemicals. Unfortunately, the collective discharges
from smaller sources, including many municipalities, small industries, and
farms, have not yet been controlled in like manner. Similarly, the huge num-
ber of septic tanks that exist are collectively a major source of nitrate, bacte-
ria, viruses, detergents, and household cleaners to groundwater.
Nitrate Contamination of Groundwater

The inorganic contaminant of greatest concern in groundwater is the nitrate
ion, NO3, which commonly occurs in both rural and suburban aquifers.
Although uncontaminated groundwater generally has nitrate nitrogen levels
of 4–9 ppm, about 9% of shallow aquifers—from which water is often
extracted via privately owned wells—in the United States now have nitrate
levels that exceed the 10-ppm nitrogen MCL value. Indeed, elevated levels
of about 100 ppm can result from agricultural activity. The location of areas
in the United States that have a high risk of nitrate contamination of
groundwater is shown in Figure 14-4. Exceeding the 10-ppm MCL limit is
much rarer (1%) for public U.S. groundwater supplies, partially because they
are drawn from deeper aquifers; these are generally less contaminated because
of their depth, because their location is remote from large sources of contam-
ination, and because natural remediation via denitrification of nitrate in the
low-oxygen conditions can occur.
The expenditure of public money on nitrate-level reductions in drinking
water has become a controversial subject. In Great Britain, in particular, hun-
dreds of millions of dollars have been spent on achieving the 50-ppm maxi-
mum level of nitrate ion set by the European Union. Because nitrate removal
from well water is very expensive, water contaminated with high levels of the
ion are not normally used for human consumption, at least in public supplies.
P R O B L E M 14-4
Convert the EU nitrate standard of 50 ppm to its nitrogen content alone.
Is the EU standard more or less stringent than the U.S. regulatory limit of
10 ppm nitrogen as nitrate per liter?
FIGURE 14-4 The risk of

Nitrogen Aquifer nitrate contamination of the
input vulnerability
groundwaters in the United
Increasing risk of
High High States. [Source: B. T. Nolan

contamination
groundwater
et al., “Risk of Nitrate in

High Low
Groundwaters of the
Low High United States—A National
Low Low Perspective,” Environmental
(1997): 2229.]
Nitrate in groundwater originates mainly from four sources:

• application of nitrogen fertilizers, both inorganic and animal manure, to
cropland,
• cultivation of the soil,
• human sewage deposited in septic systems, and
• atmospheric deposition.
Concern has been expressed about the increasing levels of nitrate ion in
drinking water, particularly in well water in rural locations; the main source
of this NO3 is runoff from agricultural lands into rivers and streams. Almost
12 million tons of nitrogen is applied annually as fertilizer for agriculture in
the United States, and manure production contributes almost 7 million tons
more. Initially, oxidized animal wastes (manure), unabsorbed ammonium
nitrate, NH4NO3, and other nitrogen fertilizers were thought to be the cul-
prits in nitrate contamination of groundwater, since reduced nitrogen unused
by plants is converted naturally to nitrate, which is highly soluble in water
and can easily leach down into groundwater. It now appears that intensive
cultivation of land, even without the application of fertilizer or manure, also
facilitates the oxidation of reduced nitrogen to nitrate in decomposed organic
matter in the soil by providing aeration and moisture. The original, reduced
forms of nitrogen become oxidized in the soil to nitrate, which, being mobile,
then migrates down to the groundwater, where it dissolves in water and is
diluted. Denitrification of nitrate to nitrogen gas (see Chapter 6) and uptake
of nitrate by plants can occur in forested areas that separate agricultural farms
from streams, thereby lowering the risk of contamination in areas with signif-
icant woodland. However, rural areas with high nitrogen input, well-drained
soil, and little woodland are at particular risk for nitrate contamination of
groundwater.
The atmospheric deposition of nitrate results from its production in the
atmosphere when NOX emissions from vehicles and power plants, and its
natural sources in thunderstorms, are oxidized in air to nitric acid and then
neutralized to ammonium nitrate (see Chapters 3 and 5).
In urban areas, the use of nitrogen fertilizers on domestic lawns and golf
courses, parks, etc. contributes nitrate to groundwater. Septic tanks and
cesspools also are significant contributors where they exist.
Excess nitrate ion in wastewater flowing into seawater, e.g., the Baltic
Sea, has resulted in algal blooms that pollute the water after they die. Nitrate
ion normally does not cause this effect in bodies of fresh water, where phos-
phorus rather than nitrogen is usually the limiting nutrient; increasing the
nitrate concentration there without an increase in phosphate levels does not
lead to an increased amount of plant growth. There are, however, instances
where nitrogen rather than phosphorus temporarily becomes the limiting
nutrient even in fresh waters.
P R O B L E M 14-5
The nitrate concentration in an aquifer is 20 ppm, and its volume is 10 mil-
lion liters. What mass of ammonia upon oxidation would have produced this
mass of nitrate?
Health Hazards of Nitrates in Drinking Water

Excess nitrate ion in drinking water is a potential health hazard since it can
result in methemoglobinemia in newborn infants as well as in adults with a
specific enzyme deficiency. The pathological process, in brief, runs as follows.
Bacteria, e.g., in unsterilized milk-feeding bottles or in the baby’s stomach,
reduce some of the nitrate to nitrite ion, NO2:
NO3 2 H 2 e 9: NO2 H2O
The nitrite combines with and oxidizes the iron ions in the hemoglobin in
blood from Fe2 to Fe3 and thereby prevents the proper absorption and
transfer of oxygen to cells. The baby turns blue and suffers respiratory failure.
(In almost all adults, the oxidized hemoglobin is readily reduced back to its
oxygen-carrying form, and the nitrite is readily oxidized back to nitrate; also,
nitrate is mainly absorbed in the digestive tract of adults before reduction to
nitrite can occur.) Methemoglobinemia, or blue-baby syndrome, is now rela-
tively rare in industrialized countries. It was a serious problem in Hungary up
until the late 1980s and in Romania.
The U.S. EPA MCL of 10 ppm of nitrate nitrogen was set in order to
avoid blue-baby syndrome. Since the syndrome is now almost nonexistent in
the United States (only two cases since the mid-1960s), some policy analysts
think this value is too stringent.
Recently, an increase in the risk of acquiring non-Hodgkin’s lymphoma
has been found for persons in some communities in Nebraska who consume
drinking water having the highest levels (long-term average of 4 ppm or more
of nitrogen as nitrate) of nitrate. As discussed in the next section, excess
nitrate ion in drinking water is also of concern because of its potential link
with stomach cancer. Recent epidemiological investigations have, however,
failed to establish any positive, statistically significant relationship between
nitrate levels in drinking water and the incidence of stomach cancer. A study
reported in 2001 found that older women in Iowa who drank water from
municipal supplies having elevated nitrate levels ( 2.46 ppm) were almost
three times as likely to be diagnosed with bladder cancer than those least
exposed ( 0.36 ppm in their drinking water). However, a recent large-scale
study from the Netherlands failed to find an association between nitrate
exposure and the risk of bladder cancer. A review of the current literature
concluded that there is also no association between nitrate exposure from
drinking water and adverse reproductive effects.
Nitrosamines in Food and Water

Some scientists have warned that excess nitrate ion in drinking water and
foods could lead to an increase in the incidence of stomach cancer in
humans, since some of it is converted in the stomach to nitrite ion. The
nitrites could subsequently react with amines to produce N-nitrosamines,
compounds that are known to be carcinogenic in animals. N-nitrosamines
are amines in which two organic groups and an 9 N " O unit are bonded to
the central nitrogen:
R H3C
N9N"O N9N"O
R H3C
N-nitrosamines NDMA
Of concern not only with respect to its production in the stomach and its
occurrence in foods and beverages (e.g., cheeses, fried bacon, smoked and/or
cured meat and fish, and beer), but also as an environmental pollutant in
drinking water, is the compound in which R in the above structure is the
methyl group CH3; it is called N-nitrosodimethylamine, or NDMA for short.
This organic liquid is somewhat soluble in water (about 4 g/L) and somewhat
soluble in organic liquids. It is a probable human carcinogen, and a potent
one if extrapolation from animal studies is a reliable guide. It can transfer a
methyl group to a nitrogen or oxygen of a DNA base, thereby altering the
instructional code for protein synthesis in the cell.
In the early 1980s, it was found that NDMA was present in beer to the
extent of about 3000 ppt. Since that time, commercial brewers have modified
the drying of malt so that the current levels of NDMA in American and
Canadian beers are now only about 70 ppt.
Large quantities of nitrate are used to “cure” pork products such as bacon
and hot dogs. In these foods, some of the nitrate ion is biochemically reduced
to nitrite ion, which prevents the growth of the organism responsible for
botulism. Nitrite ion also gives these meats their characteristic taste and color
by combining with hemoproteins in blood. Nitrosamines are produced from
excess nitrite during frying (e.g., of bacon) and in the stomach, as discussed.
Government agencies have instituted programs to decrease the residual nitrite
levels in cured meats. Some manufacturers of these foods now add vitamin C
or E to the meat in order to block the formation of nitrosamines. Based upon
average levels of NDMA in various foods and the average daily intake for each
of them, most of us now ingest more NDMA from consumption of cheese
(which is often treated with nitrates) than from any other source.
Even though the commercial production of NDMA has been phased out,
it can be formed as a by-product due to the use of amines in industrial
processes such as rubber tire manufacturing, leather tanning, and pesticide
production.
The levels of NDMA in drinking water drawn from groundwater is of
concern in some localities that have industrial sources of the compound. For
example, following the discovery that the water supply of one town had been
contaminated by up to 100 ppt NDMA from a tire factory, Ontario, Canada,
adopted a guideline maximum of 9 ppt of NDMA in drinking water, which
corresponds to a lifetime cancer risk of 1 in 100,000. By contrast, the guide-
line for water in the United States is set at 0.68 ppt, which corresponds to a
cancer risk of 1 in a million, but which actually lies considerably below the
detection limit (about 5 ppt) for the compound.
P R O B L E M 14-6
Write balanced redox half-reactions (assuming acidic conditions) for the
conversion of NH4 to NO3, and of NO2 to N2.
Perchlorates
Perchlorate ion, ClO4, is analogous to nitrate ion in that both oxyanions
involve nonmetals in their highest common oxidation numbers (7 in the
case of perchlorate; see Additional Problem 13 to generate a summary of
chlorine with its many oxidation numbers). For that reason, both ions are
oxidizing agents, and both have been used in explosives and propellants. Both
have both natural and anthropogenic sources. Perchlorate is a newly discov-
ered (late 1990s) pollutant in the drinking-water supply of about 15 million
Americans. Large quantities of ammonium perchlorate, NH4ClO4, are man-
ufactured for use as oxidizing agents in solid rocket propellants, fireworks,
batteries, and automobile air bags. Because rocket fuel has a limited shelf life,
it must be replaced regularly. Large amounts of perchlorates were washed out
of missiles and rocket boosters onto the ground or into holding lagoons in the
second half of the twentieth century.
Perchlorate contamination has been established in 23 U.S. states,
including much of the Colorado River and aquifers in the deserts of the
Southwest. Concentrations of perchlorate in drinking water in the U.S.
Southwest range from 5 to 20 ppb. The map (Figure 14-5) of perchlorate
releases in the United States indicates that most occur in the south-central
and western states, especially California. Perchlorate has also been found in
garden fertilizers at concentrations approaching 1%. It occurs naturally in
some Chilean deposits of nitrate which are exported to the United States and
elsewhere as fertilizers. Perchlorate also exists naturally in some minerals
FIGURE 14-5 Regions

Confirmed sites of perchlorate use and
Unconfirmed sites contamination in the
United States. [Source: B. E.
Urbanized areas Logan, “Assessing the Outlook
Major rivers for Perchlorate Remediation,”
Affected states Environmental Science and
Technology (1 December
2001): 484A.]
found in the U.S. Southwest. A recent analysis indicates that both its use as an
oxidizer, in fireworks, rockets, etc., and its presence in fertilizer make impor-
tant contributions to its contamination of foodstuffs in the United States.
At high doses, perchlorate affects human health by reducing hormone
production in the thyroid, where it competes with iodide ion. Its hazard
at low concentrations, if any, is not known, making the development of a
drinking-water standard for the ion a difficult problem. No federal MCL for
the ion has yet been set, but several states have set their own limits, ranging
from 1 to 18 ppb; e.g., California’s limit is 6 ppb. In 2002, a draft report by the
U.S. EPA proposed a drinking-water standard of 1 ppb as safe for human
health, but this value has been criticized as too low by the Department of
Defense and companies that make or use perchlorates. Research reported in
2002 on volunteers indicated that the no-effect level (NOEL; Chapter 10) for
the inhibition of iodine uptake corresponds to a drinking-water concentra-
tion of at least 180 ppb. The EPA based its 1-ppb recommendation on studies
indicating that mothers who drink perchlorate-contaminated water could
give birth to children whose IQs would be affected negatively because correct
maternal thyroid hormone levels are vital to fetal brain development.
Like nitrate, perchlorate is a difficult ion to remove from water supplies
since it is a highly water-soluble anion that is very inert and does not adsorb
readily either to mineral surfaces or to activated carbon. Barrier methods,
using elemental iron, etc. are not successful because the anion is so unreac-
tive. The primary technologies currently in use to remediate perchlorate in
water are ion exchange and biological treatment. Some ion exchange resins
successfully remove perchlorate, though it tends to remain in solution until
all other anions have been absorbed. Ion exchange is used especially when
perchlorate concentrations are low to begin with.
Certain bacteria found naturally in many soils, sediments, and natural
waters biodegrade perchlorate by reduction to chloride ion:
ClO4 9: 9: Cl 2 O2
Perchlorate can be biodegraded in bioreactors, large vats that are engineered
to maintain a high concentration of the appropriate bacteria in contact with
the water.
Groundwater Contamination by Organic Chemicals

The contamination of groundwater by organic chemicals is a major concern.
Many organic substances decay rapidly or are immobilized in the soil, so the
number of compounds that are sufficiently persistent and mobile to travel to
the water table and to contaminate groundwater there is relatively small.
The compounds that are most often detected in groundwater-based U.S.
community public water supplies, including those near hazardous waste sites,
are summarized in Table 14-1. Municipal landfills as well as industrial waste
Organic Compounds Commonly Found in U.S. Groundwater-Based

TABLE 14-1 Community Water Supplies and Their Properties
Chemical Density (g/mL) Water Solubility (g/L)
Present at 25 – 50% of sites:

Chloroform (trichloromethane) 1.48 8.2
Bromodichloromethane 1.98 4.4
Dibromochloromethane 2.45 2.7
Bromoform (tribromomethane) 2.89 3.0
Present at a smaller fraction of sites:
Trichloroethene 1.46 1.1
Tetrachloroethene (perchloroethene) 1.62 0.15
1,1,1-Trichloroethane 1.34 1.5
1,2-Dichloroethenes 1.26, 1.28 3.5, 6.3
1,1-Dichloroethane 1.18 5.5
Carbon tetrachloride 1.46 0.76
Dichloroiodomethane 1.58
Xylenes 0.86 – 0.88 0.18 (o)
1,2-Dichloropropane 1.16 2.8
Benzene 0.88 1.8
Toluene 0.87 0.54
Also commonly present at wells close to
hazardous waste sites:
Methylene chloride 1.33 20
Ethylbenzene 0.87 0.15
Acetone 0.79 sol
1,1-Dichloroethene 1.22 2.3
1,2-Dichloroethane 1.24 8.5
Vinyl chloride (chloroethene) gas 8.8
Methyl ethyl ketone 0.80 268
Chlorobenzene 1.11 0.47
1,1,2-Trichloroethane 1.44 4.5
Chloroethane 0.90 5.7
Fluorotrichloromethane gas 1.1
1,1,2,2-Tetrachloroethane 1.60 2.7
Methyl isobutyl ketone 0.80 19
Source: Based on U.S. EPA surveys of about 2% of U.S. water supplies.
disposal sites are often the source of the contaminants. Liquid that contains
dissolved matter that drains from a terrestrial source, such as a landfill, is called
a leachate. In rural areas, the contamination of shallow aquifers by organic
pesticides, such as atrazine (Chapter 10) leached from the surface, has become
a concern. The insecticide dieldrin (Chapter 10), which has been banned since
1992, is the pesticide found most often to exceed human-health guideline
levels in U.S. groundwater. Ironically, shallow groundwater aquifers used to
supply drinking water are often more polluted by pesticides at greater than
acceptable levels than are those in agricultural areas in the United States.
The typical organic contaminants in most major groundwater supplies are:
• Chlorinated solvents, especially trichloroethene (TCE, “tric,” also called
trichloroethylene), C2HCl3, and perchloroethene (PCE, “perc,” also called
perchloroethylene or tetrachloroethene), C2Cl4. These molecules contain a
C " C bond, with three or four of the four hydrogen atoms of ethene (ethy-
lene) replaced by chlorine:
H Cl Cl Cl
C"C C"C
Cl Cl Cl Cl
TCE PCE
By a large margin, chlorinated solvents are the most prevalent organic pollu-
tants in groundwater.
• Hydrocarbons from the BTX component of gasoline and other petro-
leum products: benzene, C6H6, and its methylated derivatives toluene,
C6H5(CH3), and the three isomers of xylene, C6H4(CH3)2. (See Chapter 7
for structures.)
• MTBE (methyl tertiary-butyl ether) from gasoline (see Chapter 8)
The chemicals in the groups mentioned above occur commonly in
groundwater at sites where manufacturing and/or waste disposal occurred,
especially from 1940 to 1980. In that period, little attention was paid to the
ultimate fate and residence following the in-ground injection of these chem-
icals. The sources of these organic substances also include leaking chemical
waste dumps, leaking underground gasoline storage tanks, leaking municipal
landfills, and accidental spills of chemicals on land.
Trichloroethene is an industrial solvent, used to dissolve grease on metal, as
is perchloroethene. The U.S. MCL for TCE in drinking water is 5 ppb, and the
same limit is now used in Canada as well. A 2006 report by the U.S. National
Academy of Sciences concluded that TCE is a possible cause of kidney cancer,
can impair neurological function, and can cause reproductive and developmen-
tal damage. A link between TCE exposure and an abnormally low sperm count
in males has been established. The International Agency for Research on
Cancer has classified TCE as “probably carcinogenic to humans.”
PCE is used not only in metal degreasing but also finds wide application
as the solvent in dry-cleaning operations, so it is released from a large number
of small sources. A group of women in Cape Cod, Massachusetts, who were
inadvertently exposed over several decades to high levels of PCE in their
drinking water were found to have small to moderate increases in their risk of
contracting breast cancer.
Gasoline enters the soil via surface spills, leakage from underground storage
tanks, and pipeline ruptures. Before 1980, underground gasoline storage tanks
were made from steel; almost half of them were sufficiently corroded to leak
by the time they were 15 years old. Once they descend to groundwater, the
water-soluble components of the gasoline are preferentially leached into the
water and can migrate rapidly in the dissolved state. The BTX component,
which is the most soluble of the hydrocarbons, often occurs at concentrations
of 1–50 ppb in groundwater. However, the alkylated benzenes are rapidly
degraded by aerobic bacteria and consequently are not long-lasting.
The MTBE component of gasoline (Chapter 7) is more water-soluble
than the hydrocarbons, but unlike them, it is not readily biodegraded. It is
not highly toxic. The main problem is the odor and taste that it gives to
water; as little as 15 ppb in water can be tasted or smelled. MTBE contamina-
tion of well water, albeit at low levels, has become of concern in the United
States since it has occurred at about a quarter of a million sites.
The Ultimate Sink for Organic Contaminants

in Groundwater
The subsequent behavior of the organic compounds that do migrate to the
water table depends significantly upon their density relative to that of 1.0 g/mL
of water. Liquids that are less dense (“lighter”) than water and have low solu-
bility in it form a mass that floats on the top of the water table. All hydrocar-
bons having a small or medium molecular mass belong to this group,
including the BTX fraction of gasolines and other petroleum products (see
Table 14-1). In contrast, polychlorinated solvents are more dense (“heavier”)
than water and insoluble in it, so they tend to sink deeply into aquifers;
important examples are methylene chloride, chloroform, carbon tetrachloride,
1,1,1-trichloroethane, TCE, and PCE (see Table 14-1). Nonchlorinated but
insoluble high-molecular-weight organic materials, such as creosote and coal
tar, also belong to the heavier-than-water group. These substances are some-
times referred to as dense nonaqueous-phase liquids, DNAPLs.
Although the oily liquid blobs that these organic compounds form gener-
ally are found in an aquifer at a position either directly below their original
point of entry into the soil or close to it, the implication that they are horizon-
tally immobile is misleading. Very slowly—in a process that often takes
decades or centuries to complete—these low-solubility compounds gradually
dissolve in the water that passes over the blob and so provide a continuous
supply of contaminants to the groundwater. The complete removal of such
deposits usually is not feasible since they may exist as several blobs whose
exact location is difficult to pinpoint. In addition, disturbance of the deposit
during removal or treatment may increase its net exposure to the water phase.
Even removing 90% of the substance does not necessarily result in reduction
Surface source
Water table
Aquifer BTX Plume of

BTX-polluted
water
Direction of
groundwater flow
Plume
of solvent-
Chlorinated polluted water
FIGURE 14-6 The con- solvents
tamination of groundwater
by organic chemicals.
of its groundwater concentration. Thus, plumes of polluted water grow, in the

direction of the water’s flow, and thereby contaminate the bulk of the aquifer
(see Figure 14-6). Because of such contamination, many wells used for drink-
ing water have had to be closed.
Decontamination of Groundwater:
Physical and Chemical Processes
In the last two decades, considerable energy and money have been spent in
the United States on attempts to control aquifer pollution by the oily liquids
discussed above. Dense organic leachates, especially PCE and TCE, have
contaminated the groundwater that lies below the waste sites associated with
the U.S. Superfund remediation initiative (see Chapter 16). Unfortunately,
no easy cure to the problem of contamination has been found. Control usually
consists of pump-and-treat systems that pump contaminated water from the
aquifer, treat it to remove its organic contaminants (using methods of the type
described later in this chapter), and return the cleaned water to the aquifer or
to some other water body. Alternatively, a fine mist of the contaminated
groundwater is sprayed into the air above agricultural land using a long, move-
able sprinkler system; the contaminant volatile organic compounds (VOCs)
evaporate into the air and the cleansed water is used for irrigation.
The volume of water that must be pumped and treated in a given

aquifer is huge. For organic contaminants with low water solubility, recon-
tamination of water returned to the aquifer by additional dissolution from
the blob will occur. Consequently, the treatment systems must operate in
perpetuity, and there are already thousands of them spread across the
United States.
Both in situ heating, to vaporize the organic liquids so their vapors rise
to the soil surface, and the addition of oxidants to convert the substances to
products such as carbon dioxide have been tried in some locations. Typically,
temperatures close to 100°C are used in heating, though it is not known if
this is optimal in most cases. Heating and/or the production of gases or pre-
cipitates by oxidation may inadvertently change the geologic and biological
conditions in the immediate vicinity of the treatment, with unforeseen
effects on the distribution and mobility of the remaining pollutant.
Decontamination of Groundwater:
Bioremediation and Natural Attenuation
Bioremediation is the term applied to the decontamination of water or soil
using biochemical rather than chemical or physical processes. Recently there
has been interesting progress reported in using bioremediation to cleanse
water of chlorinated ethene solvent contamination.
The biodegradation of chloroethenes by aerobic bacteria becomes less
and less efficient as the extent of chlorination increases, so it is ineffective
for perchloroethene. However, under anaerobic conditions, the reductive
biodegradation of PCE and TCE proceeds more quickly, particularly if an easily
oxidized substance such as methanol is added to supply electrons for the
reduction processes. Unfortunately, the stepwise dechlorination of these
compounds proceeds through vinyl chloride, CH2 " CHCl, a known car-
cinogen. Recently, a bacterium has been discovered that removes all the
chlorine from organic solvents such as TCE and PCE.
Owing to the high cost and limited effectiveness of many groundwater
cleanup technologies, the inexpensive process of natural attenuation—
allowing natural biological, chemical, and physical processes to treat ground-
water contaminants—has become popular. Indeed, it is now used at more
than 25% of Superfund program sites in the United States and is the leading
method to remedy the contamination of groundwater from leaking under-
ground storage sites.
However, there is great controversy about whether or not natural
attenuation is an appropriate strategy for managing groundwater contami-
nation: Many environmentalists feel that it is a cheap way for industry to
avoid expensive cleanup costs. The U.S. National Research Council in
1997 appointed a committee to determine which pollutants could be
treated successfully by this technique. Table 14-2 summarizes their results.
Likelihood of Success of Groundwater Remediation

TABLE 14-2 by Natural Attenuation for Various Substances
Dominant Attenuation Likelihood of Success Given

Chemical Class Processes Current Level of Understanding
Organic Compounds
Hydrocarbons
BTEX Biotransformation High
Gasoline, fuel oil Biotransformation Moderate
Nonvolatile aliphatic Biotransformation,
compounds immobilization Low
PAHs Biotransformation,
immobilization Low
Creosote Biotransformation,
immobilization Low
Oxygenated hydrocarbons
Low-molecular-weight Biotransformation High
alcohols, ketones, esters
MTBE Biotransformation Low
Halogenated aliphatics
PCE, TCE, carbon tetrachloride Biotransformation Low
TCA Biotransformation,
abiotic transformation Low
Methylene chloride Biotransformation High
Vinyl chloride Biotransformation Low
Dichloroethylene Biotransformation Low
Halogenated aromatics
Highly chlorinated
PCBs, tetrachlorodibenzofuran, Biotransformation,
pentachlorophenol, immobilization Low
multichlorinated benzenes
Less chlorinated
PCBs, dioxins Biotransformation Low
Monochlorobenzene Biotransformation Moderate
Inorganic Substances
Metals
Ni Immobilization Moderate
Cu, Zn Immobilization Moderate
Cd Immobilization Low
Pb Immobilization Moderate
Likelihood of Success of Groundwater Remediation

TABLE 14-2 by Natural Attenuation for Various Substances
Dominant Attenuation Likelihood of Success Given

Chemical Class Processes Current Level of Understanding
Cr Biotransformation,
immobilization Low to moderate
Hg Biotransformation,
immobilization Low
Nonmetals
As Biotransformation,
immobilization Low
Se Biotransformation,
immobilization Low
Oxyanions
Nitrate Biotransformation Moderate
Perchlorate Biotransformation Low
Source: Adapted from J. A. Macdonald, “Evaluating Natural Attenuation for Groundwater Cleanup,” Environmental Science and
Technology (1 August 2000): 346A.
Only three pollutants are highly likely to be successfully treated by natural

attenuation:
• BTEX hydrocarbons (i.e., BTX hydrocarbons plus ethylbenzene),
• low-molecular-weight oxygen-containing organics, and
• methylene chloride.
In all three cases, biotransformation is the dominant process by which atten-
uation occurs. Notice that neither MTBE nor highly chlorinated organics,
including TCE and PCE, are usually successfully treated in this way, nor is
mercury or perchlorate ion.
Decontamination of Groundwater: In Situ Remediation

Scientists have developed a promising in situ technique for treating ground-
water contaminated by volatile (mainly C1 and C2) chlorinated organics.
They construct an underground permeable “wall” of material (mostly coarse
sand) along the path of the water. The water is cleansed as a result of its
passage through the wall and never has to be pumped out of the ground (see
Figure 14-7).
The ingredient that is placed within the sand bed and that chemically
cleans the water is metallic iron, Fe0, in the form of small granules, a common
Permeable subsurface
treatment wall composed
of iron filings and sand Chemical source
Stream of
chemicals
Clean
groundwater
Direction of
groundwater
FIGURE 14-7 In situ Gravel flow
purification of groundwater
using an “iron wall.”
waste product of manufacturing processes. When placed in contact with cer-

tain chlorinated organics dissolved in water, the iron acts as a reducing agent,
giving up electrons to form the ferrous, or Fe(II), ion Fe2, which dissolves
in the water:
Fe(s) 9: Fe2(aq) 2 e
Usually, these electrons are donated to chloroorganic molecules that are tem-
porarily adsorbed onto the metal’s surface; the chlorine atoms contained in
these molecules are consequently reduced to chloride ions, Cl, which are
released into aqueous solution. This technique is an example of reductive
degradation. For example, the reduction of trichloroethene to its completely
dechlorinated form, ethene, can be written in unbalanced form as
C2HCl3 9: C2H4 3 Cl
Upon application of a standard redox balancing technique for alkaline solu-
tion, we obtain the balanced half-reaction
C2HCl3 3 H2O 6 e 9: C2H4 3 Cl 3 OH
Combination of the half-reactions (after tripling the oxidation step to ensure
the number of electrons lost and gained is the same) yields the overall reaction
3 Fe(s) C2HCl3 3 H2O 9: 3 Fe2(aq) C2H4 3 Cl 3 OH
One of the by-products of the reaction is hydroxide ion, OH. Recall
from Chapter 13 that in limestone-rich areas, the groundwater contains
significant concentrations of dissolved calcium bicarbonate, Ca(HCO3)2.

The hydroxide ions produced in the groundwater remediation reaction react
with bicarbonate to produce carbonate ion, CO32, which combines with dis-
solved calcium ions to produce insoluble calcium carbonate, CaCO3, which
then precipitates in the sand–iron mixture.
Field trials indicate that this new technology can work successfully for
several years at least, and it may replace the pump-and-treat methods for
many applications involving chlorinated methanes and ethanes dissolved in
underground water.
Recently, it has been found that coating the iron filings with nickel
speeds up the rate of degradation of the organic compounds by a factor of 10;
with this modification, the technique may be even more useful than first
imagined. In addition, it has been discovered that the elemental iron in the
barriers will reduce soluble Cr6 ions to insoluble Cr3 oxides and can therefore
remediate groundwater contaminated by Cr6. (The environmental chem-
istry of chromium is discussed in more detail in Chapter 15). A technique for
the in situ creation of elemental iron from its ions (Fe2 and Fe3) by the
injection of aqueous reducing agents has also been tested.
An in situ technique of treating TCE and PCE by hydrogenation has
been developed. The process uses dissolved H2 gas to rapidly dechlorinate
these two organics, eventually forming ethane and HCl. The reaction, which
uses a palladium catalyst, can be done within a well bore so that the water
need not be brought up to the surface.
P R O B L E M 14-7
The dissolution of iron in the process described above produces some molecular
hydrogen gas, H2. Show by balanced equation(s) how the hydrogen could
arise from the reduction of water rather than of TCE.
P R O B L E M 14-8
Suppose that this “iron wall” technology reduced an appreciable fraction
of TCE to vinyl chloride rather than completely to ethene. Why would this
be an unacceptable result environmentally? (Note that in practice a suffi-
ciently thick wall of iron is used to convert any vinyl chloride by-product to
ethene.)
P R O B L E M 14-9
Deduce the overall reaction by which perchloroethene is converted to
ethene by metallic iron.
P R O B L E M 14-10
At one test site for this remediation process, the water contained 270 ppm
TCE and 53 ppm perchloroethene. Calculate the mass of iron required to
remediate 1 L of this groundwater.
The Chemical Contamination and

Treatment of Wastewater and Sewage
Most municipalities treat the raw sewage collected from homes, buildings,
and industries (including food processing plants) through a sanitary sewer
system before the liquid residue is deposited into a nearby source of natural
waters, whether a river, lake, or ocean. In contrast, since the rainwater and
melted snow that drain from streets and other paved surfaces are usually not
highly contaminated, they are often collected separately by storm sewers and
deposited directly into a body of natural water. Unfortunately, in some
municipalities, storm-driven overflow occurs in the sanitary sewer system
and the overflow is combined with storm water and deposited, untreated,
into waterways.
The main component of sewage—other than water—is organic matter of
biological origin. It occurs mainly as particles—ranging from those of macro-
scopic size large enough to be trapped (together with such objets d’art as facial
tissues, stones, socks, tree branches, condoms, and tampon applicators) by
mesh screens to those which are microscopic in size and are suspended in the
water as large colloids.
Sewage Treatment
In the primary (or mechanical) treatment stage of wastewater (see the
schematic diagram in Figure 14-8), the larger particles—including sand and
silt—are removed by allowing the water to flow across screens and slowly
along a lagoon or settling basin. A sludge of insoluble particles forms at the
bottom of the lagoon, while “liquid grease” (a term which here includes not
only fat, oils, and waxes but also the products formed by the reaction of soap
with calcium and magnesium ions) forms a lighter-than-water layer at the top
and is skimmed off. About 30% of the biochemical oxygen demand (BOD,
Chapter 13) of the wastewater is removed by the primary treatment process,
even though this stage of the process is entirely mechanical in nature. The
treatment and disposal of the sludge is discussed later.
After passing through conventional primary treatment, the sewage water
has been much clarified but still has a very high BOD—typically several
hundred milligrams per liter (ppm)—and is detrimental to fish life if released
at this stage (as occurs in some jurisdictions that discharge into the ocean).
The high BOD is due mainly to organic colloidal particles. In the secondary
(biological) treatment stage, most of this suspended organic matter as well as
The Chemical Contamination and Treatment of Wastewater and Sewage 637
Primary treatment Secondary treatment Tertiary

treatment
Microorganism-
Grease catalyzed oxidation
Waste- River
water or lake
Sludge Sludge
Water Removal
Grease of various
Solid matter Disposal chemicals
FIGURE 14-8 The

that actually dissolved in the water is biologically oxidized by microorganisms common stages in the
to carbon dioxide and water or converted to additional sludge, which can treatment of wastewater.
readily be removed from the water. Either the water is sprinkled onto a bed of
sand and gravel or of plastic covered with the aerobic bacteria (trickling filters),
or it is agitated in an aeration reactor (activated sludge process) in order to
effect the microorganism-driven reaction. The system is kept well-aerated to
speed the oxidation. In essence, by deliberately maintaining in the system a
high concentration of aerobic microorganisms, especially bacteria, the same
biological degradation processes that would require weeks to occur in open
waters are accomplished in several hours.
The biological oxidation processes of secondary treatment reduce the
BOD of the polluted water to less than 100 ppm, which is about 10% of the
original concentration in the untreated sewage. For comparison, Canadian
wastewater quality standards require that the BOD in treated water be 20 ppm
or less. The process of nitrification also occurs to some extent, converting
organic nitrogen compounds to nitrate ion and carbon dioxide (see below). In
summary, the secondary treatment of wastewater involves biochemical reactions
that oxidize much of the oxidizable organic material that was not removed in
the first stage. Treated water diluted with a greater amount of natural water
can support aquatic life. Normally, municipalities take the water produced by
secondary treatment and disinfect it by chlorination or irradiation with UV
light before pumping it into a local waterway. Recent research in Japan has
shown that chlorination of the effluent before its release produces mutagenic
compounds, presumably by interaction of chlorine-containing substances with
the organic matter that remains in the water.
A few municipalities employ tertiary (or advanced or chemical) waste-
water treatment as well as primary and secondary ones. In the tertiary phase,
specific substances are removed from the partially purified water before its
final disinfection. In some cases, the water produced by tertiary treatment is
of sufficiently high quality to use as drinking water. Alternatively, river

water into which the effluent from sewage treatment plants has been
deposited is used by municipalities downstream as drinking water. The reuse
of water after it has been cleansed is particularly prevalent in Europe, where
less fresh water is available than in North America and the population
density is high.
Depending upon locale, tertiary treatment can include some or all of the
following chemical processes:
• further reduction of BOD by removal of most remaining colloidal mate-
rial, using an aluminum salt in a process that operates in the same manner as
described previously for the purification of drinking water;
• removal of dissolved organic compounds (including chloroform) and
some heavy metals by their adsorption onto activated carbon, over which the
water is allowed to flow (see Box 14-1);
• phosphate removal (as discussed in the next section; some phosphorus is
removed in the secondary treatment stage since microbes incorporate it as a
nutrient for their growth);
• heavy metal removal by the addition of hydroxide or sulfide ions, S2, to
form insoluble metal hydroxides or sulfides, respectively (see Chapter 15);
• iron removal by aeration at a high pH to oxidize it to its insoluble Fe3
state, possibly in combination with use of a strong oxidizing agent to destroy
organic ligands bound strongly to the Fe2 ion, which would otherwise pre-
vent its oxidation; and
• removal of excess inorganic ions, as discussed below.
In some wastewaters, the further removal of nitrogen compounds—usually
either ammonia or organic nitrogen compounds—is deemed necessary. Ammo-
nia removal can be achieved by raising the pH to about 11 (with lime) to con-
vert most ammonium ion to its molecular form, ammonia, NH3, followed by
bubbling air through the water to air-strip it of its dissolved ammonia gas. This
process is relatively expensive, however, because it is energy-intensive. Ammo-
nium ion can also be removed by ion exchange, using certain resins that have
their exchange sites initially populated by sodium or calcium ions.
Alternatively, both organic nitrogen and ammonia can be removed by
first using nitrifying bacteria to oxidize all the nitrogen to nitrate ion. Then
the nitrate is subjected to denitrification by bacteria to produced molecular
nitrogen, N2, which bubbles out of the water. Since this reduction step
requires a substance to be oxidized, methanol, CH3OH, is added if necessary
to the water and is converted to carbon dioxide in the process:
bacteria
5 CH3OH 6 NO3 6 H 9: 5 CO2 3 N2 13 H2O
BOX 14-4 Time Dependence of Concentrations

in the Two-Step Oxidation of Ammonia
he bacteria-catalyzed oxidation of ammo- whose rate is proportional to the first power of
T nia (or of other reduced organic nitrogen
compounds) to nitrate is a reaction with two
its concentration, we can write
d[B]
main steps, with nitrite ion, NO2, an inter- k1[A] k2[B]
mediate: dt
These differential equations can be cou-
Step 1 NH3 32 O2 9:
pled and integrated to yield the following
NO2 H H2O expressions for the evolution of [A] and [B]
Step 2 NO2 12 O2 9: NO3 with time, relative to [A]0, the original con-
centration of A:
If sufficient oxygen is available, the rate of
each reaction is first-order only in the con- [A]/[A]0 ek1t
centration of the nitrogen reactant, so the [B]/[A]0 k1(ek1t ek2t)/(k2 k1)
sequence can be represented as
As can be seen from the solution to Problem 1,
k1 k2 the concentration of B (nitrite) rises expo-
A 9: B 9: C
nentially at first, reaches a peak value, then
where A stands for ammonia, B for nitrite ion, declines slowly. Thus significant concentra-
and C for nitrate ion, and k1 and k2 are the tions of nitrite ion occur in water undergoing
pseudo-first-order rate constants. Since the rate the two-step conversion of ammonia to
of step 1 depends on the first power of the ammo- nitrate.
nia concentration, then the rate of disappear-
ance of this species is PROBLEM 1
d[A] (a) Derive a general expression relating the

k1[A] time at which [B] reaches a peak to k1 and k2.
dt
(b) Draw a graph showing the evolution of
Since B (nitrite) is produced at this rate by [A] and of [B] with time for the values k1 1
step 1, but is consumed in step 2 by a process and k2 2.
Of course, water contaminated by nitrate ion can also be treated by this lat-
ter step. A mathematical analysis of the kinetics of the transformations is
given in Box 14-4.
P R O B L E M 14-11
Given that the Kb value for ammonia is 1.8 105, deduce a formula giving
the ratio of ammonia to ammonium ion as a function of the pH of water.
What is the value of this ratio at pH values of 5, 7, 9, and 11?
The Origin and Removal of Excess Phosphate

One of the world’s most famous cases of water pollution involves Lake Erie,
which in the 1960s was said to be dying. Indeed, one of the authors of this
book can recall visiting a once-popular beach on Lake Erie’s north shore in the
early 1970s and being repulsed by the sight and smell of dead, rotting fish on
the shoreline. Lake Erie’s problems stemmed primarily from an excess input of
phosphate ion, PO43, in the waters of its tributaries. The phosphate sources
were the polyphosphates in detergents (as explained in detail later), raw
sewage, and the runoff from farms that used phosphate products. Since there is
commonly an excess of other dissolved nutrients in lakes, phosphate ion usu-
ally functions as the limiting (or controlling) nutrient for algal growth: The
larger the supply of the ion, the more abundant the growth of algae—and its
growth can be quite abundant indeed. When the vast mass of excess algae
eventually dies and starts to decompose by oxidation, the water becomes
depleted of dissolved oxygen, with the result that fish life is adversely affected.
The lake water also becomes foul-tasting, green, and slimy, and masses of dead
fish and aquatic weeds rot on the beaches. The series of changes, including
rapid degradation and aging, that occur when lakes receive excess plant nutri-
ents from their surroundings is called eutrophication. When the enrichment
arises from human activities, it is called cultural eutrophication.
To correct the regional problem, the United States and Canada in 1972
signed the Great Lakes Water Quality Agreement. Since that time, over $8 bil-
lion has been spent in building sewage treatment plants to remove phosphates
from wastewater before it reaches the tributaries and the lake itself. In addition,
the levels of polyphosphates in laundry detergents were restricted in Ontario
and in many of the states that border the Great Lakes. The total amount of
phosphorus entering Lake Erie has now decreased by more than two-thirds. As
a result, Lake Erie has sprung back to life: Its once-fouled beaches are regaining
popularity with tourists, and its commercial fisheries have been revived.
As we have pointed out, the presence of excess phosphate ion in natural
waters can have a devastating effect on an aquatic ecology because it overfer-
tilizes plant life. Formerly, one of the largest sources of phosphate as a pollu-
tant was detergents, and in the material that follows, the role of such
phosphates is discussed.
The reaction of synthetic detergents with calcium and magnesium ions,
forming complex ions, diminishes the cleansing potential of the detergent.
Polyphosphate ions, which are anions containing several phosphate units
linked by shared oxygens, are added to detergents as builders that preferen-
tially form soluble complexes with these metal ions and thereby allow the
molecules of the detergent to operate as cleansing agents rather than being
complexed with the Ca2 and Mg2 naturally present in the water. Another
role of the builder is to make the wash water somewhat alkaline, which helps
remove the dirt from certain fabrics. With soap itself, the ions form insoluble
complexes that foul the cleaning water.
O O O O O O
O
FIGURE 14-9 Structure
(a)
O9P9O9P9O9P9O
(b) P Ca 2
O P

of the polyphosphate ion:
O O (a) uncomplexed and
O O O O9P (b) complexed with
O O calcium ion.
Great quantities of sodium tripolyphosphate (STP), Na5P3O10, were

formerly added as the builder in most synthetic detergent formulations. As
shown in Figure 14-9a, STP contains a chain of alternating phosphorus and
oxygen atoms, with one or two additional oxygens attached to each phospho-
rus. In solution, one tripolyphosphate ion can form a complex with one cal-
cium ion by forming interactions between three of its oxygen atoms and the
metal ion (Figure 14-9b).
Substances like STP, which have more than one site of attachment to the
metal ion and thereby produce ring structures that each incorporate the
metal, are called chelating agents (from the Greek word for “claw”). Because
several bonds are formed, the resulting chelates are very stable and do not
normally release their metal ions back into the free form. The use of chelat-
ing agents to remove metals from the human body is discussed in Chapter 15.
Tripolyphosphate ion, P3O105, like phosphate ion itself, is a weak base
in aqueous solution and thus provides the alkaline environment that is
required for effective cleaning:
P3O105 H2O 9: P3O10H4 OH
Unfortunately, when wash water containing STP is discarded, the excess
tripolyphosphate enters waterways, where it slowly reacts with water and is
transformed into phosphate ion (sometimes called orthophosphate):
P3O105 2 H2O 9: 3 PO43 4 H
Note that when tripolyphosphate decomposes, STP behaves as an acid rather
than a base (since H is formed in the reaction).
Because of environmental concerns, polyphosphates are now used only
sparingly as builders in detergents in many areas of the world. In Canada and
parts of Europe, STP was replaced largely by sodium nitrilotriacetate (NTA)
(see Figure 14-10a). The anion of NTA acts in a similar fashion to that of
STP, chelating calcium and magnesium ions using three of its oxygen atoms
and the nitrogen atom (Figure 14-10b). NTA is not used as a builder in the
United States because of concerns that its slow rate of degradation might lead
to health hazards in drinking water. However, the early experiments with test
animals that led to this concern are open to question, as are fears about its
persistence and its tendency to solubilize heavy metals into water supplies.
Other builders now used include sodium citrate, sodium carbonate (washing
soda), and sodium silicate. Currently, substances called zeolites are also
employed as detergent builders. Zeolites are abundant aluminosilicate minerals
O
O C
CH2 9 C H2C O

O
N O
(a) (b) N Ca2
FIGURE 14-10 Structure O CH2 CH2 9 C H2C
O O
of the nitrilotriacetate ion: C CH2 C O
(a) uncomplexed and C
(b) complexed with
O O
calcium ion. O
(see Chapter 16) consisting of sodium, aluminum, silicon, and oxygen. The
latter three elements are bonded together to form cages, which the sodium ions
can enter. In the presence of calcium ion, zeolites exchange their sodium ions
for Ca2 (though not for Mg2), thereby sequestering it in a manner similar to
polyphosphates. Like polyphosphates, they also control pH. One disadvantage
to the use of zeolites is that they are insoluble, so their use increases the amount
of sludge that must be removed at wastewater treatment plants.
Phosphate ion can be removed from municipal and industrial waste-
water by the addition of sufficient calcium as the hydroxide Ca(OH)2, so
that insoluble calcium phosphates such as Ca3(PO4)2 and Ca5(PO4)3OH
are formed as precipitates that can then be readily removed. Phosphate
removal could be a standard practice in the treatment of wastewater, but it
is not yet practiced in all cities. Some policymakers believe that the opti-
mum environmental solution is to use polyphosphates, rather than some
other builder, in detergents and then to efficiently remove phosphates at
wastewater treatment plants.
Geographically, phosphate ion enters waterways from both point and non-
point sources. Point sources are specific locations such as factories, landfills,
and sewage treatment plants that discharge pollutants. Nonpoint sources are
numerous large land areas such as farms, logged forests, septic tanks, golf courses
and individual domestic lawns, stormwater runoff, and atmospheric deposition.
Although each nonpoint source may provide a small amount of pollution, on
account of the large number of them involved they can generate larger total
quantities than do point sources. For example, now that sewage treatment
plants and detergent controls have been instituted, much of the remaining
phosphate arises from nonpoint agricultural sources in many areas.
Green Chemistry: Sodium Iminodisuccinate—

A Biodegradable Chelating Agent
Because most chelating agents are not biodegradable or are only slowly
biodegradable, not only do they place a load on the environment (e.g., phos-
phates acts as nutrients), but it may be necessary to remove them during
treatment of wastewater in a wastewater O O

O
treatment plant. Unlike many chelating
agents, sodium iminodisuccinate (IDS, see NH3 NaO ONa
Figure 14-11) [also known as D,L-aspartic-N- O
NaOH NaO ONa
(1,2-dicarboxylethyl) tetrasodium salt] readily NH
degrades in the environment. Not only is IDS O
biodegradable, it is also nontoxic. O O
IDS can be used as an effective chelating maleic anhydride sodium iminodisuccinate
agent for absorption of agricultural nutrients,
FIGURE 14-11 Synthesis
metal ion scavenging in photographic processing, groundwater remediation, and structure of sodium
and as a builder in detergents and household and industrial cleaners. The iminodisuccinate, a
Bayer Corporation won a Presidential Green Chemistry Challenge Award in biodegradable chelating
2001 for the development of IDS as a chelating agent and for its synthesis agent.
from maleic anhydride (Figure 14-11). This synthesis is accomplished under
mild conditions, in water as the only solvent. The excess ammonia is recycled
back into the production of more IDS. This synthesis stands in stark contrast
to typical syntheses of aminocarboxylate chelating agents, which employ
hydrogen cyanide as a reagent. Bayer markets IDS as a chelating agent under
the name Baypure.
Reducing the Salt Concentration in Water

The decomposition of organic and biological substances during the secondary
phase of wastewater treatment usually results in the production of inorganic
salts, many of which remain in the water even after the techniques listed
above have been applied. Water can also become salty due to its use in irriga-
tion or because water softener units have been recharged and their discharge
disposed of as sewage. Inorganic ions can be removed from water by desalination
by using one of the techniques listed below or using the precipitation meth-
ods mentioned above.
• Reverse osmosis As previously mentioned, this technique is also used to
produce drinking water from salty water, such as seawater.
• Electrodialysis Here a series of membranes permeable either only to
small inorganic cations or only to small inorganic anions are set up vertically
in an alternating fashion (see Figure 14-12) within an electrochemical cell.
Direct current is applied across the water, so cations migrate toward the cath-
ode and anions toward the anode. The liquid in alternating zones becomes
more concentrated (enriched) or less concentrated (purified) in ions; eventu-
ally the ion-concentrated water can be disposed of as brine and the purified
water released into the environment. This technology is also used to desali-
nate seawater for drinking purposes.
• Ion exchange Some polymeric solids contain sites that hold ions relatively
weakly, so one type of ion can be exchanged for another of the same charge that
happens to pass by it. Ion exchange resins

Outgoing
can be formulated to possess either cationic
purified or anionic sites that function in this manner.
Outgoing water Outgoing The exchange sites of a cationic resin of this
brine brine type are initially occupied by H ions, and
+
–
–
the exchange sites of an anionic exchange
–
–
+ +
+
resin are occupied by OH ions. When water
– + – + polluted by M and X ions is passed sequen-
–
–
+
– +
– +
+ tially through the two resins, the H ions on
–
– + –
+
+ the first are replaced by M, and then the
+ – OH ions on the second resin are replaced by
Cathode Anode
X. Thus the water that has passed through
Incoming
salty water
contains H and OH ions, rather than
those of the salt, which remain behind in
Cation- Anion- the resins. Of course, these two ions imme-
+ Cations
permeable permeable diately combine to form more water mole-
– Anions membrane membrane cules. Thus ion exchange can be used to
remove salts, including those of heavy
metals, from wastewater.
FIGURE 14-12 Electro-
dialysis unit (schematic) for
the desalination of water.
[Adapted from S. E. Manahan. P R O B L E M 14-12
1994. Environmental Chem-
Water polluted by inorganic ions could be purified by distilling it or by freez-
istry, 6th ed. Boca Raton, FL:
Lewis Publishers.] ing it. Why do you think such techniques are not generally used on a mass
scale to purify water?
Transition metal cations can be removed from water using either precip-
itation or reduction techniques, in either case to form insoluble solids. Pre-
cipitation of sulfides or hydroxides has already been mentioned; a disadvantage
of the latter is the production of a voluminous sludge that must be disposed of
in an acceptable manner. Electrolytic reduction of metals leads to their dep-
osition on the cathode. If, instead of the elemental metal, a concentrated
aqueous solution of it is desired, the deposited metal can be reoxidized chem-
ically by adding hydrogen peroxide or electrolytically by reversing the polar-
ity of the cell.
The Biological Treatment of Wastewater and Sewage

An alternative to the processing of wastewater through a conventional treat-
ment plant in small communities is biological treatment in an artificial marsh
(also called a constructed wetland) that contains plants such as bullrushes and
reeds. The decontamination of the water is accomplished by the bacteria and
other microbes that live among the plants’ roots and rhizomes. The plants
themselves take up metals through their root systems and concentrate

contaminants within their cells. In facilities that have been constructed to
deal with sewage, primary treatment to filter out solids, etc. in a lagoon is
usually implemented before the wastewater is pumped to the marsh, where
the equivalent of secondary and tertiary treatment occurs. The plant growth
uses up the pollutants and increases the pH—which serves to destroy some
harmful microorganisms.
One advantage of biological treatment is that great amounts of sludge are
not generated, in contrast to conventional treatments. Furthermore, it requires
neither the addition of synthetic chemicals nor the input of commercial
energy. Among the problems in such facilities are decaying vegetation, which
must be limited so that the BOD of the processed water does not rise too
much, and the fact that the marshes usually require a great deal of land unless
they are constructed so that part of the routing is vertical.
In many rural and small communities, septic tanks are used to decontam-
inate sewage since central sewage facilities are not available. These under-
ground concrete tanks receive the wastewater, often from only one home.
Although solids settle in the tank, grease and oil rise to the top, from which
they are periodically removed. The bacteria in the wastewater feed on the
bottom sludge, thereby liquefying the waste. Partially purified water flows out
of the tank into an underground drain, where further decontamination takes
place. The system is relatively passive, compared to central facilities, and as
in the case of artificial marshes, time is required for the processes to occur. In
addition, nitrogen compounds are converted to nitrate, but the latter is not
reduced to molecular nitrogen, so groundwater under the septic system can
become contaminated by nitrate, as discussed earlier in this chapter.
Drugs in Wastewater from Sewage Treatment Plants

In recent years, trace concentrations of various drugs—prescription, over-
the-counter, illegal, and veterinary—have been detected in the waters lead-
ing from sewage treatment plants, and in rivers and streams into which this
water then flows, at concentrations up to the ppb level. About 100 sub-
stances have been detected in various rivers, lakes, and coastal waters. The
substances—commonly including estradiol, ibuprofen, the antidepressant drug
Prozac (fluoxetine), the anti-epileptic drug carbamazepine, and degradation
products associated with cholesterol-reducing pharmaceuticals—are present
in raw sewage after their excretion in urine or feces from humans and animals
since most drugs are poorly absorbed and metabolized by the body. They also
result from the disposal of unused or expired medication in toilets.
Most commonly, concentrations of drugs in drinking water are at the
parts-per-trillion level, so their risk to human health is probably small.
Research is under way to determine whether there could be effects on human
health from sustained exposure to a combination of these substances. The
synthetic hormones are thought to pose the greatest risk to aquatic species.
Certain fish have been found to undergo some skewed sexual development
due to exposure to sewage effluent containing the synthetic estrogen in birth
control pills (see Chapter 12).
The Treatment of Cyanides in Wastewater

The cyanide ion, CN, binds strongly to many metals, especially those of
the transition series, and is often used to extract them from mixtures. Conse-
quently, cyanide is widely used in mining, refining, and electroplating metals
such as gold, cadmium, and nickel. Unfortunately, cyanide ion is very poi-
sonous to animal life since it binds strongly to metal ions in living matter,
e.g., to the iron in proteins that are necessary for molecular oxygen to be uti-
lized by cells.
Cyanide is a very stable species and does not quickly decompose on its
own or in the environment. Thus it is an important water pollutant and
should be destroyed chemically rather than simply disposed of in a waterway.
We can deduce the type of treatment that will be effective for cyanide by
considering its acid–base and redox characteristics. Cyanide ion is the conjugate
base of the weak acid hydrocyanic acid, HCN, which has limited solubility
in water. Thus, acidification of cyanide solutions will result in the release of
poisonous HCN gas from it and therefore is not a good solution to the problem
of cyanide contamination.
The redox chemistry of cyanide ion can be predicted by considering the
oxidation numbers of the two atoms involved. If nitrogen, the more elec-
tronegative atom, is considered to be in its fully reduced 3 oxidation form,
then the carbon must be 2. Thus one way to destroy cyanide ion is to oxi-
dize the carbon more fully, to 4 as it is in CO2 and HCO3. This oxidation
can be accomplished by dissolved molecular oxygen if high temperatures and
elevated air pressures are used:
2 0 4 2
2 CN O2 4 H2O 2 HCO3 2 NH3
The use of stronger oxidizing agents, such as Cl2 or ClO, not only oxidizes
the carbon from 2 to 4, but can also oxidize the nitrogen from the 3
state to the zero oxidation number of molecular nitrogen:
2 3 0 4 0 1
2 CN 5 Cl2 8 OH 2 CO2 N2 10 Cl 4 H2O
(Four of the ten electrons gained collectively by the chlorines are used by the
carbons and six by the nitrogens in this overall process.) Other oxidizing
agents that are used in cyanide treatment include hydrogen peroxide, H2O2,
and/or molecular oxygen, in both cases with a copper salt added as a catalyst.
The process can also be carried out electrochemically for high cyanide con-
centrations; the remaining low concentration can be subsequently oxidized
by ClO.
Sodium cyanide is now used in some shallow tropical waters such as those
in Indonesia to stun reef fish so that they can be captured and sold live as
seafood or pets. Unfortunately, the cyanide kills smaller fish and destroys the
coral.
P R O B L E M 14-13
If an oxidizing agent even more powerful than chlorine or hypochlorite were
to be used in the treatment of cyanide, what other possibilities for the nitrogen-
containing product would there be?
P R O B L E M 14-14
For HCN in water, Ka 6.0 1010. Calculate the fraction of cyanide that
exists as the anion rather than in the molecular form at pH values of 4, 7,
and 10.
The Disposal of Sewage Sludge

The sludge from both the primary and secondary treatment stages of sewage
is principally water and organic matter. It can be digested anaerobically, in
a process that takes several weeks to complete. Bacteria levels in the sludge
are not thereby completely eliminated, but the levels are reduced about a
thousandfold. The sludge that remains after this further organic decompo-
sition has occurred and after the supernatant water is removed is sometimes
then incinerated or simply dumped into a landfill or into a water body such
as the ocean. However, sludge is high in plant nutrients, so about half the
sewage sludge in North America and Europe is spread on farm fields, golf
courses, and even residential lawns as low-grade fertilizer sometimes called
biosolid.
Unfortunately, sewage sludge may contain toxic substances, which poten-
tially could be incorporated into food grown on the land or could contaminate
groundwater under the fields. In particular, heavy metal concentrations often
are higher in sewage sludge than in soil, principally because industrial wastes
are sometimes released directly into sewage lines shared by households. For
example, the lead level in municipal sludge can range from several hundred
to several thousand parts per million, compared to an average of about 10 ppm
in the Earth’s crust. In a few communities, an attempt is made to eliminate
these toxic materials before final disposal occurs. Some scientists have wor-
ried that food crops grown in soil fertilized by sewage sludge may incorporate
some of the increased amounts of heavy metals. Control experiments indicate

that vegetables vary greatly in the extent to which they will absorb increased
amounts of the metals; e.g., the uptake of lead by lettuce is particularly large,
but that by cucumbers is negligible. The concentration of arsenic in agricultural
soils is greatly increased if arsenic pesticides are applied to them; crops
planted on these soils subsequently absorb some of the adsorbed arsenic.
Other substances of concern in using sewage sludge as fertilizer for food are
alkylphenols from detergents, brominated fire retardants, and pharmaceuticals—
especially antibiotics given to farm animals.
Modern Wastewater and

Air Purification Techniques
The most important chemical (as opposed to biological) pollutants dissolved
in wastewater are usually chloroorganics, phenols, cyanides, and heavy metals.
Below we describe some of the high-tech methods that have recently been
developed and put into practice to purify wastewater, particularly for removal
of chloroorganics. Some of these same techniques are also used to cleanse the
compounds from contaminated air.
The Destruction of Volatile Organic Compounds

The major stationary sources in North America of VOCs (Chapter 3) are the
evaporation of organic solvents, the manufacture of chemicals, and the petro-
leum industry and its storage activities. Wastewater effluent that is contami-
nated with VOCs, e.g., the water emanating from chemical or petrochemical
plants, is commonly treated by a two-step process:
1. The VOCs are removed from the wastewater by air stripping. In this
process, air is passed upward into a downward stream of the water, and
the volatile materials are transferred from the liquid to the gas phase. This
technique does not work well for compounds that are highly water soluble.
2. The resulting VOCs, now present in low concentration in a contained
mass of humid air, are destroyed by a process of catalytic oxidation. For
example, air heated to 300–500°C is passed for a short time over platinum
or, depending upon the VOC, some other precious metal that is supported
on alumina. The energy costs of this step are very high since it involves
heating a large volume of humid air. Note that the outlet air from such
processes contains hydrogen chloride, HCl, if the VOCs originally contained
chlorine; this compound must be removed by scrubbing with a basic substance
before the air is released into the atmosphere.
The removal of VOCs from gaseous emissions from industries usually
operates by the same catalytic oxidation process; typically the concentration
of VOCs in the air stream is thereby reduced by 95%. A primary heat

exchanger recovers and reuses the VOCs’ heat of combustion to warm
incoming gases to the operating temperature.
The adsorption of compounds onto activated carbon (see Box 14-1) or
onto synthetic carbonaceous adsorbents is a cost-effective technology used
for the removal of low-level VOC concentrations from both liquid and vapor
streams; it is also useful for nonvolatile organic compounds. These adsorbents
can be easily regenerated by treatment with steam or by other thermal tech-
niques as well as by solvents; the concentrated pollutants can be subsequently
destroyed by catalytic oxidation.
Advanced Oxidation Methods for Water Purification

Conventional water purification methods often do not successfully deal with
synthetic organic compounds such as chloroorganics that are dissolved at low
concentrations; examples include the common groundwater pollutants
trichloroethene and perchloroethene. The conventional method for the
treatment of water containing such pollutants is adsorption of the chloro-
organics onto activated carbon; this removes the compounds but doesn’t
destroy them. The wastewater from pulp-and-paper mills also contains
organochlorines that are resistant to conventional treatments.
In order to cleanse water of these extra-stable organics, so-called
advanced oxidation methods (AOMs) have been developed and deployed.
The aim of these methods is to mineralize the pollutants, i.e., to convert
them entirely to CO2, H2O, and mineral acids such as HCl. Most AOMs are
ambient-temperature processes that use energy to produce highly reactive
intermediates of high oxidizing or reducing potential, which then attack and
destroy the target compounds. The majority of the AOMs involve the
generation of significant amounts of the hydroxyl free radical, OH, which
in aqueous solution is a very effective oxidizing agent, as it is in air (see
Chapters 1–5). The hydroxyl radical can initiate the oxidation of a molecule
by extraction of a hydrogen atom or addition to one atom of a multiple bond,
as it does in air (Chapter 5); in water, as an additional alternative, it can also
extract an electron from an anion.
Since the generation of OH in solution is a relatively expensive process,
it is economical to use AOMs to treat only the components of the wastes that
are resistant to the cheaper, conventional treatment processes. Thus, inte-
grating an AOM with pretreatment of the wastewater by biological or other
processes to first dispose of the easily oxidized materials is often appropriate.
Ultraviolet (UV) light is often used to initiate the production of hydroxyl
radicals and thus to begin the oxidations. Commonly, hydrogen peroxide,
H2O2, is added to the polluted water and UV light from a strong source in the
200–300-nm range is shone on the solution. The hydrogen peroxide absorbs
the ultraviolet light (especially that closer to 200 nm than to 300 nm) and
uses the energy obtained to split the O9O bond, resulting in the formation
of two OH radicals:
UV
H2O2 9: 2 OH
Alternatively, and less commonly, ozone is produced and then photochemi-
cally decomposed by UV light. The resulting oxygen atom reacts with water
to efficiently produce OH via the intermediate production of hydrogen perox-
ide, which is photolyzed:
UV
O3 9: O*2 O*
UV
O* H2O 9: H2O2 9: 2 OH
A fraction of the oxygen atoms produced by ozone photolysis are electroni-

cally excited, and these react with water to directly produce hydroxyl radi-
cals, as discussed in Chapter 1.
P R O B L E M 14-15
Given that the enthalpies of formation for H2O2 and OH are, respectively,
136.3 and 39.0 kJ mol1, calculate the heat energy required to dissociate
one mole of hydrogen peroxide into hydroxyl free radicals. What is the max-
imum wavelength of light that could bring about this transformation? [Hint:
See Chapter 1]. Given that light of 254-nm wavelength is usually used, and
that all the energy of each photon that is in excess of that required to disso-
ciate one molecule is lost as waste heat, calculate the maximum percentage of
the input light energy that can be used for dissociation itself.
Hydroxyl radicals for wastewater treatment can also be efficiently pro-

duced without the use of UV light by combining hydrogen peroxide with
ozone. The chemistry of the intermediate processes is complex, but the over-
all reaction between these two species is
H2O2 2 O3 9: 2 OH 3 O2
This ozone/H2O2 method is more cost-effective and easier to adapt to existing
water treatment systems than is any other AOM system.
It is also possible to generate the hydroxyl radical electrolytically. In most
such applications, a metal ion (such as Ag or Ce3) is first oxidized to a
more positively charged ion (Ag2 or Ce4 in our examples) that will subse-
quently oxidize water to H and OH.
The biggest liability associated with advanced oxidation processes is that
their action produces toxic chemical by-products. For example, in the ozone/
peroxide and peroxide/UV treatments of groundwater contaminated with
trichloroethene and perchloroethene, the toxic intermediates trichloroacetic

acid, CCl3COOH, and dichloroacetic acid, CHCl2COOH, are formed in about
1% yield.
Photocatalytic Processes
Another innovative technology for wastewater treatment involves the irradi-
ation by UV light of solid semiconductor photocatalysts such as titanium
dioxide, TiO2, small particles of which are suspended in solution. Titanium
dioxide is chosen as the semiconductor for such applications since it is non-
toxic, is very resistant to photocorrosion, is cheap and plentiful, absorbs light
efficiently in the UV-A region, and can be used at room temperature. Irradi-
ation at wavelengths less than 385 nm produces electrons, e, in the conduction
band and holes, h, in the valence band of the metal oxide. The holes in the
semiconductor can react with surface-bound hydroxide ions or with water
molecules, thereby producing hydroxyl radicals in both cases:
h OH 9: OH
h H2O 9: OH H
The holes can also react directly with adsorbed pollutants, producing radical
cations that readily engage in subsequent degradation reactions.
Normally, O2 molecules dissolved in the water react with the electron
produced at the semiconductor surface, a process that eventually produces
more reactive free radicals but is relatively slow. If hydrogen peroxide is added
to the water instead, it will react with the electron to form the anion radical
and generate reactive radicals more quickly.
The cost of the electrical energy required to generate the needed UV
light is usually the major expense in operation of AOM systems. On this
basis, the titanium dioxide methods are even less cost-effective than those
described previously, since considerably more electricity is required per pollu-
tant molecule destroyed. Sunlight could be used to supply the UV light, but
only about 3% of its light lies in the appropriate UV-A range and is absorbed
by the solid. Another problem with the TiO2 processes is the difficulty in sep-
arating the various reactants and products from the TiO2 particle if the metal
oxide has been used in the form of a fine powder. However, there are now
closed systems in which the titanium dioxide slurry is efficiently separated
from the purified water and recycled back to the inlet stream.
Some scientists have experimented with immobilizing TiO2 as a thin film
(1 mm thick) on a solid surface such as glass, tile, or alumina. Indeed,
TiO2-coated tiles are now used on walls and floors in some buildings. The
low-level UV light from fluorescent lighting in such rooms is sufficient to
allow the destruction of gaseous and liquid-phase pollutants that touch the
oxide on the tiles! For example, odors that upset people are usually present in
air at concentrations of only about 10 ppm; at such levels, the UV from

normal fluorescent lighting should be sufficient to destroy them with TiO2
photocatalysts. Bacterial infections such as those that cause many secondary
infections in hospitals can also be eliminated by spraying walls and floors (in
rooms lit by fluorescent bulbs) to give them a titanium dioxide film. Photo-
catalysts are quiet, unobtrusive cleansing materials.
Other Advanced Oxidation Methods

A process called direct chemical oxidation has been proposed for the destruc-
tion of solid and liquid organic wastes in the aqueous phase, particularly in
environments such as those under buildings, where the light required for
UV processes cannot conveniently be supplied. It uses one or another of
the strongest known chemical oxidants—e.g., acidified peroxydisulfate
anion, S2O82, under ambient pressure and moderate temperatures to oxidize
the wastes. Such a process needs no catalysts and produces no secondary
wastes of concern. The sulfate that results from the peroxydisulfate can be
recycled back to the oxidant. Other very strong oxidizing agents that have
been tested are the peroxymonosulfate anion, HSO5, and the ferrate ion,
FeO42; in the latter, iron has an oxidation number of 6, so it is not surpris-
ing that it is a strong oxidizing agent. Unfortunately, ferrate ion suffers from
the problem of instability.
P R O B L E M 14-16
Deduce the balanced half-reaction (acidic media) in which the peroxydisul-
fate ion is converted into sulfate ion. Repeat the exercise for the conversion of
oxalic acid, C2H2O4, into carbon dioxide. Combine these half-reactions into
a balanced equation, and calculate the volume of 0.010 M peroxydisufate that
is required to oxidize one kilogram of oxalic acid.
Review Questions
1. Describe the function of (a) aeration and 4. What two other chemical methods, other than
(b) addition of aluminum or iron sulfate in the chlorination, are used to disinfect water? What are
purification of drinking water. some advantages and disadvantages to these
alternatives?
2. Describe the chemistry underlying the removal
of excess calcium and magnesium ions from drinking 5. Explain the chemistry underlying the disin-
water. fection of water by chlorination. What is the
active agent in the destruction of the pathogens?
3. Describe how water can be disinfected by
What are the practical sources of the active
(a) membrane filtration and (b) ultraviolet
ingredient?
irradiation.
6. Explain why pH control of water in swimming 18. Define the term plume and describe how it
pools is important. What compounds are formed forms in an aquifer.
when the chlorinated water reacts with ammonia?
19. Why are the BTX and MTBE components
7. Discuss the advantages and disadvantages of of gasoline the ones that are most often found
using chlorination to disinfect water, including the in groundwater? Are both components easily
nature of the THM compounds. biodegraded?
8. What is meant by the terms groundwater and 20. What is meant by reductive degradation?
aquifer? How does the saturated zone of soil differ Describe the in situ technique by which chloroor-
from the unsaturated? ganics in aquifers can be destroyed by reductive
dechlorination.
9. Why did concern about groundwater pollution
lag far behind that about surface water? 21. What procedures are involved in primary
wastewater treatment? In secondary treatment?
10. Name three important sources of nitrate ion
to groundwater. 22. List five possible water purification processes
that are associated with the tertiary treatment
11. Construct a table that shows the common
of wastewater, including one that removes
oxidation numbers for nitrogen. Deduce in which
phosphate ion.
column the following environmentally important
compounds belong: HNO2, NO, NH3, N2O, N2, 23. What polyphosphate was commonly used in
HNO3, NO3. Which of the species become detergents, and why did its use lead to environ-
prevalent in aerobic conditions in a lake? Under mental problems? What are the other main sources
anaerobic conditions? What is the oxidation of phosphate to natural waters? What other
number of nitrogen in NH2OH? builders are used in detergents?
12. Explain why excess nitrate in drinking water 24. Describe two important methods that are used
or food products can be a health hazard; include to desalinate wastewater.
the relevant balanced chemical reaction showing
25. Describe the chemical processes by which
how nitrate becomes reduced.
cyanide ion can be removed from wastewater.
13. What is an N-nitrosamine? Write the structure
26. Describe how VOCs dissolved in wastewater
and the full name for NDMA.
are usually removed and destroyed.
14. What is the formula for the perchlorate ion?
27. Describe what AOMs stands for, and state the
What is the origin of perchlorate ion in U.S.
most common reactive agent in such processes.
drinking water?
Describe three methods by which this reactive
15. Define leachate. species can be generated.
16. Name two types of organic contaminants 28. Describe two photocatalytic methods that can
found in groundwater, and give two examples of destroy organic wastes.
each type.
29. What is direct chemical oxidation? What are
17. Explain the difference in vertical location in two of the strong oxidizing agents that can be used
an aquifer between compounds such as chloroform for such procedures?
and those such as toluene.

See the discussion of focus areas and the princi- (a) Into which of the three focus areas for these
ples of green chemistry in the Introduction before awards does this award best fit?
attempting these questions. (b) List at least three of the twelve principles of
1. What are the environmental advantages of using green chemistry that are addressed by the green
iminodisuccinate compared to most chelating agents? chemistry developed by Bayer.
2. The development of iminodisuccinate by

Bayer won a Presidential Green Chemistry
Challenge Award.
Additional Problems
1. Given that for HOCl, Ka 2.7 108, deduce laundry detergents used were about 50%, calculate
the fraction of a sample of the acid in water that the volume that was required annually to dispose
exists in the molecular form at pH values (predeter- of its waste laundry phosphate.
mined by the presence of other species) of 7.0, 7.5, 4. Calculate the oxidation number of the
8.0, and 8.5. [Hint: Derive an expression that relates chlorine in molecular chlorine, HOCl, chlorine
the fraction of HOCl that is ionized to the concentration dioxide, monochloramine (NH2Cl), and
of hydrogen ions.] Would it be a good idea to allow sodium chloride. Given that the last item is
the pool water’s pH to rise to 8.5? the most stable form of chlorine, predict whether
2. The equilibrium constant for the reaction of the other substances mentioned are likely to be
dissolved molecular chlorine with water to give oxidizing agents or reducing agents, and rank
hydrogen ions, chloride ions, and HOCl is 4.5 them in likely order of this redox behavior. Using
104, where as usual the concentration of water is this analysis and the section on chlorine com-
included in the K value. If the pH of the solution is pounds in your introductory chemistry textbook,
determined by other processes so that the amount suggest other compounds that might be useful to
of hydrogen ion contributed by the chlorine reac- disinfect water.
tion is negligible, calculate the fraction of the origi- 5. Given their names, can you deduce the nature
nal 50 ppm chlorine which remains as Cl2 at pH of the similarity in molecular structure between
values of 0, 1, and 2. [Notes: (1) The dissociation of hydrogen peroxide and the sulfur compounds that
HOCl into ions is negligible at these low pH val- are used in direct chemical oxidation methods?
ues. (2) Approximate solutions to the quadratic By calculating the oxidation number of the atoms
equation involved in these calculations will not be in hydrogen peroxide, deduce why it can act as an
accurate due to the high percentage of reaction.] oxidizing agent.
3. Calculate the volume of Ca5(PO4)3OH, the 6. What could be done to dispose of the solvents
density of which is 3.1 g/mL, which is produced for that are used to extract VOCs from adsorbents?
each gram of sodium tripolyphosphate present in a
detergent when it is removed in tertiary wastewater 7. Write the initial reaction step that occurs if
treatment. Estimate the annual mass of detergent methyl chloroform, CH3CCl3, were to be
used for laundry purposes for a typical household of destroyed by (a) reductive degradation and (b)
four persons. Assuming that the phosphate levels in hydroxyl radical attack.
8. Water samples from three wastewater streams 11. At a particular temperature, Ka for HOCl is
were analyzed, and the important pollutants 3.5 108. What would be the pH values for
determined to be those listed below. In each case, 1.00 M and 0.100 M concentrations of HOCl at
devise economical, practical processes (other than this temperature? What percentages of the HOCl is
activated carbon treatment) for purifying the water undissociated at these two concentrations?
of the three pollutants:
12. To desalinate seawater by reverse osmosis,
(a) Phosphate ion, ammonium ion, and salt pressure in excess of a solution’s osmotic pressure,
(in water containing bicarbonate ion) p, must be applied across the membrane. The total
(b) Nitrite ion, PCE, and Fe(II) osmotic pressure exerted in a solution is determined
by the total molar concentration, M, of its solutes,
(c) Cadmium ion, carbon tetrachloride, and glucose
and is given by the equation p MRT. Using the
9. Write the reaction that occurs between hydroxyl composition of seawater listed in Chapter 13, deter-
radical and carbonate ion dissolved in water. What mine the minimum pressure that must be exerted
are two alternative substances that you could add to on seawater to desalinate it using reverse osmosis at
the water to decrease the carbonate ion concentra- 20°C. Recall that R 0.082 L atm mol1 K1.
tion, one that operates by elimination of carbon diox-
13. Chlorine-containing substances covering a wide
ide and the other by precipitation of the ion, so as to
variety of oxidation numbers have been encoun-
decrease the amount of hydroxyl radical destroyed by
tered, some within this chapter and others previ-
this reaction? Given the solubility product constants
ously in the book. For each substance in the list
in this chapter, estimate the lowest practical carbon-
below, write out its formula, deduce the oxidation
ate concentration you could reach by this process,
number of its chlorine, and fill in the appropriate
and comment on the desirability of the ions that you
row of the table below, as in the example shown:
have introduced into the water.
chlorite ion perchlorate ion
10. Treated drinking water should contain
0.5 mg/L of Cl2 after most of the chlorine has molecular chlorine hypochlorous acid
been converted to HOCl. What pressure of Cl2(g)
chlorine dioxide chlorine monoxide
is required to maintain this concentration?
KH 8.0 103 M for Cl2. chloride ion chlorate ion
Oxidation Number Formula of Example Name of Example
1
0
1
2
3
4
5
6 ClO3 Chlorine trioxide
7
Further Readings
1. A. Kolch, “Disinfecting Drinking Water with UV Countries,” Environmental Science and Technology
Light,” Pollution Engineering (October 1999): 34. 41 (2007): 17.
2. F. Bove et al., “Drinking Water Contaminants 12. B. T. Nolan et al., “Risk of Nitrate in Ground-
and Adverse Pregnancy Outcomes: A Review,” waters of the United States—A National Perspec-
Environmental Health Perspectives 110 (supplement 1) tive, Environmental Science and Technology 31
(2002): 61. (1997): 2229.
3. J. R. Nuckols et al., “Influence of Tap Water 13. J. A. MacDonald, “Evaluating Natural Atten-
Quality and Household Use Activities on Indoor uation for Groundwater Cleanup,” Environmental
Air and Internal Dose Levels of Trihalomethanes,” Science and Technology (August 1, 2000): 346A.
Environmental Health Perspectives 113 (2005): 863.
14. L. W. Canter, R. C. Knox, and D. M.
See also ibid, 114 (2006): 514.
Fairchild, Groundwater Quality Protection (Boca
4. U. van Gunten, “Ozonation of Drinking Water,” Raton, FL: Lewis Publishers, 1987).
Parts I and II, Water Research 37 (2003): 1443, 1469.
15. E. K. Nyer, Groundwater Treatment Technology,
5. S. D. Richardson et al., “Identification of New 2nd ed. (New York: Van Nostrand Reinhold, 1992).
Ozone Disinfection Byproducts in Drinking
16. D. M. Mackay and J. A. Cherry, “Ground-
Water,” Environmental Science and Technology 33
water Contamination: Pump-and-Treat Remedia-
(1999): 3368.
tion,” Environmental Science and Technology 23
6. R. F. Service, “Desalination Freshens Up,” (1989): 630.
Science 313 (2006): 1088.
17. R. J. Gilliom, “Pesticides in U.S. Streams
7. “Chlorinated Solvent Source Zones,” Environ- and Groundwater,” Environmental Science and
mental Science and Technology (June 1, 2003): 225A. Technology 41 (2007): 3409.
8. P. B. Hatzinger, “Perchlorate Biodegradation for 18. “Environmental Processes ’96: A Special
Water Treatment,” Environmental Science and Tech- Report,” Hydrocarbon Processing Magazine (Interna-
nology (June 1, 2005): 239A. tional Edition) 75 (1996): 85 [reviews many emerg-
ing technologies that can handle water and air
9. L. Fewtrell, “Drinking-Water Nitrate, Methe-
pollution problems].
moglobinemia, and Global Burden of Disease: A
Discussion,” Environmental Health Perspectives 112 19. D. Simonsson, “Electrochemistry for a cleaner
(2004): 1371. environment,” Chemical Society Reviews 26 (1997):
181.
10. M. P. Zeegers et al., “Nitrate Intake Does Not
Influence Bladder Cancer Risk: The Netherlands 20. N. C. Baird, “Free Radical Reactions in Aque-
Cohort Study,” Environmental Health Perspectives ous Solutions: Examples from Advanced Oxida-
114 (2006): 1527. tion Processes for Wastewater and from the
Chemistry in Airborne Water Droplets,” Journal of
11. M. A. Montgomery and M. Elimelech,
Chemical Education 74 (1997): 817.
“Water and Sanitation in Developing
Ion Chromatography of Environmentally Significant Anions 657
Environmental Ion Chromatography of Environmentally

Instrumental
Analysis V
Significant Anions
The quantitative determination of levels of environ- microparticles of silica coated with compounds
mentally important ions, such as those discussed in containing an anionic functional group such
the preceding chapters, can be accomplished using as a quaternary amine, ¬N(CH3)3OH, or a
chromatographic methods described in this box. primary amine, ¬NH3OH, when they are
to be used for anion separation.
he need to determine the prevalence of The actual process of chromatographic
T common anions like phosphate (PO43),
nitrate (NO3), or fluoride (F) isn’t immedi-
separation occurs after a sample containing
analyte anions (and their associated cations)
ately clear. The biospheric significance of is injected onto the chromatographic column.
these ubiquitous ions is not as obvious as is, for With gas chromatography (see Environmental
example, the presence of PCBs, pesticides, or Instrumental Analysis Box II), the mobile
toxic metals like lead, mercury, or cadmium. phase is an inert gas that does not chemically
These ionic components are important interact with the chromatographic surface.
because they give an indication of the relative The mobile phase in ion chromatography, on
reduction–oxidation potential in an aqueous the other hand, is a solution of cations and
sample taken from an environment such as a anions with a carefully controlled pH; often
stagnant lake (PO43), or of the contamina- buffers are used. This complex mixture of
tion of groundwater from fertilizer runoff mobile-phase ions—carefully chosen for each
(NO3), or of whether municipal water sup- group of analyte ions to be separated—interacts
plies need to be supplemented with fluoride with the analyte ions and the functional
(F) for the health of children’s teeth. groups of the column’s chromatographic
Although these charged ions can be detected surface. That interaction involves competi-
by widely available ultraviolet detectors tion of the mobile-phase anions and the ana-
common in most high-performance liquid lyte anions for chromatographic sites on the
chromatographic systems (Janos and Aczel, packing material (the charged functional
1996), a more sensitive means of detection groups such as ¬N(CH3)3 or ¬SO3). This
involves ionic conductivity. This chromato- competition yields different overall travel
graphic method is called ion chromatography times for each of the analytes as they pass down
with ionic conductivity detection. Although the column; some are retained longer than
cations can also be separated by ion chro- others. (The overall down-column movement
matography (IC), only anionic separations is provided by a pumping of the mobile
will be discussed here. phase by an external pump.) Different analyte
The heart of the separation process in travel times—as in gas chromatography—
an ion chromatograph is a short column translate into different exit (or retention)
(10–15 cm) packed with small-diameter parti- times for each anion in the original mixture.
cles called ion exchange resins. These are often The result is chromatographic separation of
made of a styrene/divinylbenzene polymer or anions.
658 Environmental Instrumental Analysis V

Instrumental
Analysis V
Significant Anions (continued)
The process for anionic ion chromato- the end of the IC column is normally not
graphic retention by ion exchange resins can practical. The problem is especially difficult
be represented by the equation because, in order to obtain adequate separa-
tion of some important anions, the mobile
RN(CH3)3HCO3(s) anion⫺(aq) 9: phase often has to have high ionic content to
RN(CH3)3 anion⫺(s) HCO3(aq) displace the analyte anions from the chro-
matographic surface—something that is
In this equation, the term anion⫺ represents obviously required for separation. Therefore,
any of the analyte anions mentioned above. most of the ionic conductivity passing through
When a sample is injected onto the column, the detector is attributable to the mobile-
this anion is quickly retained by complexation phase ions and not the analyte—an unwork-
with the stationary phase near the head of the able situation when trying to detect the
column. The next step in the chromatographic analyte anions by their conductivity.
process takes place as a mobile phase, with a An ingenious solution to this problem is
carefully controlled amount of anionic ion called conductivity suppression or eluent (mobile-
such as bicarbonate, HCO3, is pumped phase) suppression. This technology converts
through the column. The presence of the bicar- the mobile-phase anions from an easily disso-
bonate anion in the mobile phase forces the ciated ionic form to a (soluble) molecular form
equilibrium in the above equation to the left; that does not strongly influence the signal
the retained analyte anion is freed and moves produced by the conductivity detector. The
down the column in the flowing mobile phase. suppression module is placed after the chro-
As the analyte moves along, it repeatedly matographic column but before the conduc-
undergoes this same process of retention and tivity detector. In an anion exchange system,
movement (or exchange between the stationary the suppression module might carry out the
and mobile phases). Most importantly, differ- following reaction:
ent analyte anions (e.g., fluoride or phosphate
or chloride) undergo this exchange process to Na(aq) HCO3(aq) resin⫺H⫹(s) 9:
differing degrees and therefore travel at differ- resin– Na(s) H2CO3(aq)
ent overall rates during their time in the IC
column. The result is that different analytes Here resin⫺H⫹ represents a cation exchange
exit the chromatographic column at different resin that will exchange cations—instead of
times, i.e., separation has taken place. anions as in the chromatographic column
The task of detecting analyte anions in described. This process basically prevents (or
the presence of the anions always present in suppresses) the mobile phase’s anions from
the mobile phase is by no means a trivial one. contributing to the conductivity by converting
Since both kinds of anions—the analytes’ and current-conducting bicarbonate anion into
the mobile phase’s—conduct electricity, using relatively undissociated H2CO3. Therefore, the
an ordinary conductivity cell as a detector at conductivity detector’s signal is based almost
Ion Chromatography of Environmentally Significant Anions 659
Injector
Ion exchange
Mobile- column Eluent
phase suppression Conductivity
pump module detector
Sample is Analytes’ Mobile-phase Analyte ions

introduced. retention times ions are are detected
based on converted against a quiet,
interaction to molecular stable back-
of analyte, forms that do ground by
ion exchange not produce their electrical
column, and significant conductivity.
mobile-phase signals
ions. in detector.
completely on the passage of analyte anions detector and chose an analytical wavelength at
through the detector cell. (Those anions are which neither the mobile phase nor other
not affected by the cation ion exchange resin.) anions would absorb (205 nm). Surprisingly,
This results in lower (i.e., better) detection dew had the highest concentrations of these
limits for the analytes of interest and a more
stable baseline (less noise and drift) than a
similar system without eluent suppression. Phosphate
The figure above is a schematic of an ion
Chloride
chromatographic system. Detailed are an injec-

tor, chromatographic column, eluent suppres-
Fluoride
sion module, and conductivity detector, as well

Detector signal
Nitrate
as the processes that occur at each step.

The figure at right is an example of the
kind of chromatogram that a system of this
type would generate. The anions detected are
fluoride, chloride, phosphate, and nitrate. As
with all chromatograms, detector signal inten-
sity is plotted versus time.
Researchers have used this method 0 4 8 12 16 20
recently to determine nitrate and nitrite anions Time (minutes)
in dew, rain, and snow collected in Massachu-
setts (Zuo et al., 2006). Instead of conductivity
detection, these authors used a UV absorption (continued on p. 660)
660 Environmental Instrumental Analysis V

Instrumental
Analysis V
Significant Anions (continued)
Sample Date Nitrite (ppb) Nitrate (ppm)
Dew 1 27.09.2005 640 4.87

2 27.09.2005 620 4.79
3 26.09.2005 830 5.99
Rain 1 02.10.2005 < DL* 2.63

2 02.09.2005 < DL* 2.62
3 28.05.2005 140 1.20
Snow 1 29.01.2005 21 0.320

2 18.01.2005 32 0.376
3 12.01.2005 32 0.60
4 12.01.2005 26 0.56
* Detection limit for nitrite 10 ppb.
anions compared to rain and snow collected at have concluded that 40% of hydroxyl radial
the same site (see table above). The authors pro- production in dew on those trees originates
posed that these dew nitrate concentrations, from nitrite and nitrate (Nakatani et al.,
ranging from 4.79 to 5.99 ␮g/mL, suggest that 2001).
dew is acting as a nighttime sink for these
anionic species; they also note that this may be
References: P. Janos and P. Aczel, “Ion Chromato-
important for vegetation because these anions graphic Separation of Selenate and Selenite Using a
are held in contact with the leaf surface for long Polyanionic Eluent,” Journal of Chromatography A 749
time periods as dew forms, and the concentration (1996): 115–122.
may spike as dew evaporates in the morning. T. Kobayashi, N. Natanani, T. Hirakawa, M. Suzuki,
Since photolysis of both these anions in T. Miyake, M. Chiwa, T. Yuhara, N. Hashimoto,
shallow aqueous solution can lead to the for- K. Inoue, K. Yamamura, N. Agus, J. R. Sinogaya,
K. Nakane, A. Kume, T. Arakaki, and H. Sakugawa,
mation of hydroxyl radical and hydrogen per- Environmental Pollution 118 (2002): 383–391.
oxide, this may be a source of oxidative stress
N. Nakatani, T. Miyake, M. Chiwa, M. Hashimoto,
for plants on which the dew forms (Kobayashi T. Arakaki, and H. Sakugawa, “Photochemical For-
et al., 2002): mation of OH Radicals in Dew Formed on the Pine
Needles at Mt. Gokurakuji,” Water, Air and Soil
NO2 H2O light 9: OH NO OH Pollution 130 (2001) 397–402.
NO3 H2O light 9: OH NO2 OH Y. Zuo, C. Wang, and T. Van, “Simultaneous Determi-
nation of Nitrite and Nitrate in Dew, Rain, Snow and
Studies of this process on red pine needles on Lake Water Sample by Ion-Pair High-Performance
trees on Mount Gokurakuji in western Japan Liquid Chromatography,” Talanta (2006): 281–285.
PART V
METALS, SOILS,
SEDIMENTS, AND
WASTE DISPOSAL
Contents of Part V
Chapter 15 Toxic Heavy Metals
Chapter 16 Wastes, Soils, and Sediments
Environmental Instrumental Analysis VI

 Inductively Coupled Plasma Determination of Lead

 Mapping Mercury
C H A P T E R
15
TOXIC HEAVY METALS
In this chapter, the following introductory chemistry topics

are used:
 Redox half-reactions
 Electrolysis
 Half-life calculations
 Solubility product and acid–base equilibrium constant
calculations, including manipulations for multiple
equilibria

 Steady state; UV and visible light wavelengths
(Chapter 1)
 Synergism (Chapter 4)
 Bioaccumulation; LD50; dose–response curves;
maximum contaminant level (Chapter 10)
 Aerobic, anaerobic, and calcareous waters (Chapter 13)
Introduction
In chemistry, heavy metal refers not to a type of rock music but rather to a
type of chemical element, many examples of which are poisonous to humans.
The five main ones discussed here—mercury (Hg), lead (Pb), cadmium (Cd),
chromium (Cr), and arsenic (As)—present the greatest environmental hazard
due to their extensive use, their toxicity, and their widespread distribution.
None have yet pervaded the environment to such an extent as to constitute
a widespread danger. However, each one has been found at toxic levels in cer-
tain locales in recent times. Metals differ from the toxic organic compounds
663
664 Chapter 15 Toxic Heavy Metals
Densities of Some Important Heavy

TABLE 15-1 Metals and Other Substances
Substance Density (g/cm3)

Hg 13.5
Pb 11.3
Cu 9.0
Cd 8.7
Cr 7.2
Sn 5.8 – 7.3
As 5.8
Al 2.7
Mg 1.7
H2O 1.0
we discussed in Chapters 10–12 in that they are totally nondegradable to

nontoxic forms, although they ultimately may be transformed to insoluble
forms, which therefore are biologically unavailable unless they are again con-
verted into more soluble substances. The ultimate sinks for heavy metals are
soils and sediments.
The heavy metals occur near the middle and bottom of the periodic
table. Their densities are high compared to those of other common materials.
The densities of the metals of interest here are collected in Table 15-1, as are
values for water and two common “light” metals for contrast.
Although we commonly think of heavy metals as water pollutants, they
are for the most part transported from place to place via the air, either as gases
or as species adsorbed on, or absorbed in, suspended particulate matter. As we
shall see later in the chapter, the deposition of airborne lead into European
lake sediments dates back to the time of the ancient Greeks. These days, over
half the heavy-metal input into the waters of the Great Lakes, for example, is
due to deposition from the air.
Speciation and the Toxicity of Heavy Metals

Although mercury vapor is highly toxic, the heavy metals Hg, Pb, Cd, Cr, and
As are not particularly toxic as the condensed free elements. However, all are
dangerous in the form of their cations and most are also highly toxic when
bonded to short chains of carbon atoms. Biochemically, the mechanism of
the toxic action usually arises from the strong affinity of the cations for sulfur.
Thus, sulfhydryl groups, 9SH, which occur commonly in the enzymes that
control the speed of critical metabolic reactions in the human body, readily
Introduction 665
attach themselves to ingested heavy-metal cations or to molecules that con-

tain the metals. Because the resultant metal–sulfur bonding affects the entire
enzyme, it cannot act normally and, as a result, human health is adversely
affected, sometimes fatally. The reaction of heavy-metal cations M2 (where
M is Hg, Pb, or Cd) with the sulfhydryl units of enzymes R9S9H to produce
stable systems such as R9S9M9S9R is analogous to their reaction with
the simple inorganic chemical hydrogen sulfide, H2S, with which they yield
the insoluble solid MS.
P R O B L E M 15-1
Write the balanced chemical reactions that correspond to the reaction of an
M2 ion (a) with H2S and (b) with R9S9H to produce hydrogen ions and
the products mentioned above.
A common medicinal treatment for acute heavy-metal poisoning is the

administration of a compound that binds to the metal even more strongly
than does the enzyme; subsequently the metal–compound combination is sol-
ubilized and excreted from the body. One compound used to treat mercury
and lead poisoning is British Anti-Lewisite (BAL); its molecules contain
two 9SH groups that together capture the metal. Also useful for this purpose
is the calcium salt of ethylenediaminetetraacetic acid (EDTA), a well-known
compound that extracts and solubilizes most metal ions. The metal ions are
complexed by the two nitrogens and the charged oxygens to form a chelate
(Chapter 14) which is subsequently excreted from the body.
CH2 9 CH 9 CH2
OH SH SH
British Anti-Lewisite
Treatment of heavy-metal poisoning by chelation therapy is best begun early,

before neurological damage has occurred. The calcium rather than the
sodium salt is used in order that calcium ion is not inadvertently leached from
the body by the EDTA.
The toxicity for all four heavy metals depends very much on the chemical
form of the element, i.e., upon its speciation. Substances that are almost
totally insoluble pass through the human body without doing much harm.
The most devastating forms of the metals
• cause immediate sickness or death (e.g., a sufficiently large dose of arsenic
oxide) so that therapy cannot exert its effects in time, and
• can pass through the membrane protecting the brain—the blood–brain
barrier—or the placental barrier that protects the developing fetus.
For mercury and lead, the forms that have alkyl groups attached to the metal
are highly toxic. Because such compounds are covalent molecules, they are
soluble in animal tissue and can pass through biological membranes, whereas
charged ions are less able to do so; e.g., the toxicities of lead as the ion Pb2
and in covalent molecules differ substantially.
The toxicity of a given concentration of a heavy metal present in a natural
waterway depends not only on its speciation but also on the water’s pH and
on the amounts of dissolved and suspended carbon in it, since interactions
such as complexation and adsorption may well remove some of the metal ions
from potential biological activity.
Bioaccumulation of Heavy Metals

Recall from Chapter 10 that some substances display the phenomenon of
biomagnification: Their concentrations increase progressively along an eco-
logical food chain. The only one of the five heavy metals under consideration
that is indisputably capable of doing this is mercury. Many aquatic organisms
do, however, bioconcentrate (but do not biomagnify) heavy metals. For
example, oysters and mussels can contain levels of mercury and cadmium that
are 100,000 times greater than those in the water in which they live.
The concentrations of most heavy metals in drinking water are usually
small and cause no acute health problems; however, exceptions do occur and
will be discussed later. As is the case with toxic organic chemicals, the amounts
of metals that are ingested through our food supply are usually of much greater
concern than is the intake attributable to drinking water. Paradoxically, the
heavy metals in the fish that we ingest usually originate in fresh water.
Mercury
Mercury Vapor
Elemental mercury was employed in hundreds of applications, many of which
(e.g., electrical switches) took advantage of the unusual property that it is a
liquid that conducts electricity well. In automobiles built before 2000, electri-
cal switches that operate convenience and trunk lighting contained mercury,
as did instrument panels and antilock brakes; all of this mercury is lost to the
environment when the cars are recycled for their steel unless the element is
specifically collected, as is required in some locales.
Elemental mercury is still used in fluorescent light bulbs, including the
small ones now used domestically to replace incandescent bulbs, and in the
mercury lamps employed for street lighting. Although energized mercury
atoms emit light in the ultraviolet rather than the visible wavelength region
of the spectrum (Chapter 1), the bulbs are coated with a material that absorbs
the UV and re-emits it from the bulb as visible light. The metal is released
Mercury 667
into the environment if such light bulbs are broken, though the mercury
content of fluorescent lamps has been reduced by about 80% since the mid-
1980s, down to 5–10 mg each today. This amount of mercury is less than the
additional quantity of the metal that would have been emitted into the air by
a coal-fired power plant if an incandescent light bulb, with its much lower
efficiency in converting electricity to light, had been used instead. Fluorescent
bulks are virtually the only use of mercury for which a suitable alternative has
not been found. For street lighting, there has been a shift toward the use of
sodium vapor lamps, since such bulbs present a lower toxicity hazard and are
even more efficient light sources than mercury bulbs.
Mercury is the most volatile of metals, and its vapor is highly toxic.
Adequate ventilation is required whenever mercury is used in closed quarters,
since the equilibrium vapor pressure of mercury is hundreds of times the max-
imum recommended exposure. Mercury vapor consists of free, neutral atoms.
If inhaled, the atoms diffuse from the lungs into the bloodstream; then, because
they are electrically neutral, they readily cross the blood–brain barrier to
enter the brain. The result is serious damage to the central nervous system,
manifested by difficulties with coordination, eyesight, and tactile senses. Liquid
mercury itself is not highly toxic, and most of what is ingested is excreted.
Nevertheless, children should not be allowed to play with droplets of the
metal because of the danger from breathing the vapor.
The latter part of the twentieth century saw a substantial decline in
anthropogenic emissions of mercury into the water and land environments
from many sources in developed countries, resulting from governmental
attempts to reduce its uses and emissions. Emissions of mercury from large
industrial operations in developed countries have been successfully curtailed.
The overall use of mercury has decreased in the United States by more than
95% in the last three decades. For example, mercury has been eliminated from
batteries. In the United States, the reduction of mercury emissions arising
from disposal of mercury-containing products has resulted mainly from
• emission controls on municipal and medical waste incinerators, and
• removal of batteries and paint from the waste stream.
In Canada, emission reductions have come from controls on metal smelting,
the near-complete closure of the chlor-alkali industry (which had used mercury
electrodes), and controls on waste incineration.
Over the 1990s, the global concentration of airborne mercury increased
by about 1.5% per year, notwithstanding the decline in industrial emissions.
Large amounts of mercury vapor are released into the air as a result of the
unregulated burning of coal and fuel oil, both of which always contain trace
amounts of the element, and of incinerating municipal waste that contains
mercury in products such as batteries. Currently, coal-fired power plants
and municipal and medical waste incinerators are the biggest sources of
mercury emissions to the atmosphere in North America. The vaporized

mercury is eventually oxidized and returns in rain, often falling far from
the site of the original emissions. The issue of Mercury Emissions from Power
Plants is discussed in detail in the online Case Study associated with this
chapter.
In air, the great majority of elemental mercury is in the vapor (gaseous)
state, with only a fraction of it bound to airborne particles. Airborne gaseous
mercury can travel long distances before being oxidized and then dissolving
in rain and subsequently being deposited on land or in water bodies. This
global cycling of mercury results in its being distributed even to remote parts
of the planet.
U.S. Emission Controls on Power Plants

The 1100 coal-burning power plants in the United States are its last unregu-
lated major emitters of mercury into the environment. As a result of legal
pressure from environmental groups, by court order the U.S. EPA was forced
in 2005 to issue regulations that will reduce these emissions. The reductions
are scheduled to occur in two phases:
• By 2010, total mercury emissions are to be reduced from the current 48 tons
a year to 38 tons. This will be accomplished as a “co-benefit” of the new reduc-
tions in sulfur dioxide and nitrogen oxide emissions from the plants that must
be implemented by that date, as discussed in Chapters 3 and 4.
• By 2018, annual mercury emissions must be reduced to 15 tons.
Each state has been assigned an emissions budget and is required to develop
a plan for meeting its assigned emission reduction. States and power plants
can trade reductions among themselves, as long as overall goals are achieved.
Critics of the new program point out that averaging of reductions between
years is allowed, so that higher emissions could occur in later years if greater-
than-regulated reductions occur early. They also point out that “hot spots”
of mercury deposition may be perpetuated because of the trading provisions
and that the overall reduction in emissions will be quite small for many years
to come.
Mercury Amalgams
Mercury readily forms amalgams, which are solutions or alloys with almost
any other metal or combination of metals. The dental amalgam that has been
used to fill cavities in teeth for more than 150 years initially has a putty-like
consistency. It is prepared by combining approximately equal proportions of
liquid mercury and a solid mixture that is mainly silver with variable amounts
of copper, tin, and zinc. The slight expansion of volume that accompanies
its solidification ensures that the final amalgam fills the cavity. When a filling
Mercury 669
is first placed in a tooth, and whenever the filling is involved in the chewing
of food, a tiny amount of the mercury is vaporized. Some scientists believe
that mercury exposure from this source causes long-term health problems in
some individuals, but an expert panel of the U.S. National Institutes of
Health concluded that dental amalgams do not pose a health risk. A recent
study of adults found that no measure of exposure to dental mercury—neither
the concentration of the element in the urine nor the number of dental
fillings—correlated with any measure of mental functioning or fine-motor
control; another study found that no IQ or other neurological problems cor-
related with the use of amalgams for filling teeth in children.
Some countries in Europe such as Germany have banned the use of mer-
cury in fillings, at least for pregnant women and small children. Mercury-free
“amalgams” for use in dentistry are under development; porcelain fillings are
already common, though expensive. Some fears have been expressed about
the release of elemental mercury vapor into the atmosphere when cremating
deceased persons who had amalgam-filled teeth, since the amalgam decom-
poses at high temperatures. In countries such as Sweden, crematoria are fitted
with selenium filters that remove most mercury from emissions by forming
mercury selenide crystals.
In some areas, dentists are now required to install a separator to capture
mercury from their wastewater rather than have it flow down drains and
become part of municipal sewage. On average, each dentist produces about
one kilogram of mercury waste per year. Dentists collectively release about
the same amount of the metal as is emitted by coal-fired power plants.
Because of the control of emissions by dentists, the sewage sludge used by
farmers as fertilizer (Chapter 16) will have a much lower concentration of
mercury in the future.
In working some ore deposits, tiny amounts of elemental gold or silver are
extracted from much larger amounts of the denser particles of soil or sediment
by adding elemental liquid mercury to the mixture. The mercury extracts the
gold or silver by forming an amalgam, which is then roasted to distill off the
mercury. From 1570 until about 1900, this process was used to extract silver
from ores in Central and South America. About one gram of mercury was lost
to the environment for every gram of silver so produced, resulting in the
release of almost 200,000 tonnes of mercury. The mercury was shipped to
these regions from Almaden, Spain, and from Peru. Until recently, the corre-
sponding process of extracting gold by amalgamation with mercury was car-
ried out in China in both large-scale and small-scale operations. The ratio of
mercury to gold in such workshops, some of which continue illegally today in
remote regions, averaged 15 to 1.
Today, the gold extraction procedure using mercury is carried out on a
large scale in Brazil to obtain gold from muddy sediments; it results in sub-
stantial mercury pollution both in the air and, because of careless handling
practices, in the Amazon River itself. The health hazards to those whose
work involves the vaporization of mercury are significant, since the element
is so toxic in its gaseous form. Indeed, mercury vaporized from such opera-
tions currently makes up more than 10% of the anthrogogenic emissions of
mercury in air. People who live in mining regions often inhale air in which
the concentration of elemental mercury exceeds 50 mg/m3, which is 50 times
the public exposure guideline of the World Health Organization (WHO). As
a consequence, many “amalgam burner” workers exhibit tremors and other
signs of mercury poisoning. In addition, mercury in surface sediments dis-
turbed by slash-and-burn deforestation and agriculture in the region enters the
aquatic environment, where some of it enters the food chain. The European
Union has undertaken initiatives to incorporate inexpensive technology into
the process to prevent the massive release of mercury into the air and to the
Amazon river during the extraction of gold.
Mercury and the Industrial Chlor-Alkali Process

An amalgam of sodium and mercury is used in some industrial chlor-alkali
plants in the process that converts aqueous sodium chloride into the com-
mercial products chlorine, Cl2, and sodium hydroxide, NaOH, (and gaseous
hydrogen) by electrolysis. In order to form a concentrated, pure solution of
NaOH, flowing mercury is used as the negative electrode (cathode) of the
electrochemical cell. The metallic sodium that is produced by reduction in
the electrolysis immediately combines with the mercury and is removed from
the NaCl solution without having reacted with the aqueous medium:
Hg
Na(aq) e 99: Na (in a Na–Hg amalgam)
When metals such as sodium are dissolved in amalgams, their reactivity
is greatly lessened compared to that for the free state, so that the otherwise
highly reactive elemental sodium in the Na–Hg amalgam does not react with
the water in the original solution. Instead, the amalgam is removed and later
induced by the application of a small electrical current to react with water in
a separate chamber, thereby producing sodium hydroxide that is free of salt.
The mercury is recovered after NaOH production and is recycled back to
the original cell. The recycling of mercury is not complete, however, and
some finds its way into the air and into the water body from which the plant’s
cooling water is obtained and to which it is returned. Although liquid mercury
is not soluble in water or in dilute acid, it can be oxidized to soluble form by
the intervention of bacteria that are present in natural waters. By this means,
the mercury becomes accessible to fish.
The mass of mercury lost to the environment from the average chlor-
alkali plant has decreased enormously since the problem was identified in the
1960s. Nevertheless, installations in North America that use mercury
electrodes have largely been phased out. They were replaced by ones that
use a fluorocarbon membrane that separates the NaCl solution from the
Mercury 671
chloride-free solution at the negative electrode. The membrane is designed

such that Na, but not anions, can pass through it. In both types of cells, the
overall reaction is
2 NaCl(aq) H2O(l) 9: 2 NaOH(aq) Cl2(g) H2(g)
The 2⫹ Ion of Mercury

Like its partners zinc and cadmium in the same subgroup of the periodic
table, the common ion of mercury is the 2 species, Hg2, the mercuric or
mercury(II) ion. An example of a compound containing the mercuric ion is
the red ore cinnabar, HgS, i.e., Hg2S2. Like most sulfides, this salt is very
insoluble in water; indeed, the wastewater at chlor-alkali plants is sometimes
treated by adding a soluble salt such as Na2S that contains the sulfide ion,
since this action precipitates ionic mercury as HgS.
Hg2 S2 9: HgS(s)
P R O B L E M 15-2
The solubility product, Ksp, for HgS is 3.0 1053. Calculate the solubility of
HgS in water in moles per liter and transform your answer into the number
of mercuric ions per liter. According to this calculation, what volume of
water in equilibrium with solid HgS contains a single Hg2 ion?
Most of the mercury in the environment is inorganic, in the form of the

Hg2 ion. The levels of ionic mercury even in remote areas are two to five times
as great as preindustrial values, with local polluted sites having levels 10 or more
times greater. In natural waters, much of the Hg2 is attached to suspended
particulates, so it is eventually deposited in sediments—a topic considered in
further detail when soil and sediment chemistry is discussed (Chapter 16).
The nitrate salt of Hg2 is water soluble and was at one time used to treat
the fur used to make felt for hats. The fur was immersed in a hot solution of
mercuric nitrate, which made the fibers rough and twisted so they would then
mat together easily. As a consequence of this constant exposure to mercury,
workers in the felt trade often displayed nervous disorders: muscle tremors,
depression, memory loss, paralysis, and insanity (giving rise to the expression
“mad as a hatter,” a concept familiar to fans of Lewis Carroll’s Alice in Wonder-
land). Mercury vapor and, to a lesser extent, mercury salts attack the central
nervous system, but the main target organs for Hg2 are the kidney and the
liver, where it can cause extensive damage.
Mercuric oxide, HgO, is present in a paste in mercury cell batteries such
as those used in hearing aids. If the discarded spent batteries are subsequently
incinerated as garbage, the volatile mercury can be released into the air. The
amount of mercury used in ordinary flashlight batteries, added as a minor
constituent in the zinc electrode to prevent its corrosion and thereby extend
the shelf life of the product, was first drastically curtailed—typically from
about 10,000 ppm to about 300 ppm in alkaline batteries—and in many cases
has been completely eliminated, thereby halving the mercury in domestic
garbage. In North America, only some “button batteries” used in watches,
calculators, hearing aids, etc. still have significant mercury content.
The other inorganic ion of mercury, Hg22, is not very toxic since it com-
bines in the stomach with chloride ion to produce insoluble Hg2Cl2.
Methylmercury Toxicity
When in combination with anions that are capable of forming covalent
bonds, the mercuric ion Hg2 forms covalent molecules rather than an ionic
solid. For example, HgCl2 is a molecular compound, not a salt of Hg2 and
Cl. As chloride ion forms a covalent compound with Hg2, so does the
methyl anion, CH3, yielding the volatile molecular liquid dimethylmercury,
Hg(CH3)2. The process of dimethylmercury formation occurs in the muddy
sediments of rivers and lakes, especially under anaerobic conditions, when
anaerobic bacteria and microorganisms convert Hg2 into Hg(CH3)2. The
active agent in the biomethylation process is a common constituent of
microorganisms; it is a derivative of vitamin B12 with a CH3 anion bound to
cobalt and is called methylcobalamin.
The less volatile mixed compounds CH3HgCl and CH3HgOH, collec-
tively called methylmercury (or monomethylmercury), are often written as
CH3HgX, or somewhat misleadingly as CH3HgX, since these substances,
like most of those written as Hg2, consist of covalent molecules, not ionic
lattices. In fact, the methylmercury ion CH3Hg exists as such only in com-
pounds with anions such as nitrate or sulfate. Methylmercury compounds are
even more readily formed in the same way as dimethylmercury at the surface
of sediments in anaerobic water. Methylmercury production predominates
over dimethylmercury formation in acidic or neutral aqueous systems. Sulfate
ion, SO42, stimulates the sulfate-reducing bacteria that methylate mercury;
in contrast, the presence of sulfide ion results in formation of mercury sulfide
complexes that do not undergo methylation.
Due to its volatility, dimethylmercury evaporates from water relatively
quickly unless it is transformed by acidic conditions into the monomethyl
form. The pathways for the production and fate of dimethylmercury and
other mercury species in a body of water are illustrated in Figure 15-1. Methy-
lation of inorganic mercury does occur in anaerobic regions of lakes, especially
near the interface of the epilimnion and the hypolimnion, and at the interface
of the latter with sediments, but not in aerobic water. Organic-rich sediments
at the bottom of warm, shallow lakes are important sites of methylmercury
production. Wetlands are also active sites of methylmercury production.
Methylmercury in surface water is photodegraded (to as yet unknown prod-
ucts) and is the most important sink for this substance in some lakes.
Mercury 673
Air Hg0 Hg(II) CH3HgCH3
Water
Fish
?
Light
Hg0 Hg(II) CH3Hg+ CH3HgCH3
FIGURE 15-1 The cycling
of mercury in fresh-water
Sediment lakes. [Source: Adapted from
Hg0 Hg(II) CH3Hg+ CH3HgCH3
M. R. Winfrey and J. W. M.
H2S Rudd, “Environmental Factors
Affecting the Formation of
Organic and HgS Methylmercury in Low pH
inorganic complexes Lakes,” Environmental Toxicology
and Chemistry 9 (1990):
853–869.]
Mercuric ion itself is not readily directly transported across biological

membranes. Methylmercury is a more potent toxin than are salts of Hg2
because it is soluble in fatty tissue in animals, bioaccumulates and biomagni-
fies there, and is more mobile. Once ingested, the original covalent CH3HgX
compound is converted to substances in which X is a sulfur-containing amino
acid; in some of these forms, it is soluble in biological tissue and can cross both
the blood–brain barrier and the human placental barrier, presenting a twofold
hazard. Methylmercury is, in fact, the most hazardous form of mercury, fol-
lowed by the vapor of the element. The main toxicity of methylmercury
occurs in the central nervous system. In the brain, methylmercury is converted
to Hg2, which is probably responsible for the brain damage. Mercury vapor is
also oxidized to this ion once it has entered the cell. Thus the usual barriers in
the cell to Hg2 are circumvented by Hg0 and CH3HgX, which by their elec-
tric neutrality can penetrate through the defenses and which later can be con-
verted to the highly toxic 2 ionic form.
Most of the mercury present in humans is in the form of methylmercury.
Almost all methylmercury originates from the fish in our food supply: Mercury
in fish is usually at least 80% methylmercury. Mercury contamination is the
reason behind about 97% of the advisories against eating fish caught in various
regions of North America. In contrast to organochlorines, which predomi-
nate in the fatty portions of fish, methylmercury can bind to the sulfhydryl
group in proteins and so is distributed throughout the fish. Consequently, the
mercury-containing part cannot be cut away before the fish is eaten.
Fish absorb methylmercury that is dissolved in water as it passes across
their gills (bioconcentration); they also absorb it from their food supply
(biomagnification). The ratio between methylmercury in fish muscle and

that dissolved in the water in which the fish swims is often about 1 million to
1, and can exceed 10 million to 1. The highest methylmercury concentrations
(over 1 ppm) are usually found in large, long-lived predatory marine species
such as shark, king mackerel, tilefish, swordfish, and large tuna (sold as steaks
and sushi), as well as in fresh-water species such as bass, trout, and pike.
Indeed, the U.S. Food and Drug Administration warns women of childbearing
age not to eat the first four types of marine fish in the list above. On average,
the older the fish, the more methylmercury it will have bioaccumulated.
Noncarnivorous species such as whitefish do not accumulate very much mer-
cury since biomagnification in their food chain operates to a much lesser
extent than in carnivorous fish. On average, most Americans take in almost
half their methylmercury from tuna (mostly of the canned variety), followed
by swordfish, pollock, shrimp, and cod. Canada has recently limited the max-
imum concentration of mercury in six species of ocean fish to one part per
million; this concentration is not uncommon in swordfish, although most fish
have levels of 0.10–0.15 ppm. The U.S. EPA has set a criterion of 0.3 ppm
maximum for methylmercury in fish tissue.
In lakes, the mercury content in fish is generally greater in acidic water,
probably because both the solubility of mercury is greater and the methyla-
tion of mercury is faster at lower pH. In this way, the acidification of natural
waters indirectly increases the exposure of fish-eaters to methylmercury. The
relationship between mercury levels in small fish and the pH of the water is
illustrated in Figure 15-2. The data in this figure are from a collection of lakes
in Wisconsin, eastern Ontario, and Nova Scotia; most of the acidic lakes are
in Nova Scotia.
700
600
Concentration of mercury (ppb)
500
400
300
FIGURE 15-2 The rela-
tionship between pH and
200
mercury concentration in
a fish for a standard fish
length for 48 lakes from 100
Ontario, Nova Scotia,
and Wisconsin. 0
[Source: D. Lean, “Mercury
4.0 5.0 6.0 7.0 8.0 9.0 10.0
Pollution,” Canadian Chemical pH
News (January 2003): 23.]
Mercury 675
Methylmercury Accumulation in the

Environment and in the Human Body
The half-life of methylmercury compounds in humans, about 70 days, is much
longer than that for Hg2 salts, due in part to the compounds’ greater solubil-
ity in a lipid environment. Consequently, methylmercury can accumulate in
the body to a much higher steady-state concentration, even if on a daily basis
a person consumes amounts that individually would not be harmful.
P R O B L E M 15-3
If the half-life of methylmercury in the human body is 70 days, what is its
steady-state accumulation in a person who consumes daily 1.0 kg of fish
containing 0.5 ppm methylmercury? [Hint: Recall the discussion of steady-state
concentrations in Chapter 6.]
Most of the well-publicized environmental problems involving mercury

have arisen from the fact that in the methylated form it is a cumulative poison.
However, in high enough concentration it can be acutely fatal. In 1997, cancer
researcher Karen Wetterhahn of Dartmouth College died from mercury poi-
soning several months after a drop or two of pure dimethylmercury apparently
seeped through latex gloves she was wearing while using the compound in
experiments. Dialkylmercury compounds, including dimethylmercury, are
sometimes called supertoxic because they are lethal even in small amounts.
At the fishing village of Minamata, Japan, a chemical plant employing
Hg2 as a catalyst in a process that produced polyvinyl chloride discharged
mercury-containing residues into Minamata Bay. The methylmercury com-
pounds, mainly CH3Hg9SCH3, that subsequently formed from the inorganic
mercury by biomethylation by microorganisms in the bay’s sediments then
bioaccumulated. Concentrations were as high as 100 ppm in the fish, which
were the main component of the diet for many local residents. (By way of
contrast, the current U.S. recommended limit for methylmercury in fish to be
consumed by humans is 0.3 ppm.) Thousands of people in Minamata were
affected in the 1950s by mercury poisoning from this source, and hundreds
of them died from it. Because the onset of symptoms in humans is delayed,
the first signs of Minamata disease were observed in cats who ate discarded
fish: They began jumping around and twitching, ran in circles, and finally
threw themselves into the water and drowned. Symptoms in humans arise
from dysfunctions of the central nervous system, since the target organ for
methylmercury is the brain; they include numbness in arms and legs, blurring
and even loss of vision, loss of hearing and muscle coordination, and lethargy
and irritability.
Since methylmercury can be passed to the fetus, children born to Minamata
mothers poisoned even slightly by mercury showed severe brain damage,
some to a fatal extent. The infants showed symptoms similar to those of cerebral
palsy: mental retardation, seizures, motor disturbance, and even paralysis. Just
as in the case of high PCB levels, discussed in Chapter 11, the developing
fetuses were much more affected by methylmercury than were the mothers
themselves. The poisonings at Minamata must surely rank as one of the major
environmental disasters of modern times.
Other Sources of Methylmercury

Organic compounds of mercury have been used as fungicides in agriculture
and in industry and enter the environment as a side effect of these applications.
However, as a result of contact with soil, the compounds are eventually broken
down and the mercury becomes trapped as insoluble compounds by attachment
to sulfur ions present in clays and organic matter.
Hundreds of deaths in Iraq in 1956, 1960, and 1972, and a few in China
and the United States, resulted from the consumption of bread made from
seed grain (intended for planting) that had been treated with mercury-based
fungicides to reduce seedling losses from fungus attack. The fungicides con-
tained compounds of ethylmercury, CH3CH2Hg, the toxicity of which is
presumed to be similar to that of methylmercury. In Sweden and Canada, the
use of mercury compounds to treat seeds led to a significant reduction in the
number of birds of prey that consumed the smaller birds and mammals that
fed on the scattered seed. The use of ethylmercury products in agriculture has
now been curtailed in North America and western Europe.
Mercury is leached from rocks and soil into water systems by natural
processes, some of which are accelerated by human activities. Flooding of
vegetated areas can release mercury into water. For example, after the flooding
of huge areas of northern Quebec and Manitoba in constructing hydroelec-
tric power dams, the newly submerged surface soils (and to a lesser extent the
vegetation) released a considerable quantity of soluble methylmercury,
formed from the “natural” mercury content of these media. The additional
methylmercury resulted from contact of soil-bound Hg2 with anaerobic bac-
teria produced by the decomposition of the immersed organic matter. In this
way, previously insoluble inorganic mercury was converted to methylmercury,
which readily dissolved in the water. The methylmercury subsequently
entered the food chain through its absorption by fish, and native persons who
ate fish from these flooded areas now have substantially elevated levels of
mercury in their bodies. Indeed, the methylmercury concentration in fish
from these areas, 5 ppm or more, approaches that previously associated only
with regions of industrial mercury pollution.
In 1999, the safety of using a mercury-based preservative to prevent micro-
bial growth in many vaccine preparations administered to infants was ques-
tioned by the American Academy of Pediatrics and the U.S. Public Health
Service. The preservative, Thimerosal, is CH3CH29Hg9S9C6H4COOH; it
is sometimes said to contain the ethylmercury ion, but presumably, like most
Mercury 677
methylmercury systems, it is actually a covalent compound. This substance has

now been removed by its manufacturer in all vaccines destined for use in young
children in the United States, with the exception of inactivated influenza
vaccine. The preservative was also widely used as a topical disinfectant.
The Use of Mercury in Preservatives and as Medications

Compounds of the phenylmercury ion, C6H5Hg, with acetate or nitrate as
the anion, have been used to preserve paint while in the can and to prevent
mildew after application of latex paint, particularly in humid areas. The
phenylmercury salts are not as toxic to humans as are methylmercury com-
pounds, since they break down quickly into compounds of the less toxic
Hg2. However, mercury compounds have been banned from indoor latex
paints in North America for more than a decade because some ingestion of
the element from this source is inevitable. Phenylmercury compounds were
also formerly used as slimicides in the pulp-and-paper industry in order to prevent
the growth of slime on wet pulp; because this practice has now been curtailed
and because mercury-containing wastes are now usually treated, mercury
releases from such sources have greatly decreased.
Because of their antiseptic and preservative qualities, however, some
mercury compounds are still used in pharmaceuticals (especially topical
antiseptics) and cosmetics. Elemental mercury was also used in some phar-
maceuticals in the old days. Indeed, the antidepressant pills that Abraham
Lincoln took, mainly in the years before becoming president, contained the
element; indeed, some medical historians think the leaching of mercury into
his bloodstream can account for his often bizarre behavior in that period.
The mercury ore cinnabar is still used today in China, as a drug, pigment,
and preservative.
P R O B L E M 15-4
A quantity of a mercury–chlorine compound is included in a shipment of
waste to a toxic waste disposal dump. Before it can be disposed of properly,
the owners of the dump need to know whether it is HgCl2, or Hg2Cl2, or
some other compound. They send a sample of it for analysis and find that it
contains 26.1% chlorine by mass. What is the empirical formula of the
compound?
Safe Level of Mercury in the Body

It is somewhat reassuring that both the direct effects of methylmercury on
humans and the prenatal effects probably have thresholds below which no
effects are observed. Currently the daily methylmercury intake of 99.9% of
Americans lies below the WHO’s “safe limit.” Nonetheless, some effects of
methylmercury consumption on human vision are observed even when the

concentration of (total) mercury in hair lies below the generally recognized
threshold of 50 ppm.
However, if prenatal health is the main consideration and if a safety fac-
tor of 10 is applied, a substantial fraction of the population of the United
States would exceed the safe limit. The WHO has concluded that levels of
10–20 ppm of methylmercury in hair indicate that a pregnant woman has
sufficient methylmercury in her blood to represent a threat to a developing
fetus. This places at risk the developing fetus of more than 30% of the women
in some native communities in northern Canada, for example, in which
fish play a large part in the diet. Although it is clear that high levels of
methylmercury can result in developmental disabilities, there is continuing
controversy over whether methylmercury acquired through a diet high in fish
and marine mammals can cause significant neurological damage to an adult
or a developing fetus. The epidemiological studies of this question have, to
this point, produced inconsistent results.
P R O B L E M 15-5
What is the mass, in milligrams, of mercury in a 1.00-kg lake trout which just
meets the Northern American standard of 0.50 ppm Hg? What mass of fish,
each at the 0.50-ppm Hg level, would you have to eat in order to ingest a total
of 100 mg of mercury?
P R O B L E M 15-6
The new U.S. EPA oral reference dose for methylmercury is 0.1 micrograms
per kilogram body weight per day. What mass of fish can a 60-kg woman safely
eat each week if the average methylmercury level in the fish is 0.30 ppm?
Approximately how many average servings of fish does this correspond to?
International Controls on Mercury

Although atmospheric emissions now dominate mercury concerns in most
countries, especially developed ones, other sources also contribute signifi-
cantly elsewhere. Mercury is still used extensively in the extraction of gold
and silver, as well as in the production of chlorine in chlor-alkali plants, in
developing countries.
In 2005 the United Nations Environment Programme considered devising
a global treaty to curb the production of mercury and to ban completely the
export of mercury between countries. However, the United States led a
movement, which ultimately was successful, that instead proposed voluntary
partnerships between countries to improve their management of mercury.
Lead 679
Lead
Although the environmental concentration of lead, Pb, is still increasing in
some parts of the world, the uses that result in its uncontrolled dispersion
have been greatly reduced in the last few decades in many developed coun-
tries. Consequently, its concentration in soil, water, and air has decreased
substantially.
Lead’s relatively low melting point of 327°C allows it to be readily
worked—it was the first metal to be extracted from its ores—and shaped.
Lead was used as a structural metal in ancient times as well as for weather-
proofing buildings, in water pipes and ducts, and for cooking vessels. Lead is
still used for roofing and flashing and for soundproofing in buildings. When
combined with tin, it forms solder, the low-melting alloy used in electronics
and in other applications (e.g., tin cans) to connect solid metals.
Analysis of ice-core samples from Greenland indicates that atmospheric
lead concentration reached a peak in Roman times that was not equaled
again until the Renaissance. The history of lead’s presence in the environ-
ment can be seen in Figure 15-3, in which the ratio of two stable lead isotopes
A.D. 1991
0 Introduction of unleaded gasoline
A.D. 1979
Introduction of leaded gasoline
–20 A.D. 1936
A.D. 1905
Industrial Revolution/
Depth (cm)
240 B.P. A.D. 1843 Australian Pb imports

–40 710 B.P. German silver mining of Pb ores
1010 B.P.
–60 1350 B.P. Post-Roman decline in European
1400 B.P. Pb mining
–80 1610 B.P.
2110 B.P. Roman Pb mining

–100
1.12 1.16 1.20
Pb mining begins (Phoenicians,
–100 Greeks)
3000 B.P.
Soil dust flux increases
–200 (deforestation, agriculture)
5320 B.P.
5790 B.P.
–300
Mid-Holocene, pre-anthropogenic FIGURE 15-3 Isotopic
background
Depth (cm)
composition of lead in a
–400
8230 B.P. Swiss peat bog and the
chronology of atmospheric
–500 lead deposition. Notice the
10,590 B.P. Early Holocene, pre-anthropogenic change in depth scale at
background 100 cm. [Source: W. Shotyk
–600 12,370 B.P. et al., “History of Atmospheric
1.12 1.16 1.20 Lead Deposition Since 14C BP
from a Peat Bog, Jura Mountain,
206Pb/207Pb
Switzerland,” Science 281
(1998): 1635, Figure 3B.]
in samples taken from a peat bog in Switzerland is plotted against the depth
at which the sample was taken. The layers of the bog were laid down gradually
over millennia, and each layer incorporated lead-containing dust particles
deposited from the air at the time. Lead originating in different geographic
locales has different isotope ratios, so we can tell the origin of atmospheric lead
at different times in the past from the graph. The 206Pb/207Pb ratio is close to
1.20 for depths exceeding 145 cm, or 3000 years ago (sediment ages being
determined by 14C dating of the peat); the variations in the ratio below that
depth reflect changes in the dominance of weathering of soils and rocks in
different areas over time. Beginning about 3000 years ago, the ratio fell to
1.18, reflecting the isotopic composition of European lead ores mined during
Roman times and thereafter. Previous to that, in Greek times, silver was first
mass-produced for use in coins; apparently the substantial amount of lead
contaminant in the crude silver escaped into the air during the refining of the
metal. In about 1860, the isotope ratio of the lead deposited in Europe began
a continual decrease, with the rate of change increasing with the introduction
of leaded gasoline in about 1940, probably as a consequence of the extensive
use of lead in it, first from Australia (ratio of 1.04) and then also from Canada.
Recently the ratio has begun to increase due to the decreased use of lead in
European gasoline.
Elemental Lead as an Environmental Risk

Elemental lead is also found in ammunition (“lead shot”) used in huge
amounts by hunters, especially of waterfowl. Many ducks and geese are
injured or die from chronic lead poisoning after ingestion of lead shot, which
dissolves in the acidic environment inside them. In addition, ducks consume
the pellets left lying on the ground or at the bottom of ponds, since they look
like food or grit. Birds (such as bald eagles) sometimes prey on ducks and
other waterfowl that have been shot by hunters but not harvested by them, or
they sometimes eat lead shot to help grind food in their gizzard; these preda-
tors become victims of lead poisoning. For these reasons, lead shot has been
banned in the United States, Canada, the Netherlands, Norway, and Denmark.
However, in North America, many loons die because they swallow and are
subsequently poisoned by lead sinkers and jigs still used in sport fishing.
Lead ammunition in the form of bullets and shotgun shells (used for
shooting wild game) also poses an environmental problem. Condors in
California suffer from lead poisoning, sometimes fatally, when they eat deer
that have been shot and then abandoned by hunters; the lead bullets explode
into many fragments on impact and contaminate the meat.
Ionic 2⫹ Lead in Water and Food as

an Environmental Hazard to Humans
Although elemental lead is not an environmental problem to most life forms, it
does become a real concern when it dissolves to yield an ionic species.
Lead 681
The stable ion of lead is the 2 species, Pb(II) as Pb2. For example,
lead forms the ionic lead sulfide, PbS, Pb2S2, which is the metal-bearing
component of the highly insoluble ore galena, from which almost all lead is
extracted.
Lead does not react on its own with dilute acids. Indeed, elemental lead is
stable as an electrode in the lead storage battery, even though it is in contact
with fairly concentrated sulfuric acid, H2SO4. However, some lead in the solder
that was commonly used in the past to seal tin cans will dissolve in the dilute
acid of fruit juices and other acidic foods if air is present—that is, once the can
has been opened—since lead is oxidized by oxygen in acidic environments:
2 Pb(s) O2 4 H 9: 2 Pb2(aq) 2 H2O

The Pb2 produced by this half-reaction contaminates the contents of the
can; for this reason, lead solder is not usually used any more for food contain-
ers in North America. Partially as a result of this change, the average daily
intake of lead for two-year-old children dropped from about 30 mg in 1982 to
about 2 mg in 1991.
The 1845 Franklin Expedition to find a Northwest Passage across the
Arctic is thought to have failed because the members all died from lead
poisoning from the solder in the tin cans that held their food. Canadian
writer Margaret Atwood has written eloquently about the incident in her
short story “The Age of Lead”:
It was the tin cans that did it, a new invention back then, a new technology, the
ultimate defence against starvation and scurvy. The Franklin Expedition was
excellently provisioned with tin cans, stuffed full of meat and soup and soldered
together with lead. The whole expedition got lead poisoning. Nobody knew it.
Nobody could taste it. It invaded their bones, their lungs, their brains, weaken-
ing them and confusing their thinking, so that at the end those that had not yet
died in the ships set out in an idiotic trek across the stony, icy ground, pulling a
lifeboat laden down with toothbrushes, soap, handkerchiefs and slippers, useless
pieces of junk. When they were found (ten years later, skeletons in tattered
coats, lying where they’d collapsed) they were headed back toward the ships. It
was what they’d been eating that had killed them.
[Margaret Atwood, “The Age of Lead,” in Wilderness Tips,
copyright 1991 by O. W. Toad Limited]
The recommended maximum levels for important heavy metal ions in
drinking water are summarized in Table 15-2. The limit for lead, 10–15 ppb, is
sometimes exceeded in water delivered to the consumer even though it was
sufficiently pure when it left the water treatment plant. Lead used in the sol-
der in the joints of domestic copper water pipes, and lead used in previous
decades and centuries to construct the pipes themselves, can dissolve in drink-
ing water during its transport to the point of consumption, particularly if the
water is quite acidic or particularly soft. This problem of contamination of
TABLE 15-2 Drinking-Water Guidelines for Heavy Metals
U.S. EPA Maximum Canadian Maximum World Health

Contaminant Acceptable Organization
Metal Level (ppb) Concentration (ppb) Guideline (ppb)
As 10 10 10
Cd 5 5 3
Cr 100 50 50
Hg (inorganic) 2 1 6
Pb 15 10 10
water by lead during transit became a controversial issue in 2007 in the home-
town (London, Ontario) of one of the authors of this book, with the concern
quickly spreading to older homes in other cities in Ontario as well. In general,
it is a good idea not to drink water that has been standing overnight in older
drinking fountains or in the pipes of older dwellings; water in such plumbing
systems should be allowed to run for a minute or so.
The contamination of water by lead is less of a problem in areas of cal-
careous water, since an insoluble layer containing compounds such as PbCO3
forms on the surface of the lead by reaction of the metal with dissolved
oxygen and the carbonate ion, CO32, in the water (Chapter 13). This layer
prevents the metal underneath from dissolving in the water that passes over
it. In some regions of England and in some cities in the northeast United
States that have soft water and networks of old lead pipes, phosphates are
added to drinking water in order to form a similar insoluble protective coat-
ing of lead phosphate on the inside of lead pipes and so reduce the concentra-
tion of dissolved lead.
Lead in water is more fully absorbed by the body than is lead in food. Now
that many other sources of lead have been phased out, drinking water
accounts for about one-fifth of the collective lead intake of Americans, whose
major source is from food. Many domestic water treatment systems successfully
remove the great majority of lead from drinking water. Bottled water sold in
plastic containers usually has very low levels of lead, averaging 16 ppt in one
recent survey, which is not much higher than those in groundwater taken from
pristine deep aquifers. Bottled water in glass containers has more lead, up to
about 1 ppb, since tiny amounts of the metal are leached from the glass.
P R O B L E M 15-7
According to an informal 1992 survey, the drinking water in about one-third
of the homes in Chicago had lead levels of about 10 ppb. Assuming that an
Lead 683
adult drinks about 2 L of water a day, calculate the total lead that residents of
these Chicago homes obtain daily from their drinking water.
Lead Salts as Glazes and Pigments

One form of the oxide PbO is a yellow solid that has been used at least as far
back in history as ancient Egypt to glaze pottery. In glazing, the material is
fused as a thin film to the surface of the pottery in order to make it waterproof
and to give it a brilliant high gloss. The oxide becomes a hazard if applied
incorrectly: Some of it will dissolve over a period of hours and days if acidic
foods and acidic liquids, such as cider, are stored in pottery containers, giving
dissolved Pb2, up to hundreds or even thousands of parts per million, in the
food:
PbO(s) 2 H(aq) 9: Pb2(aq) H2O
Indeed, lead-glazed dishware is still a major source of dietary lead, especially,
but not exclusively, in developing countries. The leaching of lead from glazed
ceramics used to prepare food is one of the major sources of the element for
children in Mexico, where lead contamination is a leading public health
problem. Nowadays, lead silicate rather than oxide or sulfate is used for
glazing in most countries since it is almost insoluble and thus much safer.
Various salts of lead have been used as pigments for millennia, since they
give stable, brilliant colors. Lead chromate, PbCrO4, is the yellow pigment
used in paints applied to school buses and for the yellow stripes on roads.
Red lead, Pb3O4, is used in corrosion-resistant paints and has a bright red
color. It was used in great quantity in the past to produce a rust-resistant sur-
face coating for iron and steel. Lead acetate is often used in preparations to
cover gray hair, since the Pb2 ion of this soluble salt will combine with the
SH group of hair proteins to give a dark color.
Lead pigments have been used to produce the colors used in glossy mag-
azines and food wrappers. In past centuries, lead salts were used as coloring
agents in various foods. White lead, Pb3(CO3)2(OH)2, was extensively used
until the middle of the twentieth century as a major component of white
indoor paint. Since it was more durable than unleaded paint, it was often
used on surfaces subject to punishment such as kitchen cabinets and window
trim. However, when the paint peels off, small children may eat the paint
flecks since Pb2 has a sweet taste. Persons who renovate old homes are urged
to ensure that dust from layers of old paint is properly contained. Children in
inner-city slums, in which old coats of paint continue to peel, are often found
to have elevated blood levels of lead. In indoor paint, white lead has now
been replaced by the pigment titanium dioxide, TiO2. Although now banned
from use in indoor paints (since 1978 in the United States), lead pigments
continue to be used in exterior paints, with the result that soil around houses
may eventually become contaminated. Some of this lead-contaminated soil
may be ingested by small children because of its sweet taste. Lead is still
widely used in indoor paint sold in China, India, and some other Asian coun-
tries, sometimes at levels exceeding 180,000 ppm (as compared to the U.S.
standard of 600 ppm maximum for new paints).
An additional source of sweet lead-containing dust was the surface of
some types of PVC miniblinds that had lead incorporated as a stabilizer in the
plastic and that underwent partial decomposition from exposure to UV in
sunlight. Lead is used as a stabilizer in a variety of other PVC products as well,
including children’s toys.
Lead dust, which originates as soil containing tiny particles of lead com-
pounds, is now the biggest source of lead for children in U.S. inner cities. The
lead collectively originates from individually small but numerous contribu-
tions from many sources already mentioned—paint flakes, ceramics, plastics,
gasoline, recycling plants, and even lead salts used in hair coloring prepara-
tions for people with graying hair. The use of lead arsenate, Pb(AsO4)2, as a
pesticide was another former source of Pb2 in soil.
Green Chemistry: Replacement of Lead

in Electrodeposition Coatings
Sheet metal surfaces made of steel undergo corrosion very rapidly unless they
are covered with a protective coating. Since the 1960s a technique called
electrodeposition has competed with spray painting for coating steel. In 1976
the first automobiles were treated by electrodeposition. In this technique, the
surface to be treated is dipped in a bath, with the surface acting as a cathode
or anode, and the coating is deposited electrophoretically. Electrodeposition
has many advantages over spray painting, including:
• lower air pollution, due to decreased solvent emissions;
• better corrosion protection, due to better coverage of poorly accessible
areas;
• reduced waste, due to high transfer efficiency; and
• more uniform coating thickness.
Virtually all primer coats for automobiles are done using this method.
Red lead, mentioned previously, offers significant corrosion resistance, and
primer coats use large amounts of this material. Although lead has been
banned from house paints in the United States since 1972, the demand for
corrosion resistance for motor vehicles has resulted in exemptions from envi-
ronmental regulations regarding lead in automobile and truck paints.
PPG Industries has discovered that yttrium oxide serves as an excellent
replacement for lead as a corrosion inhibitor and won a Presidential Green
Chemistry Challenge Award in 2001. On a weight basis, yttrium is twice as
Lead 685
effective in inhibiting corrosion as red lead but is only 1/120th as toxic. An

additional consideration is the pretreatment process that is used to assist in
adhesion and corrosion resistance prior to the application of the electrocoat.
The use of yttrium eliminates chromium from metal pretreatments and
reduces the amount of nickel compared to the lead process. It is estimated
that employing yttrium in automobile electrodeposition will eliminate not
only the use of 1 million pounds of lead but also 25,000 pounds of chromium
and 50,000 pounds of nickel on an annual basis. As of September 2006, more
than 38 million motor vehicles have been coated with the yittrium-containing
product since its introduction in 2001. According to PPG Industries, no cus-
tomers in either the United States or Europe purchase any lead-containing
coating product for any application, including automotive.
Dissolution of Otherwise Insoluble Lead Salts

The presence of significant concentrations of lead in natural waters is seem-
ingly paradoxical, given that both its sulfide, PbS, and its carbonate, PbCO3,
are highly insoluble in water:
PbS(s) Δ Pb2 S2 Ksp 8.4 1028

PbCO3(s) Δ Pb2 CO32 Ksp 1.5 1013
However, the anions in both salts are fairly strong bases. Thus both of the
above dissolution reactions are followed by the reaction of the anions with
water:
S2 H2O Δ HS OH

CO32 H2O Δ CO3 OH
Because these reactions reduce the concentrations of the original anions pro-
duced by dissolution of the salt PbS or PbCO3, the position of equilibrium in
the original reactions shifts to the right side, thereby dissolving more of the salt,
in analogy with the process involving CaCO3 that we analyzed in Chapter 13.
Thus the solubilities of PbS and PbCO3 in water are substantially increased by
the reaction of the anion with water.
If highly acidic water comes into contact with minerals such as PbS, the
“insoluble” solid dissolves to a much greater extent than in neutral waters.
This occurs because the sulfide ion initially produced is subsequently con-
verted almost entirely to bisulfide ion, HS, which in turn is converted by
the acid to dissolved hydrogen sulfide gas, H2S, since both S2 and HS act
as bases in the presence of acid:
S2 H Δ HS K 1兾Ka (HS) 7.7 1012
HS H Δ H2S K
1兾Ka (H2S) 1.0 107
When these two reactions are added to that for the dissolution of PbS into
Pb2 and S2, the overall reaction is seen to be
PbS(s) 2 H Δ Pb2 H2S(aq)
Since the equilibrium constant Koverall for an overall process which is the sum
of several others is the product of their equilibrium constants, in this case
Koverall KspKK
6.5 108. By application of the law of mass action to
this reaction, we find the expression for the equilibrium constant in terms of
concentrations:
Koverall [Pb2] [H2S]兾[H]2
Under conditions in which no significant amount of hydrogen sulfide gas is
vaporized, but which are sufficiently acidic that almost all the sulfur exists as
H2S rather than as S2 or HS, the stoichiometry of the reaction allows us to
write that [Pb2] [H2S]. By substitution of this relationship into the above
equation, we obtain
[Pb2]2 6.5 108 [H]2
or
[Pb2] 2.5 104 [H]
Thus the solubility of PbS increases linearly with the H concentration in
acidic water. At pH 4, the solubility of PbS and the concentration of
Pb2 ion in water is calculated to be 2.5 108 M, whereas at pH 2, the
solubility is 2.5 106 M. We conclude that dangerous concentrations of
lead ion can occur in highly acidic bodies of water that are in contact with
“insoluble” lead minerals.
P R O B L E M 15-8
By calculations similar to those for PbS above, deduce the relationship
between the solubility of mercuric sulfide, HgS (Ksp 3.0 1053), and the
hydrogen ion concentration in acidic water. Is the solubility of HgS increased
by exposure to acid?
Ionic 4ⴙ Lead in Automobile Batteries

In highly oxidizing environments, lead can occur as the 4 ion, one form of
Pb(IV). Thus the oxide PbO2, written in ionic form as Pb4(O2)2, exists, as
do the mixed oxides Pb2O3 and Pb3O4, which are combinations of Pb(II) as
PbO and Pb(IV) as PbO2.
The elemental lead and the lead oxide PbO2 employed as the two elec-
trodes in storage batteries in vehicles together now constitute the major use
of the element. Storage batteries that are not recycled constitute the main
Lead 687
source of lead in municipal waste; some states and countries have banned the
discarding of such batteries. The majority of used lead storage batteries are
recycled for their lead content. During the recycling operation, lead can be
expelled into the environment if careful controls are not maintained. Indeed,
such recycling operations often constitute urban “hot spots” of lead emission
into the surrounding communities. Although lead recycling operations in the
United States are carried out under strict control, this is not necessarily the
case in developing countries, where batteries are often shipped for recycling.
Tetravalent Organic Lead Compounds

as Gasoline Additives
Whereas the compounds of Pb(II) are ionic, most Pb(IV) compounds are
covalent molecules rather than ionic compounds of Pb4. In this respect,
tetravalent lead is similar to the corresponding form of the other elements
(C, Si, Ge, Sn) in its group of the periodic table.
Commercially and environmentally, the most important covalent com-
pounds of lead(IV) are tetraalkyl compounds, PbR4, especially those formed
with the methyl group, CH3, and the ethyl group, CH2CH3—namely tetra-
methyllead, Pb(CH3)4, and tetraethyllead, Pb(C2H5)4. In the past, both
compounds found widespread use as additives to gasoline—about a gram per
liter—to produce leaded gasoline. As discussed in Chapter 7, this practice has
now been phased out in North America and in many other developed coun-
tries, except in some types of aviation fuel, for which no acceptable substitute
for lead has yet been found.
Since tetraalkyl lead compounds are volatile, they evaporate to some
extent from gasoline and enter the environment in gaseous form. They are
not water-soluble, but they are readily absorbed through the skin. In the
human liver, PbR4 molecules are converted into the more toxic compounds
of PbR3, which are neurotoxins because they can cross the blood–brain bar-
rier. In substantial doses, these organic compounds of lead cause symptoms
that mimic psychosis. It is not clear what the effects may be, if any, of chronic
low-level exposure to them. At very high exposures, tetraalkyllead com-
pounds are fatal, as was discovered many years ago when several employees of
the companies that originally produced these compounds died. In contrast to
mercury, little or no methylation of inorganic lead occurs in nature. Thus
almost all the tetraalkylated lead in the environment probably originated
from leaded gasoline.
Environmental Lead from Leaded Gasoline

When these additives are used in gasoline, the atoms of lead that are liberated
by the combustion of the tetraalkyl compounds must be removed before they
form metallic deposits and damage the vehicle’s engine. In order to convert
the combustion products into volatile forms that can leave the engine in the
exhaust gases, small quantities of ethylene dibromide and ethylene dichlo-
ride are also added to the leaded gasoline. As a result, the lead is removed
from the engine and enters the atmosphere from the tailpipe in the form of a
mixture of the mixed dihalide PbBrCl and the dihalides PbBr2 and PbCl2.
Subsequently, under the influence of sunlight, these compounds form PbO,
which then exists in particulate form as an aerosol in the atmosphere for
hours or days. Consequently, not all of it is deposited in the immediate sur-
roundings of the roadway. As a result, PbO can enter the food chain at more
distant sites if deposited on vegetables or on fields used by grazing animals.
Furthermore, a small fraction of the ethylene dihalides are converted into
dioxins and furans and enter the environment in these forms.
A high proportion of environmental lead in many parts of the world is
that emitted from vehicles; it occurs in the environment mainly in inorganic
form. The conversion to nonleaded gasoline in North America and Europe,
the initial impetus for which was the inter-
ference of lead in exhaust gases with the
300
proper functioning of catalytic converters,
has had the welcome side effect of greatly
250 decreasing the average amount of lead
ingested by urban inhabitants. Indeed, the
Metric tons of lead (thousands)
noted environmentalist Barry Commoner

200 has called the elimination of lead from
gasoline “one of the [few] environmental
150
success stories.” European scientists have
traced the rise and fall of atmospheric alky-
lated lead by analyzing different vintages of
100 a French red wine (Chateauneuf-du-Pape)
that used grapes grown near two busy auto
routes. They found that the concentration
50
of trimethyllead, PbR3—the degradation
product of the tetramethyl compound—
0 rose steadily to a maximum in the mid-
1920 1930 1940 1950 1960 1970 1980 1990 1970s, which was followed by a steady
Year decline to about one-tenth of the peak
concentration by the early 1990s as the
FIGURE 15-4 The histori- compound was phased out of gasoline.
cal consumption of lead in This pattern of usage is consistent with the variation in the U.S. consump-
gasoline in the United tion of lead for gasoline use; it is plotted in Figure 15-4 and shows a sharp rise
States. [Source: C. E. Dunlop from 1930 to 1970, followed by an even sharper decline thereafter.
et al., “Past Leaded Gasoline
Many countries still use leaded gasoline. In these areas, the air is the
Emissions as a Nonpoint Source
Tracer in Riparian Systems,”
major source of lead ingested by humans, as it was in the past in North
Environmental Science and America and Europe. For example, in Mexico airborne lead from vehicu-
Technology 34 (2000): 1211.] lar emissions is a major source of the elevated lead levels found in the
Lead 689
bloodstream of many Mexican children. Some of the gasoline-based lead

enters the body directly from inhaled air, and some enters indirectly from
food into which lead has been incorporated. Microorganisms do bioconcen-
trate lead, but in contrast to mercury, lead does not undergo biomagnifica-
tion in the food chain.
Lead’s Effects on Human Reproduction and Intelligence

Most ingested lead in humans is initially present in the blood, but that amount
eventually reaches a plateau. Any excess enters the soft tissues, including the
organs, particularly the brain. Eventually lead becomes deposited in bone,
where it replaces calcium, because Pb2 and Ca2 ions are similar in size.
Indeed, lead absorption by the body increases in persons having a calcium (or
iron) deficiency and is much higher in children than in adults. A study in
Mexico indicated that pregnant women can decrease the lead levels in their
blood—and presumably in the blood of their developing fetus—by taking cal-
cium supplements.
At high levels, inorganic lead (Pb2) is a general metabolic poison. The
toxicity of lead is proportional to the amount present in the soft tissues, not
to that in blood or bone. Lead remains in human bones for decades; thus it
can accumulate in the body. The dissolving of bone, as occurs with old age or
illness such as osteoarthritis and advanced periodontal disease or in times
of stress such as pregnancy and menopause, results in the remobilization of
bone-stored lead back into the bloodstream where it can produce toxic
effects. Excess lead may lead to the deterioration of bones in adults. Recently
a correlation has been found between periodontal bone loss and blood lead
levels in U.S. adults, particularly in those who smoke. Children exposed to
environmental lead also have more dental cavities.
Although there is some evidence that too much lead can slightly increase
the blood pressure of adults, the humans most at risk from Pb2 even at rela-
tively low levels are fetuses and children under the age of about seven years.
Both these groups are more sensitive to lead than are adults, partly because
they absorb a greater percentage of dietary lead and partly because their
brains are growing rapidly. The metal readily crosses the placenta and thus is
passed from mother to unborn child. Because of the immaturity of the fetus’s
blood–brain barrier, there is little to prevent the entry of lead into its brain.
In addition, lead is transferred postnatally from the mother in her breast milk
and/or from the tap water used to prepare formula for bottle-fed babies.
The principal risk to children from lead is interference with the normal
development of their brains. A number of studies have found small but con-
sistent and significant neuropsychological impairment in young children
due to environmental lead absorbed either before or after birth. Lead appears
to have deleterious effects on children’s behavior and attentiveness, and pos-
sibly also on their IQs. This is illustrated in Figure 15-5, where a mental
120
development score is plotted as a function of age for
groups of young children differentiated by the amount
of lead in their umbilical cord at birth. A study of
children in a lead-smelting community (Port Pirie) in
Low Australia indicates that children with a blood lead
116
Mental development index score
level of 300 ppb had an average IQ 4 to 5 points lower

than those whose level was 100 ppb. This result is
Medium consistent with other studies that indicate an IQ
deficit of about 2–3 points for each increase by
112 100 ppb of blood lead. Some studies indicate that
prenatal exposure to lead—especially during the first
trimester of pregnancy—has the greatest detrimental
effect on the IQs measured in children in primary
High
grades, some indicate it is the lead level at the age of
108
two (when blood concentrations usually peak) that is
predominant, and others that it is the concurrent lead
level—even if lower than that in early childhood—
that is the dominant factor. No threshold for the
104 effects of lead upon IQ are apparent in the studies.
6 12 18 24
Age at testing (months)
A survey in 1976–1980 of American children
aged six months to five years found that about 4% of
them had blood lead levels in excess of 300 ppb and
FIGURE 15-5 The effect
that an additional 20% had levels over 200 ppb
of prenatal exposure to (see Figure 15-6a). These concentrations represent two of the cutoffs that
lead on the mental devel- had been proposed in the past as “safe” levels, but it appears that there may
opment of infants. Lead be no level at which lead does not produce a deleterious effect (i.e., there is
exposure is measured by its no threshold) in young and unborn children. A second survey, in 1988–1991,
concentration in the blood
of the child’s umbilical
indicated that blood lead levels in U.S. children had fallen substantially;
cord. [Source: D. Bellinger less than 9% of those aged one to five years had blood lead levels greater than
et al., “Longitudinal Analyses of 100 ppb (see Figure 15-6b). The average American adult blood lead level fell
Prenatal and Postnatal Lead from about 150 ppb in the 1970s to about 10–20 ppb today.
Exposure and Early Cognitive
The effects of lead poisoning were known to the ancient Greeks, who
Development,” New England
Journal of Medicine 316 (1987):
realized that drinking acidic beverages from containers coated with lead-
1037–1043. Reprinted by containing substances could result in illness. This information was not available
permission of the New England to the Romans. Indeed, they sometimes deliberately adulterated overly acidic
Journal of Medicine.] wine with sweet lead salts to improve the flavor. The concentration of lead
in the bones of Romans is almost 100 times that found in modern North
Americans. Some historians have hypothesized that chronic lead poisoning of
upper-class Romans, from wine and other sources, contributed to the eventual
downfall of the Roman Empire because of the metal’s detrimental effects on the
neurological and reproductive systems. The latter effects include dysfunctional
sperm in males and an inability to bring the fetus to term in females. Indeed,
in the past women who worked in the lead industry suffered higher-than-
average rates of miscarriages and stillbirths. Due primarily to the contamina-
tion of beverages by lead from the distillation of alcohol in lead vessels, episodes
Lead 691
(a)
20
Percentage of children
15
10
0
0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 >300
(b)
20
Percentage of children
15 FIGURE 15-6 The distri-

bution of blood lead levels
10 in U.S. children aged one to
five years (a) in 1976–1980
and (b) in 1988–1991.
5 [Source: R. A. Goyer, “Results
of Lead Research: Prenatal
0 Exposure and Neurological
0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 >300 Consequences,” Environmental
Blood lead level (ppb) Health Perspectives 104 (1996):
1050–1054.]
of colic and gout due to lead poisoning were recorded through the Middle Ages
and even until recent times.
In summary, on an atom-for-atom basis, lead is not as dangerous as mer-
cury. However, the general population is exposed to lead from a greater vari-
ety of sources and generally at higher levels than those associated with
mercury. Overall, more people are adversely affected by lead, though on aver-
age to a lesser extent, than those fewer individuals exposed to mercury. Both
metals are more toxic in their organic compound form than in the simple
inorganic cation form. In terms of its environmental concentration, lead is
much closer—within a factor of 10—to the level at which overt signs of poi-
soning become manifest than is any other substance, including mercury. Thus
it is appropriate that society continues to take steps to further reduce human
exposure to lead.
P R O B L E M 15-9
The concentrations of lead in blood samples are often reported in units of micro-
grams of Pb per deciliter of blood or in micromoles of lead per liter of blood.
Calculate the value of the concentration in these units of a blood sample con-
taining 60 ppb lead, assuming that the density of blood is one gram per milliliter.
Cadmium
Cadmium, Cd, lies in the same subgroup of the periodic table as zinc and
mercury, but it is more similar to the former. Like zinc, the only common ion
of cadmium is the 2 species. In contrast to mercury, cadmium’s compounds
with simple anions such as chloride are ionic salts rather than covalent
molecules.
Environmental Sources of Cadmium

Most cadmium is produced as a by-product of zinc smelting, since the two
metals usually occur together. Some environmental contamination by cad-
mium often occurs in the areas surrounding zinc, lead, and copper smelters. As
is the case for the other heavy metals, burning coal introduces cadmium into
the environment. The disposal by incineration of waste materials that contain
cadmium is also an important source of the metal to the environment.
A major use of cadmium is as an electrode in rechargeable nicad
(nickel–cadmium) batteries used in calculators and similar devices. When cur-
rent is drawn from the battery, the solid elemental metal cadmium electrode
partially disintegrates to form insoluble cadmium hydroxide, Cd(OH)2, by
incorporating hydroxide ions from the medium into which it dips. When the
battery is being recharged, the solid hydroxide, which was deposited on the
metal electrode, is converted back to cadmium metal:
Cd(s) 2 OH Δ Cd(OH)2(s) 2 e
Each nicad battery contains about 5 g of cadmium, much of which is
volatilized and released into the environment if the spent batteries are incin-
erated in garbage. The metallic cadmium preferentially condenses on the
smallest particles in the incinerator smoke stream, which are precisely the ones
that are difficult to capture by pollution-control devices inserted in the gas
stack. In order to avoid releasing airborne cadmium into the environment
upon combustion, some municipalities require nicad batteries to be separated
from other garbage. The recycling of metals from such batteries has also
begun in some areas. However, the European Union has banned the use of
nicad batteries, except in cordless power tools and systems used for safety and
medical purposes. Some U.S. states have banned the disposal of nicad batter-
ies. Battery manufacturers hope to replace nicad batteries soon with ones that
do not contain cadmium.
In ionic form, the main use of cadmium is as a pigment. Because the color
of cadmium sulfide, CdS, depends on the size of the particles, cadmium pig-
ments of many hues can be prepared. Both CdS and CdSe have been used
extensively to color plastics. For several centuries, painters have used cad-
mium sulfide pigments in paints to produce brilliant yellow colors and thus
oppose any ban on them, since at present there are no suitable replacements.
Cadmium 693
Van Gogh could not have painted his famous Sunflowers canvas without
cadmium yellows, although it is speculated that cadmium poisoning may
have contributed to the painter’s anguished mental state.
Cadmium is released into the environment during the incineration of
plastics and other materials that contain it as a pigment or as a stabilizer. It
is also released into the atmosphere when cadmium-plated steel is recycled,
since the element is fairly volatile when heated (its boiling point is 765°C).
Human Intake of Cadmium

Cd2 is rather soluble in water, unless sulfide ions are also present to precipi-
tate the metal as CdS. Thus humans usually ingest only a small proportion of
their cadmium directly from drinking water or from air, except for individuals
who live near mines and smelters, particularly those that process zinc. The
maximum containment level (MCL) for cadmium in drinking water is 5 ppb
in the United States and Canada (Table 15-2).
Smokers are also exposed to cadmium that is absorbed from soil and
irrigation water by tobacco leaves and then released into the smoke stream
when a cigarette is burned. Heavy smokers have approximately double the
net cadmium intake of nonsmokers.
Owing to its similarity to zinc, plants absorb cadmium from irrigation
water. The use on agricultural fields of phosphate fertilizers, which contain
ionic cadmium as a natural contaminant, and of sewage sludge contami-
nated with cadmium from industrial releases increases the cadmium level in
soil and subsequently in plants grown in it. In the future, cadmium may be
removed from phosphate fertilizer before it is sold to the consumer (see also
Chapter 16). Soil also receives cadmium from atmospheric deposition.
Since cadmium uptake in plants increases with decreasing soil pH, one
effect of acid rain is to increase cadmium levels in food.
For most of us, the greatest proportion of our exposure to cadmium comes
from our food supply. Seafood and organ meats, particularly kidneys, have
higher cadmium levels than do most other foods. However, the majority of
cadmium in the diet usually comes from potatoes, wheat, rice, and other
grains, since most people consume so much more of them than of seafood and
kidneys. An exception is the Inuit people of Canada’s Northwest Territories;
a prized component of their diet is caribou kidneys, organs which are highly
contaminated by cadmium that has reached the Arctic regions on the wind
from industrial regions in Europe and North America.
Historically, all episodes of serious cadmium contamination resulted from
pollution from nonferrous mining and smelting. The most acute environ-
mental problem involving cadmium occurred in the Jintsu River Valley
region of Japan, where rice for local consumption was grown with the aid of
irrigation water drawn from a river that was chronically contaminated with
dissolved cadmium from a zinc mining and smelting operation upstream.
Hundreds of people in this area, particularly older women who had borne
many children and who had poor diets, contracted a degenerative bone dis-
ease called itai-itai or “ouch-ouch,” so named because it causes severe pain in
the joints. In this disease, some of the Ca2 ions in the bones are replaced by
Cd2 ions since they have the same charge and are virtually the same size.
The bones slowly become porous and can subsequently fracture and collapse.
The intake of cadmium by itai-itai sufferers was estimated at about 600 mg per
day, about 10 times the average ingestion of North Americans.
Protection Against Low Levels of Cadmium

Cadmium is acutely toxic: The lethal dose is about 1 g. Humans are protected
against chronic exposure to low levels of cadmium by the presence of the sulfur-
rich protein metallothionein, the usual function of which is the regulation of
zinc metabolism. Because it has many sulfhydryl groups, metallothionein can
complex almost all ingested Cd2; the complex is subsequently eliminated in
the urine. If the amount of cadmium absorbed by the body exceeds the capac-
ity of metallothionein to complex it, the metal is stored mainly in the liver
and kidneys. Indeed, there is evidence that chronic exposure to cadmium
eventually leads to an increased chance of acquiring kidney disease.
The average cadmium burden in humans is increasing. Although cad-
mium is not biomagnified, it is a cumulative poison since, if not eliminated
quickly (by metallothionein, as discussed above), its lifetime in the body is
several decades. The geographic areas at greatest risk from cadmium exposure
are Japan and central Europe; in both regions, the pollution of the soil by cad-
mium is particularly high due to contamination from industrial operations.
Rice grown in many areas of Japan is often contaminated with rather high
cadmium levels. As a consequence, the dietary intake of cadmium by resi-
dents of Japan is substantially greater than for peoples of other developed
countries. Indeed, in Japan the average daily amount of ingested cadmium is
beginning to approach the maximum level recommended by health authori-
ties, although this limit has a large built-in safety factor relative to levels at
which health effects would occur.
Arsenic
Arsenic is not actually a metal; it is a metalloid—its properties are intermedi-
ate between those of metals and nonmetals. However, for convenience we
discuss it in this chapter.
Arsenic compounds such as the oxide As2O3, white arsenic, were common
poisons used for murder and suicide from Roman times through the Middle
Ages. In the seventeenth century, arsenic was believed in some European
societies to be not only a poison but also a magical substance that was a cure
for certain ailments, including impotence, and to be a prophylactic against
Arsenic 695
the plague. Indeed, arsenic compounds have been used therapeutically for
2000 years, and even today about 50 Chinese drugs contain the element.
There are small background levels of arsenic in many foods, and a trace
amount of this element apparently is essential to good human health.
Arsenic(III) Versus Arsenic(V) Toxicity

Arsenic occurs in the same group of the periodic table as phosphorus and so
also has an s2p3 electron configuration in its valence shell. Loss of all three p
electrons gives the 3 ion, whereas sharing of the three electrons gives triva-
lent arsenic; collectively, these two forms are designated As(III). Arsenic(III)
commonly exists in aqueous solution and in solids as the arsenite ion, AsO33
(which can be considered to be As3 bonded to three surrounding O2 ions),
or one of its successively protonated forms: HAsO32, H2AsO3, or H3AsO3.
Alternatively, loss of all five valence shell electrons gives the 5 ion, and
sharing them all gives pentavalent arsenic; collectively, these two forms are
designated As(V). Arsenic(V) also commonly exists as an oxyanion, the
arsenate ion, AsO43 (equivalent to As5 bound to four O2 ions), or one of
its successively protonated forms: HAsO42, H2AsO4, or H3AsO4.
O
As As
–
O O– –
O O–
O– O–
arsenite arsenate
AsO33– AsO43–
Overall, arsenic acts much like phosphorus, which commonly exists in the
analogous oxyanion forms PO33 and PO43, called phosphite and phosphate,
respectively. However, arsenic has more of a tendency than phosphorus to
form ionic rather than covalent bonds, since it is more metal-like. Due to the
similarity in properties, arsenic compounds coexist with those of phosphorus
in nature. Consequently, arsenic often contaminates phosphate deposits and
commercial phosphates.
Arsenic’s lethal effect when consumed in an acute dose is due to gastroin-
testinal damage, resulting in severe vomiting and diarrhea. Inorganic As(III)
is more toxic than As(V), although some of the latter is converted by reduc-
tion to the former in the human body. It is thought that the greater toxicity
of As(III) is due to its ability to be retained in the body longer since it
becomes bound to sulfhydryl groups in one of several enzymes. Due to the
subsequent inactivity of the enzymes, energy production in the cell declines
and the cell is damaged. Once the arsenic becomes methylated in the liver, it
does not bind tightly to enzymes and hence is largely detoxified.
Anthropogenic Sources of Arsenic to the Environment

Anthropogenic environmental sources of arsenic stem from
• the continuing use of its compounds as pesticides;
• its unintended release during the mining and smelting of gold, lead,
copper, and nickel, in whose ores it commonly occurs (the leachate from
abandoned gold mines of previous decades and centuries can still be a signif-
icant source of arsenic pollution in water systems);
• the production of iron and steel;
• the combustion of coal, of which it is a contaminant; and
• arsenic-contaminated water brought to ground level by wells.
The arsenic present in raw coal can become a serious pollutant, espe-
cially around areas where the fossil fuel is burned. The total pollution from
arsenic can be substantial where the coal is burned in small, unventilated
stoves rather than in large power plants. In these cases, which occur in some
developing countries, the arsenic not only becomes an indoor air pollutant
but also contaminates the food and water stored indoors. A particularly acute
example occurs in the Chinese province of Guizhou, where arsenic levels in
the coal are extraordinarily high, exceeding 1% (i.e., 10,000 ppm) in some
cases. Many of the residents of Guizhou suffer arsenic-related health prob-
lems, since they use this coal for domestic cooking and heating. By contrast,
the level of arsenic in U.S. coal averages about 22 ppm, and most coal world-
wide has arsenic levels of less than 5 ppm.
Arsenic compounds found widespread use as pesticides before the mod-
ern era of organic chemicals. Although its use in these applications has
decreased, arsenic contamination from pesticides remains an environmental
problem in some areas of the world. The common arsenic-based pesticides
include the insecticide lead arsenate, Pb3(AsO4)2, and the herbicide calcium
arsenate, Ca3(AsO4)2, both of which contain As(V) as AsO43. The herbi-
cides sodium arsenite, Na3AsO3, and Paris Green, Cu3(AsO3)2, both con-
tain As(III) as AsO33. An organic compound containing As(V) is routinely
used in chicken feed to stimulate growth and prevent disease; some scientists
have worried about the contamination of soil and water by arsenic leached
from chicken litter. Some methylated derivatives of arsenic acids are still used
as herbicides, even in developed countries. The sodium salt of the arsenate
ion in which one 9OH has been replaced by a methyl group, producing the
methanearsonate ion, O “ As(OH) (CH3)O - , is a herbicide widely used on
golf courses and cotton fields in the United States. Such As(V) compounds
act as weedkillers because they enter into plant metabolism in place of phos-
phate ion. The environmental consequences of using another heavy metal,
tin, in a pesticide are discussed in Box 15-1.
Arsenic 697
BOX 15-1 Organotin Compounds
A lthough inorganic compounds of tin (Sn)

are relatively nontoxic, the bonding of
one or more carbon chains to the metal results
oxide, Cu2O, in such applications since their
effectiveness lasts longer than a single season.
Unfortunately, some of the tributyltin
in substances that are toxic. Such organotin compound leaches into the surface waters in
compounds have some common uses, such as contact with the coatings or paint, particularly
additives to stabilize PVC plastics and fungi- in harbors where the boats are moored, and
cides to preserve wood, and therefore are of subsequently enters the food chain via the
environmental concern. microorganisms that live near the surface.
Tin forms a series of compounds of gen- This can lead to sterility or death for fish and
eral formula R3SnX, which are molecular sub- some types of oysters and clams that feed on
stances though often shown in formulas as if these microorganisms. Some countries have
they were ionic, e.g., (R3Sn) (X), where R is restricted the use of tributyltin compounds to
a hydrocarbon group and X is a monatomic large ships. Thus, although the concentration
anion; corresponding compounds such as of tributyltin has decreased in the waters of
(R3Sn)2O also occur. All these compounds are small harbors and marinas, the pollutant still
toxic to mammals when R is a very short alkyl tends to concentrate in marine coastal regions
chain; maximum toxicity occurs when R is the due to its use on large vessels. Scientists are
ethyl group, C2H5, and decreases progressively worried that the presence of tributyltin
with increasing chain length. compounds in these waters could affect fish
For fungi the greatest toxic activity is reproduction.
attained when each hydrocarbon chain has four For this reason, the International
carbons in an unbranched chain, i.e., when R is Maritime Organization banned new applica-
the n-butyl group, — CH2CH2CH2CH3 (or sim- tions of tributyltin to ships of any size effec-
ply n-C4H9). Tributyltin oxide, (R3Sn)2O where tive 2003 and required that this material be
R n-C4H9, and the corresponding fluoride removed from all old applications by 2008.
have both been used as fungicides; commonly Ironically, the triazine herbicide added to
they are incorporated as antifouling agents in copper-based antifoulant paints that were
the paint applied to docks, to the hulls of boats, introduced to replace those based upon
to lobster pots, and to fishing nets, etc. to pre- tributyltin degrades only slowly in water and
vent the accumulation of slimy marine organ- has now begun to accumulate there.
isms such as the larvae of barnacles. In recent Higher organisms have enzymes that
years tributyltin has been incorporated into break down tributyltin fairly rapidly, so it is
polymeric coatings for boat hulls; a thin layer of not very toxic to humans. However, most
the compound subsequently forms around the humans now have detectable levels of tribu-
hull. The tin compounds replaced copper(I) tyltin in their blood.
Since the 1970s, arsenic has been used in the form of the compound chro-
mated copper arsenate, CCA, to pressure-treat lumber in order to prevent rot
and termite damage. Unfortunately, some of the arsenic leaches out of the
wood over time. U.S. and Canadian producers of CCA-treated wood volun-
tarily phased out use of the arsenic compound at the end of 2003 for wood
destined for residential structures such as decks, picnic tables, fences, and
playground equipment. CCA is discussed in further detail in the section on
chromium. The U.S. EPA has already banned arsenic in all other pesticides.
Arsenic in Drinking Water

Arsenic—much of it from natural sources—is one of the most serious envi-
ronmental health hazards. The presence of significant levels of arsenic in
drinking-water supplies is a significant and controversial environmental
issue. Natural levels of arsenic in water can be quite high, and it is more com-
mon for health problems to arise from this source than from anthropogenic
arsenic. Although arsenic has been used for millennia as a poison, the major
health problem stemming from its presence at low levels in drinking water is
cancer. Drinking arsenic-contaminated water has also been linked to diabetes
and cardiovascular disease, perhaps by disrupting a hormonal process associ-
ated with both conditions.
Arsenic is carcinogenic in humans. Lung cancer results from the inhala-
tion of arsenic and probably also from its ingestion. Cancers of the lung, blad-
der, and skin, and perhaps also of the kidney, arise from ingested arsenic,
including that in water. The mechanism by which arsenic causes cancer is
not clear. Evidence suggests that it acts as a cocarcinogen, inhibiting the DNA
repair mechanism and thereby enhancing the cancer-causing abilities of
other carcinogens. There is evidence from Chile that smoking and simultane-
ous exposure to high levels of arsenic in drinking water act synergistically in
causing lung cancer; i.e., their effect taken together is greater than the sum of
their individual effects if each acted independently, as discussed in Chapter 4.
Other data from Chile show that exposure to arsenic during early childhood
or even in utero increases subsequent mortality in young adulthood from both
malignant and nonmalignant lung diseases. Indeed, arsenic seems to act syn-
ergistically with several cofactors—i.e., factors whose presence negatively
affects the health of an individual to an extent greater than if it or the arsenic
operated independently. Exposure to excessive levels of UV from sunlight
and a lack of selenium in the diet (stemming from malnutrition and/or low
selenium levels in local foods) are other cofactors with arsenic. The protec-
tive effect of selenium in reducing the amount of active arsenic in the body
may arise from the formation of a biomolecule containing an As “ Se bond.
Research is under way to determine whether selenium supplementation of
the diet would be effective in countering the negative health effects of excess
arsenic in the drinking water of Bangladesh and the Bengal region of India.
Drinking water, especially that derived from groundwater, is a major
source of arsenic for many people. Although anthropogenic uses of arsenic can
result in its contamination of water, by far the greatest problems occur with
Arsenic 699
that produced by natural processes. Groundwater in several parts of the world

is highly contaminated with inorganic arsenic. Unfortunately, the arsenic is
tasteless, odorless, and invisible, so its presence is not easily detected.
Major problems from high arsenic levels occur in the Bengal Delta, with
the result that tens of millions of people in Bangladesh and in the West Bengal
region of India drink arsenic-laced water. The World Health Organization has
called this the “largest mass poisoning of a population in history.” The problem
arose from the creation of tens of millions of tube wells, which mine ground-
water that was previously inaccessible. The concrete tube wells extend 20 m
(60 ft) or more into the ground. Ironically, the wells were constructed by
UNICEF in the 1970s and early 1980s in an otherwise highly successful proj-
ect to eliminate epidemics of diarrhea, cholera, and other waterborne diseases
and to reduce the high child-mortality rate caused by use of microbially unsafe
water drawn from streams, ponds, and shallow wells used in the past. About
half the tube wells—affecting about 50 million people in Bangladesh—
produce water with arsenic levels as high as 500–1000 ppb, greatly exceeding
the 10 ppb WHO guideline for drinking water (Table 15-2). The sediments
through which the groundwater travels contain the arsenic. Generally, the
deeper the well beyond about 20 m, the lower the concentration of arsenic.
Several million people living in the Bengal Delta region will probably
contract skin disorders from drinking arsenic-laced groundwater if remedial
action is not taken; a fraction of them will also suffer from the more serious
ailment of arsenicosis, which can cause cancer of the skin, bladder, kidneys,
and lungs. Skin lesions appear after 5–15 years of exposure to high levels of
arsenic in drinking water. A large number of residents of West Bengal, India,
have already developed such lesions—the usual outward sign of chronic
exposure to arsenic—that may develop into skin cancer because they con-
sumed arsenic-laced groundwater from underground wells. The main cause of
arsenic-related deaths among these people is lung cancer. It has also been
established that rice and vegetables grown in Bangladesh using irrigation
water from tube wells are also contaminated by arsenic, and this may be the
dominant source of the element for some people. Grains and beans absorb
additional arsenic from the water they absorb when they are cooked.
Recent research from Bangladesh indicates that increasing levels of
arsenic and/or of manganese in drinking water confer progressively more
and more negative effects on the intellectual levels of six- and ten-year-old
children. The Mn levels in one such study averaged 1.4 ppb, compared to the
WHO standard of 0.5 ppb. Elevated manganese levels are also present even in
the United States: Approximately 6% of domestic wells exceed the U.S. EPA
lifetime health advisory concentration of 0.3 ppb Mn in drinking water.
The origin of the dissolved arsenic in the water in Bangladesh and India
is controversial. Normally the element, as arsenate ion, is coprecipitated with
and adsorbed on the surface of iron oxides in the soil, as would have occurred
in ancient times when sediments were being laid down. However, the arsenic,
along with the iron, dissolves when insoluble Fe(III) is reduced by natural
organic carbon to the more soluble Fe(II) state. Indeed, the higher the con-
centration of dissolved iron, the higher the arsenic concentration found in
the water. The controversy centers around whether the dominant process is
the natural one, by which buried peat acts as the reducing agent and has been
doing so for millennia, or whether the release has been greatly accelerated in
recent years as an indirect effect of annually lowering the water table by
extracting massive amounts of water for crop irrigation. In the latter mecha-
nism, the subsequent recharge of the depleted aquifer transports carbon in
the water drawn down from the surface, resulting in further reduction of iron
oxides and solubilization of the arsenic. Reduction of arsenic from As(V), as
it exists when adsorbed to the iron mineral, to the more soluble As(III) form
is also believed to be a factor in solubilizing the element. The water obtained
from adjacent wells separated even by only tens of meters from each other
can differ enormously in arsenic content, apparently as a result of being
drawn from sediments initially laid down in ancient times by different
streams that had different sources of organic carbon being deposited simulta-
neously. Widespread testing in 1999 of tube wells in Bangladesh identified
those delivering high arsenic levels, and the handles on such wells were
painted red to warn people of the danger. Thousands of larger, deeper wells
that draw water from less contaminated aquifers have subsequently been
installed as centralized facilities in many villages.
Arsenic-contaminated drinking water is also a major problem in Chile,
Argentina, Mexico, Nepal, Taiwan, Cambodia, Vietnam, and large areas of
China. Indeed, 8% of the deaths of Chilean adults over 30 are attributable to
arsenic poisoning. In a study of residents of Taiwan who were exposed to high
levels of the element in their well water, a relationship between arsenic
exposure and skin cancer incidence has been established. As in Bangladesh,
arsenic only became a problem when people began to drink groundwater,
which was touted as being purer than surface water, since the latter is often
contaminated by sewage.
Drinking-Water Standards for Arsenic

Drinking water, especially groundwater, is a major source of arsenic for most
people. The global average inorganic arsenic content of drinking water is
about 2.5 ppb. The World Health Organization has set 10 ppb as the accept-
able limit for arsenic in drinking water, and the European Union adopted this
standard in 2003 (Table 15-2). The standard in many developing countries is
still 50 ppb, which is no longer considered to be protective.
In the last days (2000) of the Clinton administration, the maximum con-
taminant level for arsenic in U.S. drinking water was lowered from 50 ppb to
10 ppb. Although the Bush administration at first withdrew this regulation, it
later concluded that the reduction was warranted. As a result, the 10-ppb
limit became law in February 2002, and the compliance date was set for 2006.
Arsenic 701
The shape of the dose–response curve (see Chapter 10) at such low
concentrations of arsenic is unknown. Assuming that no threshold exists,
linear extrapolations of human cancer incidence from populations that
were exposed to high levels of arsenic leads to the conclusion that there is
a 1-in-1000 lifetime risk of dying from cancer induced by normal back-
ground levels of arsenic. This estimate makes arsenic almost equivalent to
environmental tobacco smoke and radon exposure as an environmental
carcinogen. Drinking water over a lifetime at the 50-ppb level, the old U.S.
standard, would cause bladder or lung cancer in about 1% of the popula-
tion, a much greater risk than continuously consuming any other water-
based contaminant at its MCL. Some environmentalists argue that the
arsenic standard should be lowered still further, to 3 ppb, at which the risk
is 1 in 1000, whereas at 10 ppb it is about 3 per thousand. About 57 million
Americans currently drink water containing more than 1 ppb of arsenic;
areas of the contiguous United States whose groundwater sometimes con-
tains more than 10 ppb As are shown in dark green in Figure 15-7. Most
affected systems lie in the West, Midwest, Southwest, and New England
and use groundwater having naturally occurring arsenic.
Counties with arsenic concentrations exceeding 10 ppb in 10% or more of samples.

Counties with arsenic concentrations exceeding 5 ppb in 10% or more of samples. FIGURE 15-7 Average
arsenic concentrations in
Counties with arsenic concentrations exceeding 3 ppb in 10% or more of samples. U.S. drinking water.
Counties with fewer than 10% of samples exceeding 3 ppb, representing areas of [Source: “Pressure to Set
lowest concentration. Controversial Arsenic Standard
Counties with insufficient data in the USGS database to make estimates. Increases,” Environmental
(2000): 208A.]
One of the difficulties in setting a standard for arsenic levels in drinking

water is deciding the manner in which the element operates as a carcinogen.
For carcinogens that induce cancer directly—by damaging DNA—the
assumption is made that no amount of exposure to the substance is safe, since
the risk from it rises from zero in proportion to exposure. However, as men-
tioned previously, there is evidence that arsenic does not act directly but indi-
rectly, by inducing cell damage and regrowth or by inhibiting repair of DNA
damage caused by other carcinogens such as UV light or tobacco smoke. For
carcinogens that act indirectly, there can be a threshold, a level below which
the substance can be considered safe and not cause damage.
Some scientists are not convinced that the estimates of cancer risk
quoted above are at all realistic, since the extrapolation of the cancer inci-
dence from high arsenic levels to the low environmental concentrations may
not be valid if arsenic acts indirectly as a carcinogen. It will be difficult to
resolve this issue by analyzing cancer trends in different parts of the United
States, however, since the predicted fraction of bladder and lung cancers
caused by arsenic is still a small percentage of the total for these diseases.
One argument that was advanced against making the arsenic standard
even as low as 10 ppb in the United States is that it forces some small-scale
suppliers of drinking water to shut down since they cannot afford the cleanup
costs associated with introducing equipment to remove the element. Such
shutdowns may lead consumers to turn to water supplies that are even more
unsafe in other respects. Indeed, lowering the standard to 10 ppb is estimated
to cost users of small water utilities, i.e., many of those in rural areas, several
hundred dollars per year, whereas it will cost users of large facilities only a few
dollars annually.
Removal of Arsenic from Water

The most widely used process for removing arsenic is to flow the drinking
water over activated alumina (aluminum oxide), onto the surface of which the
arsenic is adsorbed. The surface requires periodic cleaning of adsorbed species
to remain effective. Reverse osmosis can also be used to remove arsenic,
although, as previously discussed (Chapter 14), the process is expensive.
Because arsenic readily adsorbs onto iron oxide, water can be passed
through a bed of ferric oxide to remove most of the arsenic. Alternatively,
arsenic can be captured when iron hydroxide is precipitated from water, in a
technique similar to the removal of colloids described in Chapter 14. Some of
the other techniques used in villages in India and Bangladesh use the alumina
method described above or filtration of the water through sand. All removal
techniques require regular maintenance of the equipment and the proper
periodic disposal of the arsenic-laden wastes. Some analysts believe that none
of the arsenic-removal techniques work reliably in many areas, partly due to
poor maintenance; instead, people should be directed to deeper wells with
Arsenic 703
low arsenic contamination rather than trying to clean arsenic out of water
from shallower wells that contains high levels of the element. Centralized
water treatment plants using surface water are being constructed in some
areas to overcome dependence on groundwater.
Like calcium and magnesium, arsenic can be removed from drinking
water at large treatment facilities by precipitating it in the form of one of its
insoluble salts. The arsenic in surface water normally exists as As(V). Since
the salt formed between the ferric ion, Fe3, and arsenate ion is insoluble, the
soluble salt ferric chloride, FeCl3, can be dissolved in the water and the pre-
cipitated ferric arsenate, FeAsO4, can be filtered from the resulting mixture:
Fe3 AsO43 9: FeAsO4(s)
Arsenic in groundwater often exists as As(III) since reducing conditions
occur underground. Such arsenic must be oxidized to As(V) before this
removal process can occur.
Arsenic cannot be removed from water by cation exchange, since it
occurs as an anion, not a cation. However, anion exchange can be used to
remove arsenic from drinking water. Anion exchange also works better for
As(V) than As(III), since the latter exists partially as the neutral H3PO3,
rather than an anionic form at normal water pH values (6.5–8.5), whereas
As(V) is completely ionic in that range (see Additional Problem 3). Anion
exchange is problematic if appreciable amounts of sulfate ion, SO42, are also
present in the water, as these are exchanged preferentially to arsenate, thereby
tying up many sites and leaving fewer at which arsenic can exchange.
Steady State of Arsenic Levels in Natural Waters

A model for the mass balance of arsenic in a typical large water body, in this
case Lake Ontario, is shown in Figure 15-8. The lake receives 161 tonnes of
As per year, almost all of it from river and lake flows originating with land-
based sources; the rest comes from the atmosphere, mainly in the form of
arsenic dissolved in rain and snow. About three-quarters of the annual input
quantity leaves the lake by outflow (to the St. Lawrence River). The other
quarter corresponds to the net deposited into the surface sediment, after cor-
rection for the arsenic redissolved in the water column from this source. Over
time, the sediment arsenic, with a concentration of about 10 ppm, becomes
buried. The net input and output of arsenic into Lake Ontario are equal, so it
is in a steady state, and the concentration of the element in the water, about
0.5 ppb, remains constant with time.
Arsenic in Organic and Other Molecular Forms

The common environmental organic forms of arsenic are not simple methyl
derivatives, as with mercury and lead. Rather, they are water-soluble oxyacid
derivatives that can be excreted by the body and thus are less toxic than some
Atmospheric
deposition
Land- 158 Outflow 119

based 3.6
sources
Water Column
465 ng/L
FIGURE 15-8 Steady-
state model mass-balance 49 Deposition
diagram for arsenic in Lake
Ontario. [Source: Adapted Surface Sediment
from S. Thompson et al.,
Resuspension 10.4 μ g/g Burial 91
“A Modeling Strategy for
Planning the Virtual Elimination
of Persistent Toxic Chemicals (Rates are in tonnes/year)
from the Great Lakes,” Journal
42
of Great Lakes Research 25
(1999): 814.]
inorganic forms. As previously mentioned, in water arsenic occurs most com-

monly as the As(V) acid H3AsO4, i.e., (OH)3As “ O, or one of its deproto-
nated forms. Biological methylation in the environment by methylcobalamin
initially involves the replacement of one or more 9OH groups of the acid by
9CH3 groups. Monomethylation by the human liver and kidneys converts
most but not all ingested inorganic arsenic to (CH3)(OH)2As “ O and then
to the corresponding dimethyl acid, which is then readily excreted.
Although most daily exposure to arsenic by North American adults is
due to food intake, especially meat and seafood, much of the arsenic present
in food sources occurs in the organic form and is readily excreted. In seafood,
the common forms of arsenic are either the (CH3)4As ion, a form of As(III)
itself, or this ion with one methyl group replaced by 9CH2CH2OH or
9CH2COOH. The organic forms of arsenic found in seafood are probably
noncarcinogenic and are much less toxic than inorganic forms, as illustrated
in dramatic fashion by their high LD50 values, which lie in the thousands of
milligrams per kilogram, compared to those for inorganic arsenic, whose
LD50’s are about 1% of these values (see Table 15-3).
In contrast to the compounds discussed above, neutral As(III) com-
pounds such as arsine, AsH3, and trimethylarsine, As(CH3)3, are the most
toxic forms of arsenic. Curiously, the trimethyl compound is produced by the
reaction, under humid conditions, of molds in wallpaper paste with the
arsenic-containing green pigment CuHAsO3 in wallpaper. Instances of mys-
terious illnesses and even of human “death by wallpaper” due to chronic
exposure to the As(CH3)3 gas released into rooms by this mechanism have
been reported. Some historians believe Napoleon was fatally poisoned by the
Chromium 705
LD50 Values for Some Common Forms

TABLE 15-3 of Arsenic
Name Formula LD50 (mg/kg)
Arsenous acid H3AsO3 14

Arsenic acid H3AsO4 20
Methylarsonic acid CH3AsO(OH)2 700 – 1800
Dimethylarsonic (CH3)2AsO(OH) 700 – 1800
acid
Arsenocholine (CH3)3AsCH2CH2OH 6500
Arsenobetaine (CH3)3AsCH2COO 10,000
Source: X. C. Le, “Arsenic Speciation in the Environment,” Canadian Chemical News

(September 1999): 18.
trimethylarsine emitted from the wallpaper in his chronically damp house on

the island of St. Helena, where he had been exiled. There have also been
episodes of human poisoning from gaseous arsine that was accidentally gener-
ated and released when aqueous solutions of As(III) in the form of HAsO2
came into contact with an easily oxidized metal such as aluminum or zinc and
the arsenic was further reduced to As(III):
2 Al(s) HAsO2 6 H 9: 2 Al3 AsH3 2 H2O
Chromium
Chromium normally occurs in the form of inorganic ions. Its common oxida-
tion states are 3 and 6, i.e., Cr(III) and Cr(VI), known as trivalent and
hexavalent chromium, respectively.
Under oxidizing (i.e., aerobic) conditions, chromium exists in the (VI)
state, usually as the chromate ion, CrO42, though under even slightly acidic
conditions this oxyanion protonates to HCrO4.
H CrO42 Δ HCrO4
The oxyanions of Cr(VI) are highly soluble in water. Both the Cr(VI) ions
mentioned above are yellow, and they impart a yellowish tinge to water even
at chromium levels as low as 1 ppm. (At high concentrations not encountered
in the environment, chromate dimerizes to give the orange dichromate ion,
Cr2O72, familiar as a strong oxidizing agent in the laboratory and used in the
determination of the chemical oxygen demand (COD) of water samples, as
discussed in Chapter 13.)
Under reducing (i.e., anaerobic) conditions, chromium exists in the
(III) state. In aqueous solution, this state occurs as the 3 ion, i.e., Cr3.
However, the aqueous solubility of this ion is not high, and Cr(III) is often
precipitated as its hydroxide, Cr(OH)3, under alkaline, neutral, or even
slightly acidic conditions:
Cr3 3 OH Δ Cr(OH)3(s)
Thus, whether chromium occurs as an ion dissolved in water or as a precipitate
depends on whether the aqueous environment is oxidizing or reducing. The
difference is important, since hexavalent Cr(VI) is toxic and a suspected car-
cinogen, whereas trivalent Cr(III) is much less toxic and even acts as a trace
nutrient. Chromate ion readily enters biological cells, apparently because of its
structural similarity to sulfate ion, SO42. Inside the cell, chromate can oxidize
DNA and RNA bases. Because hexavalent chromium is more toxic, more
soluble, and more mobile than trivalent chromium, it is considered to pose a
greater health risk. (The term hexavalent chromium was made famous a few
years ago in the movie Erin Brockovich, the story of how a legal assistant bat-
tled successfully against pollution of local groundwater by this substance.)
Chromium Contamination of Water

Chromium is widely used for electroplating, corrosion protection, and leather
tanning. In tanning, Cr(III) binds to protein in animal skin to form leather
that is resistant to water, heat, and bacteria. As a consequence of industrial
emissions, chromium is a common water pollutant, especially of groundwater
beneath areas with metal-plating industries. It is also the second most abun-
dant inorganic contaminant of groundwater under hazardous waste sites. The
MCL for total chromium in U.S. drinking water is 100 ppb (Table 15-2).
Most dissolved heavy metals can be removed from wastewater by simply
increasing the pH, since their hydroxides are insoluble. However, Cr(VI)
does not precipitate out at any pH since it does not exist as a cation but rather
as an oxyanion in water. Owing to the low solubility and hence the low
mobility of Cr(III), however, the usual way to extract Cr(VI) from water is to
first use a reducing agent to convert Cr(VI) to Cr(III):
CrO42 3 e 8 H Δ Cr3 4 H2O

(soluble) (insoluble)
Reducing agents commonly employed for this conversion are gaseous SO2
or a solution of sodium sulfite, Na2SO3. In addition, reducing the Cr(VI)
to Cr(III) by adding iron in the form of Fe(II) and then adding base to
precipitate Cr(III) is a common practice in purifying Cr-contaminated waste-
water. Fine-grained elemental iron placed in permeable underground walls
positioned in the path of flowing polluted groundwater is another application
of this technique. The iron reduces the chromium, and then as Fe3 it forms
an insoluble Fe(III)–Cr(III) compound. This reduction process can occur
spontaneously in soils with, e.g., Fe2 or organic carbon as the reducing agent.
Chromium 707
Hexavalent chromium is quite mobile in soils, since it is not strongly absorbed

by many types of soil. However, it can be reduced to the less mobile trivalent
form by the humic substances in soils that are rich in organic matter.
The Wood Preservative CCA

Another potentially significant source of chromium to the environment stems
from its presence in chromated copper arsenate (CCA), the widely used wood
preservative previously mentioned. CCA is a waterborne mixture of metal
oxides with which wood is treated using a vacuum-pressure impregnation
process. The amount of CCA forced into the wood is almost 10% of the mass of
the lumber. The chromium used here originally is hexavalent. However, during
a period of fixation, which lasts for several weeks after treatment, almost all the
Cr(VI) is reduced to Cr(III) by reaction with carbon in the wood. This process
produces insoluble complexes that are slow to leach from the treated wood over
its lifetime, since the copper and chromium at least are bound to the wood.
Leaching of heavy metals from the wood becomes very slow a few months after
treatment, with more copper and arsenic than chromium being lost.
One use of CCA is to protect wooden structures, such as residential
docks, that are destined to be used in aquatic environments. For environmen-
tal and human-health reasons, CCA had largely replaced organic preserva-
tives such as creosote and pentachlorophenol (mentioned in Chapter 11) in
such applications. However, not only chromium but also arsenic and copper
leach from the structures into the water over time.
Green Chemistry: Removing the Arsenic and

Chromium from Pressure-Treated Wood
Wood that is used for exterior construction decays in about three to twelve
years unless it is treated with pesticides that prevent destruction from
termites, fungi, and other wood-destroying agents. Most of the preserved
exterior wood that is presently used is commonly called pressure-treated wood.
Found in over 50% of homes in the United States, pressure-treated wood is
also used in decks, fences, retaining walls, piers, docks, wooden bridges, pic-
nic tables, and playground equipment, and it lasts 20–50 years. Treatment of
wood thus results in the conservation of millions of trees each year and limits
the use of scarce woods that contain natural preservatives, such as redwoods.
Pressure-treated wood is produced by placing the wood in a horizontal
cylinder and evacuating the cylinder, which draws out much of the moisture
from the wood cells. An aqueous preservative solution is then pumped
into the cylinder and the pressure is raised, forcing the preservative solution
into the wood cells. Since the 1930s in the United States, the preservative
solution used in 95% of pressure-treated wood was copper chromated arsen-

ate (CCA), discussed in the previous section.
Although the exact composition varies, the most common formulation
for the preservative solution is 35.3% CrO3, 19.6% CuO, and 45.1% As2O3.
Treatment with CCA results in wood with copper, chromium, and arsenic
concentrations of 0.1–2.0%, 0.25–4.0%, and 0.15–4.0%, respectively. In
2001, 7 billion board feet of pressure-treated wood (enough to build 450,000
homes) was produced utilizing 150 million pounds of CCA. The CCA con-
tained 64 million pounds of hexavalent chromium and 40 million pounds of
arsenic. A 12-foot-long 2 6 board of CCA-treated wood contains from
16 to 300 g of arsenic. If all this arsenic were ingested, it would be enough to
kill many people.
Although the preservatives are “locked” into the wood, health officials
and environmentalists have long been concerned with the potential for
leaching of arsenic and chromium from pressure-treated wood and the inges-
tion of these elements by infants and children from direct contact with the
wood. Studies of the soils beneath decks made of pressure-treated wood gave
copper, chromium, and arsenic concentrations averaging 75, 43, and 76 mg/kg,
while control soils averaged 17, 20, and 4 mg/kg. Studies also indicate that
measurable amounts of arsenic can be dislodged from the surfaces of pressure-
treated wood by direct contact.
Because of the environmental and human-health concerns associated
with CCA, the U.S. EPA announced that wood producers had voluntarily
ceased production of CCA-treated wood on December 31, 2003, for products
intended for residential use. Chemical Specialties, Inc. (CSI) in 1996 intro-
duced a new wood preservative called Preserve to replace CCA, for which it
earned a Presidential Green Chemistry Challenge Award in 2002. Preserve is
formulated with an alkaline quaternary (ACQ) wood preservative. The active
ingredients in the preparation are copper and a quaternary ammonium salt,
R4NCl (either didecyl dimethyl ammonium chloride or alkyl dimethyl
benzyl ammonium chloride). According to the World Health Organization,
none of these ingredients are mammalian or human carcinogens.
Because there are no environmental and health concerns for ACQ,
under the EPA system, ACQ is registered as a nonrestricted pesticide for
treatment of wood products. Analogous formulations of copper and ACQ are
used as algaecides and fungicides in lakes, rivers, and streams, as well as in fish
hatcheries and potable water supplies. Quaternary ammonium salts are also
used as surfactants in typical household and industrial detergents and disin-
fectants, and unlike arsenic, they have low toxicity to mammals. It is also
noteworthy that the copper that is used in the ACQ formulations is obtained
from scrap copper. ACQ-treated wood not only eliminates the cancer and
toxicity concerns associated with CCA, but it offers the advantages of simpli-
fied disposal of treated wood and elimination of hazardous waste generation
at the approximately 450 treatment sites across the United States.
Review Questions
1. What is a sulfhydryl group, and how does 15. Explain why lead contamination of drinking
it interact biochemically with heavy metals? water by lead pipes is less common in hard-water
How does the interaction affect processes in areas than in soft-water areas.
the body?
16. Why were lead compounds used in
2. What is a chelate? What principle underlies the paints? Why were mercury compounds used
usual cure for heavy-metal poisoning? in paints?
3. Do heavy metals bioconcentrate? Do any 17. Explain why heavy-metal compounds such as
biomagnify? PbS and PbCO3 become much more soluble in
acidic water.
4. What are some important sources of airborne
mercury? 18. In what forms does lead exist in the lead
storage battery?
5. Is the liquid or the vapor of mercury more
toxic? Describe the mechanism by which mercury 19. What are the formulas and names of the
vapor affects the human body. two organic compounds of lead that were
used as gasoline additives? What was their
6. What is an amalgam? Give two examples and
function?
explain how they are used.
20. Discuss the toxicity of lead, especially with
7. Explain how the chlor-alkali process led to the
respect to its neurological effects. Which sub-
release of mercury in the environment.
groups of the population are at particular risk
8. Name two uses for mercury in batteries. from lead?
9. Write the formulas for the methylmercury 21. What are the main sources of cadmium in
ion, for two of its common molecular forms, the environment?
and for dimethylmercury. What is the
22. Explain how nicad batteries operate. What
principal source of human exposure to
other uses are made of cadmium?
methylmercury?
23. What is the main source of cadmium to
10. Explain why mercury vapor and methylmercury
humans?
compounds are much more toxic than other forms
of the element. 24. Describe what is meant by itai-itai disease,
and relate where it arose and why.
11. What is meant by Minamata disease? Explain
its symptoms and how it first arose. 25. What is metallothionein? What is its signifi-
cance with respect to cadmium in the body?
12. List several uses for organic compounds of
mercury. Which ones have been phased out? 26. What are some uses of arsenic that result in
contamination of the environment?
13. What are the two common ionic forms of
lead? 27. What organic compounds of arsenic are
of environmental significance? Why is arsenic
14. Explain how lead can dissolve—e.g., in
in organic acid forms not very toxic to
canned fruit juice—even though it is insoluble
humans?
in mineral acids.
28. What are the main health concerns about 33. Complete the chart shown in outline below:
arsenic in drinking water? Why is the drinking
water in many regions of Bangladesh heavily
Common
polluted with arsenic?
Common organo-
29. Describe how arsenic can be removed from ionic metallic Most toxic
water. Element forms forms forms
30. What are the two important oxidation states Mercury
of chromium? Which one is more toxic?
Lead
31. Explain how Cr(VI) can be removed from Cadmium
wastewater.
Arsenic
32. What is CCA? Name two toxic heavy metals Chromium
it contains.

See the discussion of focus areas and the princi- 3. What environmental advantages does electro-
ples of green chemistry in the Introduction before deposition offer over spray painting?
attempting these questions.
4. The removal of arsenic and chromium from
1. The replacement of lead with yttrium in electro- pressure-treated wood won Chemical Specialties,
deposition coatings won PPG a Presidential Green Inc. a Presidential Green Chemistry Challenge
Chemistry Challenge Award. Award.
(a) Into which of the three focus areas does this (a) Into which of the three focus areas for these
award best fit? awards does this award best fit?
(b) List one of the twelve principles that is addressed (b) List one of the twelve principles that is
by the green chemistry developed by PPG. addressed by the green chemistry developed by
Chemical Specialties, Inc.
2. What environmental advantages does the use of
yttrium oxide have over the use of lead oxide in
electrodeposition coatings?
Additional Problems
1. A man whose flesh weighs 50 kg eats 1 kg of comparison of this concentration to that of
fish a day. If the fish contains the legal limit of the fish, decide whether biomagnification is
0.5 ppm of methylmercury, and assuming that this occurring in the transfer of methylmercury from
substance becomes equally distributed within his the fish to the man. Would your answer to the
flesh, calculate the steady-state concentration of latter question differ if he ate only 0.2 kg of fish
methylmercury that his flesh will achieve. By a day?
2. (a) Approximately fit an exponential decay 5. How does the phenomenon of acid rain
curve to the distribution of blood lead among indirectly affect the risk to human health from
children based on the portion of the curve in mercury, lead, and cadmium?
Figure 15-6b from 20 ppb (the zero point of the
6. The 2 ions of mercury, lead, and cadmium
function) to higher levels. By integration, deter-
each form a series of complexes by attaching
mine the total percentage of children having
to themselves in successive equilibrium reactions
levels in excess of 100 ppb that your function
up to four chloride ions. Deduce the formulas
predicts.
for the species for one of these metals, including
(b) What does the fact that the curve in the net charges on the complexes. Would the
Figure 15-6b does not continue to rise as the complexes having three or four chlorines be
blood level comes close to zero tell us about the more likely to be found in fresh water or in
background level of lead in the environment? seawater?
3. (a) Since the ion AsO43 is basic, the forms 7. By reference to reliable websites or textbooks
HAsO42, H2AsO4, and H3AsO4 will all be in your library on heavy metals and/or water
present in aqueous solutions of its salts. Given pollution, determine why copper is considered
that for H3AsO4 the successive acid dissociation to be toxic, and find out what types of organisms
constants are 6.3 103, 1.3 107, and 3.2 are at risk from elevated levels in the environ-
1012, deduce the predominant form of arsenic in ment. Does speciation affect the toxicity of
waters of pH 4, 6, 8, and 10. copper?
(b) Arsenic in its As(III) form exists in solution
as H3PO3 or one of its ionized forms. Given 8. Based on the material in this chapter, write a
that the acid dissociation constant for H3PO3 is paragraph supporting your choice of which of the
6 1010, calculate the ratio of its un-ionized five metals you think still requires the most
molecular form to the ionized form H2PO3 at regulatory control for environmental reasons.
pH values of 8 and 10. 9. The equilibrium vapor pressure of mercury
4. The object of this problem is to estimate the at room temperature is about 1.6 106 atm.
mass of lead that would have been deposited annu- Imagine an old chemistry lab that, through
ally on each square meter of land near a typical, liquid mercury spills over the years, has accumu-
busy, six-lane freeway from the lead compounds lated enough mercury in cracks in the floor, etc.
emitted by cars using the roadway. Use reasonable that mercury liquid–vapor equilibrium has
estimates for the number of cars passing a point been established. What is the concentration, in
each day and their average mileage per liter or units of milligrams per cubic meter, of Hg0 in the
gallon of gasoline. Assume that the gasoline con- air of the room at 20°C? Does this value exceed
tained about 1 g of lead per gallon, or 0.2 g/L, and the limit of 0.05 mg/m3 established by the
make the approximation that half the lead was American Conference of Governmental Industrial
evenly deposited within 1000 m on each side of Hygienists for safe exposure based on a 40-hour
the freeway. workweek?
Further Readings
1. J. E. Ferguson, The Heavy Elements: Environ- 9. A. Spivey, “The Weight of Lead: Effects Add
mental Impact and Health Effects, (Oxford: Up in Adults,” Environmental Health Perspectives
Pergamon Press, 1990). 115 (2007): A31.
2. T. W. Clarkson, “The Three Modern Faces of 10. P. A. Baghurst et al. (a) “Environmental
Mercury,” Environmental Health Perspectives 110, Exposure to Lead and Children’s Intelligence at
supplement 1 (2002): 11. the Age of Seven Years,” New England Journal of
Medicine 327(18) (1992): 1279–1284; (b) “Expo-
3. G. J. Myers and P. W. Davidson, “Does
sure to Environmental Lead and Visual-Motor
Methylmercury Have a Role in Causing Develop-
Integration at Age 7 Years: The Port Pirie Cohort
mental Disabilities in Children?” Environmental
Study,” Epidemiology 6 (1995): 104.
Health Perspectives 108, supplement 3 (2002): 413.
11. W. Shotyk and M. Krachler, “Lead in Bottled
4. G.-B. Jiang, J.-B. Shi, and X.-B. Feng, “Mercury
Water: Contamination from Glass and Compari-
Pollution in China,” Environmental Science and
son with Pristine Groundwater,” Environmental
Technology 40 (2006): 3672.
Science and Technology 41 (2007): 3508.
5. T. W. Clarkson, “Mercury: Major Issues in
12. M. N. Mead, “Arsenic: In Search of an
Environmental Health,” Environmental Health
Antidote to a Global Poison,” Environmental
Perspectives 100 (1992): 31–38.
Health Perspectives 113 (2005): A378.
6. R. Hoffmann, “Winning Gold,” American
13. A. Lykknes and L. Kvittingen, “Arsenic: Not
Scientist 82 (1994): 15–17.
So Evil After All?” Journal of Chemical Education
7. R. A. Goyer, “Results of Lead Research: 80 (2003): 497.
Prenatal Exposure and Neurological Conse-
14. J. A. Hingston et al., “Leaching of Chromated
quences,” Environmental Health Perspectives 104
Copper Arsenate Wood Preservatives: A Review,”
(1996): 1050–1054.
Environmental Pollution 111 (2001): 53.
8. R. L. Canfield et al., “Intellectual Impairment
in Children with Blood Lead Concentrations
Below 10 g per Deciliter,” New England Journal of
Medicine 348 (2002): 1517.
C H A P T E R
16
WASTES, SOILS,
AND SEDIMENTS
topics are used:
 Thermochemistry
 Concept of oxidation and reduction as electron loss or
gain; oxidation number; basic electrochemistry
 Background organic chemistry (see Appendix)
 Concepts of acids and bases; pH
 Phase diagrams

 Adsorption; NOX; particulates (Chapters 3 and 4)
 Aerobic and anaerobic decompositions; methane
(Chapter 6)
 Ethanol; MTBE (Chapter 8)
 DDT; Kow (Chapter 10)
 PCBs, dioxins, and furans (Chapter 11)
 PAHs; phthalates; BTEX, chlorinated solvents
(Chapter 12)
 BOD, COD, and water carbonate chemistry (Chapter 13)
 Heavy-metal chemistry (Chapter 15)
Introduction
In this chapter, we turn our attention to the environmental aspects of the
solid state—particularly of soil and of the sediments of natural water
systems—and of ways that polluted soils and sediments can be remediated.
713
714 Chapter 16 Wastes, Soils, and Sediments
A closely related issue is the nature

and disposal of concentrated wastes of
all kinds, including both domestic
garbage and hazardous waste, and their
possible recycling.
The material in this chapter has
been arranged in the order of gener-
ally increasing toxicity and hazard.
Thus we begin with the least toxic
substances—domestic and commer-
cial garbage—and consider its dis-
posal by landfilling, incineration, or
recycling. We then consider soils and
sediments and their contamination by
A tractor moving shredded paper in the warehouse of a paper-recycling
chemicals. Finally, we look at haz-
plant. The paper can be reused or recycled in several different ways. ardous wastes and some of the high-
(Digital Vision) technology methods that are being
developed to dispose of them.
Domestic and Commercial Garbage:

Its Disposal and Minimization
The great majority of the material that we discard and that must be disposed
of is not hazardous but is simply garbage or refuse. The greatest single con-
stituent of this solid waste (defined as waste that is collected and transported
by a means other than water) is construction and demolition debris, almost
all of which is either reused or eventually buried in the ground. The second
largest volume of waste is that generated by the commercial and industrial
sectors, followed by the domestic waste generated by residences. Typically, a
North American generates about 2 kg of domestic and commercial waste a
day, twice as much as the average European. In these discussions, we will not
consider the much larger amounts of waste generated by the petroleum indus-
tries, by agriculture, as ashes from power plants, or as sewage, which was dis-
cussed in Chapter 14.
A breakdown by the type of solid waste typically generated in countries
at various levels of economic development is shown in Figure 16-1. Notice
that the fraction of the waste that is vegetable matter declines as the level
of economic development rises. The opposite is true of paper, which in
industrialized countries is the largest single component of waste and domi-
nates commercial-sector waste. Historically, the largest component of paper
waste was newspapers; now the volume of paper packaging is similar. The
amount of packaging has grown, in part, because so many goods are now
produced far from their ultimate destination and must be transported safely
over long distances.
Industrialized countries Middle-income countries Low-income countries

5% 2%
8% 14% 2%
2%
2% 4% 7%
31% 14%
8%
11%
10% 31%
2% 60%
10% 47%
13% 25%
Paper Other Plastics Textiles, rubber,

leather & wood
Vegetable Glass Metals
FIGURE 16-1 Typical composition of solid waste for countries at different levels of
economic development. [Source: “Waste and the Environment,” The Economist (29 May 1993): 5
(Environment Survey section).]
Plastics, glass, and metals each account for about one-tenth of the
volume of solid waste in developed countries, whereas organic matter (food
waste) accounts for about twice this value. These proportions would differ
significantly in areas that collect materials for recycling or composting: The
glass and metals components would be much smaller.
Burying Garbage in Landills

The main method used for disposal of municipal solid waste, MSW, is to
place it in a landfill (also variously called a garbage dump or a rubbish tip),
which is a large hole in the ground that is usually covered with soil and/or
clay after it is filled. For example, 85–90% of domestic and commercial waste
is currently landfilled in the United Kingdom, about 6% is incinerated, and
the same fraction is recycled or reused; similar figures apply to many munic-
ipalities in North America. Landfilling dominates the disposal methods
because its direct costs are substantially lower than disposal by any other
means.
In the past, landfills were often simply large holes in the ground that had
been created by mineral extraction—especially old sand or gravel pits. In
many instances, they leaked and contaminated the aquifers that lay beneath
them; this was especially true for landfills that used former sand pits, since
water easily percolates through sand. These landfills were not designed, con-
trolled, or supervised, and they accepted many types of wastes, including
hazardous materials.
Modern municipal landfills are much

Soil cover more elaborately designed and engineered,
Clay cap often accept no hazardous waste, and have
Cell their sites selected to minimize impact on
the environment. The components of a
typical modern landfill are illustrated in
Clay Clay Figure 16-2.
Cell In a sanitary landfill, the MSW is
compacted in layers (to reduce its volume)
Plastic
Clay
Leachate and is covered with about 20 cm (8 in.) of
liner collection system soil at the conclusion of each day’s opera-
tions. Thus the landfill consists of many
FIGURE 16-2 Compo-
adjacent cells, each corresponding to a
nents of a modern landfill day’s waste (Figure 16-2). After one layer of cells is completed, another is
(in the process of being begun, and the process is continued until the hole is filled. Usually, the land-
filled). fill is eventually capped by a meter or so of soil, or preferably clay, a material
that is fairly impervious to rain. A geomembrane made of plastic may be
added on top as a liner instead of the clay, or over it. The system recom-
mended by the U.S. EPA is illustrated in Figure 16-3.
During the time that municipal wastes in a landfill are decomposing—
aerobically at first, then anaerobically after a few months or a year—water
Methane gas
collection
Vegetation/soil 60 cm
top layer
Filter layer 15 cm
Drainage layer 30 cm
Geomembrane 0.5 mm
Clay layer 60 cm
Waste
FIGURE 16-3 Landfill

design with cover system
recommended by the
U.S. EPA.
from precipitation, liquid from the waste itself, and groundwater that seeps
into the landfill all percolate through the garbage, producing a liquid
called leachate. This liquid contains dissolved, suspended, and microbial
contaminants extracted from the solid waste. Leachate volume is relatively
high for the first few years after a site is covered. Typically, leachate
contains
• volatile organic acids such as acetic acid and various longer-chain fatty
acids;
• bacteria;
• heavy metals, usually in low concentration (those of most concern in
leachate are lead and cadmium); and
• salts of common inorganic ions such as Ca2.
The micropollutants present even in MSW leachate include common
volatile organic compounds such as toluene and dichloromethane.
Stages in the Decomposition of Garbage in a Landfill

There are three stages of decomposition in a municipal landfill. Operating
landfills still receiving garbage undergo all three stages simultaneously in dif-
ferent regions or depths. In practice, only food and yard waste biodegrade.
Rubber, plastics, and much of the paper content of garbage are very slow to
degrade.
• In the first, short, aerobic stage, oxygen is available to the waste; it
oxidizes organic materials to CO2 and water with the release of heat.
The internal temperature can rise to 70–80°C, since the reactions are
exothermic. The carbon dioxide released from the organic matter as it
decomposes makes the leachate acidic, thereby further facilitating its
ability to leach metals encountered in the waste. Since the majority of
biodegradable material is cellulose, whose empirical formula is approxi-
mately CH2O, we can approximate this phase of the reaction as
CH2O O2 9: CO2 H2O
Some organic matter is partially oxidized to aldehydes, ketones, and alcohols,

which give fresh waste its characteristic sweet smell.
• In the second, anaerobic acid phase, the process of acidic fermentation
occurs, generating ammonia, hydrogen, and carbon dioxide gases and large
quantities of partially degraded organic compounds, especially organic acids.
The pH of the leachate in this phase, 5.5–6.5, is chemically aggressive.
Other organic and inorganic substances dissolve in this leachate due to its
acidity. Again, carbon dioxide is released. This phase of the reaction can be
approximated by the reaction
2 CH2O 9: CH3COOH
although longer-chain fatty acids, which subsequently decompose into acetic
acid, are formed initially, as is hydrogen gas.
In this phase, the leachate has a high oxygen demand (see BOD and
COD, Chapter 13), as well as relatively high heavy-metal concentrations.
Anaerobic decomposition produces volatile carboxylic acids and esters,
which dissolve in the water present. The sickly sweet smell that emanates
from landfills during this phase is due to these esters and to thioesters.
• The third, anaerobic—or methanogenic—stage starts about six
months to a year after coverage and can continue for very long periods of
time. Anaerobic bacteria work slowly to decompose the organic acids and
hydrogen that were produced in the second stage. Since the organic acids
are consumed in the process, the pH rises to about 7 or 8, and the leachate
becomes less reactive. The main products of this stage are carbon dioxide
and methane, CH4. To a first approximation, the overall reaction is
CH3COOH 9: CH4 CO2
Methane generation usually continues for a decade or two and then drops
off relatively quickly. Some methane is also formed when hydrogen gas
combines with carbon dioxide. Much lower BOD values and a smaller
volume are associated with landfills in this phase. Because the leachate is
not acidic in this phase, the heavy-metal concentrations drop since these
substances are not as soluble at higher pH.
Often the methane gas produced by a landfill is vented to the atmosphere
by being directed into wells or gravel-packed seams in the landfill. In some
municipalities, the methane gas is burned as it is released through vents
(see Figure 16-3) rather than being released into the air. This treatment of the
methane is especially desirable, given that the greenhouse gas potential per
molecule of CH4 is much greater than that of the CO2 produced by its com-
bustion (Chapter 6). The heat produced from the combustion of this gas can
be used for practical purposes. Indeed, the second and third stages of decom-
position in landfills are identical to those used in the deliberate production of
biogas (biomethane) for energy in reactors using municipal solid waste sludge,
food processing waste, livestock waste, and other biodegradable materials.
P R O B L E M 16-1
Calculate the volume of methane gas, at 15°C and 1.0 atm pressure, that is
released annually by the anaerobic decomposition of 1 kg of garbage, assum-
ing the latter is 20% biodegradable organic in nature and that decomposition
occurs evenly over a 20-year period. [Hint: Add together the equations for the
two anaerobic stages of decomposition.]
Leachate from a Landfill

Engineering is needed to control the leachate from a landfill. Otherwise, the
liquid can flow out at the bottom of the landfill and percolate through porous
soil to contaminate the groundwater below it. Alternatively, if the soil under
the landfill is nonporous, the leachate can build up and gradually overflow
the site (the overflowing bathtub effect), possibly contaminating nearby
surface waters.
The typical components used to control the leachate consist of:
• A leachate collection and removal system, followed by treatment
of the liquid. Often the potential effect of leachate on groundwater is
monitored by digging and testing several wells in the vicinity.
• A liner placed around the walls and bottom of the landfill. The liner
material is either synthetic (e.g., a plastic such as 2-mm-thick high-density
polyethylene) or natural (e.g., compacted clay). The material chosen is
impervious to water and will largely prevent the leakage of the contaminated
leachate into the groundwater, especially if and when the collection system
fails due to clogging, etc. Since 1991 new landfills in the United States must
have at least six layers of protection between the garbage and the underlying
groundwater! Liners have been developed that consist of bentonite clay—an
excellent sealant that efficiently binds heavy metals, preventing their
migration out of the landfill—sandwiched between two layers of a plastic
such as polypropylene.
Leachate treatment systems must address all the liquid’s major compo-
nents. The treatment of leachate, usually at a sewage treatment plant, is
accomplished by aerobic degradation to rapidly decrease the BOD, some-
times using advanced oxidation methods that employ ozone (Chapter 14). In
the past, collected leachate was often simply returned to the top of the land-
fill, since, during its second percolation through the waste, much of its
organic content would be biologically degraded; however, this practice is now
discouraged in the United States.
Incineration of Garbage
Besides landfilling, the most common way to dispose of wastes, particularly
organic and biological ones, is by incineration—the oxidation by controlled
burning of materials to simple, mineralized products such as carbon dioxide
and water. The primary incentive in the incineration of municipal solid waste
is to substantially reduce the volume of material that must be landfilled. In
the case of toxic or hazardous substances, an even more important goal is to

eliminate the toxic threat from the material. Incineration of hospital wastes
is done to sterilize them as well as to reduce their volume.
Many municipalities throughout the world burn domestic garbage in
incinerators. For example, Japan and Denmark burn more than half their
domestic waste, but the practice is banned in some countries. The combustible
components of the garbage, such as paper, plastics, and wood, provide the fuel
for the fire. The most common domestic MSW incinerators are one-stage mass
burn units; the two-stage modular type is more modern. In the latter, wastes
are placed in the primary chamber and burn at a temperature of about 760°C.
The gases and airborne particles that result from the first stage are then burned
more completely, at temperatures in excess of 870°C, in the secondary combus-
tion chamber. The quantity of waste gases that must later be controlled is
greatly reduced in the two-stage units compared to the one-stage unit,
although the gases are further heated as they exit the one-stage unit to produce
more complete combustion. In some incinerators, an attempt is made to
recover some of the heat of the combustion processes and to convert it to
steam, hot water, or even electricity.
The output from municipal incinerators includes not only the final gases
but also solid residues that amount to about one-third of the initial weight of
the garbage. Bottom ash is the noncombustible material that collects at the
bottom of the incinerator. Fly ash is the finely divided solid matter that is
usually trapped by environmental pollution controls in the stack to prevent it
from being released into the outside air. Much of the ash consists of the inor-
ganic constituents of the waste, which form solids rather than gases even
when fully oxidized. Although fly ash accounts for only 10–25% of the total
ash mass, it is generally the more toxic component, since heavy metals,
dioxins, and furans readily condense onto its small particles. The low density
and small-particle character of the ash make inadvertent dispersal into the
environment a significant risk. Of particular concern are heavy metals in the
ash, which could potentially be leached from it and pollute nearby surface
water and groundwater. For many years, it was common for incinerator ash to
be taken to a hazardous waste landfill. Techniques such as the addition of an
adhesive or melting and vitrification have now been developed to solidify ash
into a leach-resistant material that need not be classified as hazardous waste.
In some countries such as Denmark and the Netherlands, the ash is mainly
recycled into asphalt.
The main environmental concern about incineration is the air pollution
that it generates, consisting of both gases and particulates. The emission
controls on MSW incinerators can control a large fraction, but not all, of
the toxic substances emitted into the air from the combustion process.
About half the capital costs of new incinerators is spent on air pollution
control equipment. Typically, the controls include a baghouse filter, which
is made of woven fabric and is used to filter particulates, especially those
with diameters over 0.5 ␮m, from the flow of output gas. Periodically, the
bags are shaken or the air flow is reversed to collect the fly ash. Also typical
is a gas scrubber, which is a stream of liquid or solid that passes through the
gas stream, removing some particles and gases. If the liquid stream consists of
lime, CaO, and water, which collectively form Ca(OH)2, or if the solid
stream consists of lime, acid gases such as HCl and SO2 are efficiently
removed since they are neutralized to salts by the lime. Heavy metals are also
captured by the alkaline environment, since they form insoluble hydroxides.
In some modern installations, nitrogen oxides are removed by spraying ammo-
nia or urea into the hot exhaust gases (recall the chemistry explained in
Chapter 3). In another new technology used in garbage incinerators, acti-
vated charcoal or lignite coke powder is blown into the exhaust gases, which
are subsequently filtered by baghouse; much of the dioxin, furan, and mer-
cury content of the exhaust gases is removed, since these components adsorb
onto the charcoal or coke surface.
Although public concern has centered on emissions from hazardous
waste incinerators (to be discussed later in this chapter), several U.S. sur-
veys in the 1990s indicated that many more dioxin and furan emissions
emanate from medical waste and municipal waste incinerators than from
hazardous waste ones, although cement kiln units used for hazardous wastes
(discussed in a later section) also make a significant contribution. There
are more than 1000 medical waste incinerators in the United States. Emis-
sions to the air from incinerators are most likely to happen during start-up
and when equipment fails. Because medical waste and backyard barrel
garbage incinerators operate in a start-and-stop mode, they tend to produce
more airborne pollutants per unit mass of incinerated waste than do larger
incinerators. Overall, municipal, backyard, and medical incinerators are
believed to be a major anthropogenic source of both mercury and
dioxins/furans in the U.S. environment and a moderately important source
of cadmium and lead.
Green Chemistry: Polyaspartate—A Biodegradable

Antiscalant and Dispersing Agent
In pipes, boilers, water cooling systems, and other devices that handle water,
scale buildup (Figure 16-4) tends to reduce water flow and heat transfer,
thereby lowering efficiency. In addition, scale may lead to corrosion and dam-
age of these devices. Scale is generally the result of the precipitation of insol-
uble compounds such as calcium carbonate, calcium sulfate, and barium sulfate.
Compounds called antiscalants or dispersants are employed to prevent the
buildup of scale. Whereas antiscalants prevent the formation of scale, disper-
sants allow its formation but maintain the scale in a state of suspension so
that it can simply be washed away.
One of the most commonly used antiscalants and dispersants is the

polyanion polyacrylate or PAC:
999 CH2 999 CH 999
C"O
O n
Short chains of this polymer act as antiscalants while longer chains act as
dispersants. The anionic carboxylate groups, 9 COO, of PAC are able to
form complexes with the cations (such as calcium and barium) normally
found in scale, thus preventing the formation of scale or dispersing it. Glob-
ally, several hundred million kilograms of PAC are produced each year, a
significant portion of which is used as a dispersant or antiscalant. Although
PAC is nontoxic, it is nonvolatile and does not degrade in the environ-
ment. When used for water treatment, it builds up in lakes and streams, or
at best it must be removed in wastewater treatment plants as a sludge and
then landfilled.
To prevent this environmental burden, biodegradable antiscalants and
dispersants such as polyasparate have been developed. Polyaspartate can be
used to replace PAC, but because it under-
goes biodegradation to innocuous products
(such as carbon dioxide and water), it elim-
inates the need for removal in wastewater
treatment plants and disposal in landfills.
Although the performance of polyas-
partate is comparable to that of PAC, its
price was formerly prohibitive. The Donlar
Corporation developed a new synthesis of
polyaspartate that lowered the cost of the
polymer so that it was competitive with
PAC. For this accomplishment, Donlar
won a Presidential Green Chemistry Chal-
lenge Award in 1996. Donlar’s synthesis
(Figure 16-5) begins by heating aspartic
acid (a naturally occurring amino acid) to
produce polysuccinimide, followed by basic
hydrolysis to produce polyaspartate. This
straightforward synthesis is not only eco-
nomically desirable but also environmen-
tally sound. The first step simply requires
heat and yields only water as a by-product,
FIGURE 16- 4 Scale while the second step uses water under
buildup in a water pipe. basic conditions to produce the desired product. The product of this synthe-
(Ward Lopes) sis is generally called thermal polyaspartate (TPA) because of the heat used
O
H polysuccinimide
N C O O
H CH OH H
N C C
H2C OH a
H CH OH heat CH
C N99 n[H2O]
H2C OH H2C b
O C C
aspartic acid O O n
NaOH, H2O
O
C CH2 NH99
999CH NH9999CH C
H2C O C O
C C O
O m nm
30% b cleavage 70% a cleavage
polyaspartate
FIGURE 16-5 Donlar Corporation synthesis of polyaspartate.
in the synthesis. Polyaspartate can also be used in fertilizers (to enhance

uptake of nutrients) and detergents (as builders).
The Recycling of Household

and Commercial Waste
In the past few decades, there has been mounting pressure in developed coun-
tries to reduce the amount of material discarded as waste after a single use.
The incentives here are to conserve the natural resources, including energy,
from which the materials are produced and to reduce the volume of material
that must be buried as garbage, incinerated, etc. The four Rs of such waste
management philosophies are:
• Reduce the amount of materials used (sometimes called source reduction).
• Reuse materials once they are formulated.
• Recycle materials to recover components that can be refabricated.
• Recover the energy content of the materials if they cannot be used in
any other way.
These principles can be and are applied to all types of wastes, including haz-
ardous ones, but in the following discussions we concentrate on their
application to domestic materials, particularly in regard to recycling.
A distinction is often made between preconsumer recycling, which
involves the use of waste generated during a manufacturing process, and post-
consumer recycling, which involves the reuse of materials that have been
recovered from domestic and commercial consumers. The postconsumer
items most often collected for recycling are
• paper (especially newspapers and cardboard),
• aluminum (especially beverage cans),
• steel (especially food cans), and
• plastic and glass containers.
The labor, energy, and pollution costs associated with collecting
the materials, sorting them, and transporting them to facilities where they
can be reused must be considered in any analysis of recycling. In addition,
historically the demand for recycled materials in these categories has been
unstable, with prices swinging wildly in response to changes in supply and
demand. For these and similar reasons, the recycling of paper, glass, and plas-
tics usually needs to be justified on noneconomic and nonenergy grounds—
such as savings in landfill space. The most economically viable forms of
recycling materials usually involve a minimum of chemical reprocessing and
correspond more closely to reuse—e.g., using newspapers to make paper-
board or insulation and reusing glass and plastic containers. Debates still rage
both in the popular press and in the scientific literature as to whether or not
recycling is a worthwhile activity.
The Recycling of Metals and Glass

From the viewpoints of both economics and energy conservation, the recy-
cling of metals makes sense. Virgin metal must be obtained by reduction
of the oxidized form of the element found in nature. The reduction process
requires energy that does not need to be expended again when the metallic
form of the element is recycled.
Consider the reduction of aluminum and iron from the oxide ores.
By definition, the enthalpies of these processes equal the negative of their
enthalpies of formation:
Al2O3 9: 2 Al 32 O2 H° Hf° (Al2O3)

1676 kJ/mol oxide
31 kJ/g metal
Recycling aluminum cans saves 95% of the energy that is needed to produce
Al metal from bauxite ore. Since the energy required for the aluminum reduc-
tion must come in the form of electricity, and since this energy accounts for
about 25% of the cost of its production, it makes good economic sense to recycle
this metal. However, the recycling rate for aluminum cans dropped from
65% in 1992 to only 45% in 2005 in the United States. In contrast, Sweden,
which requires deposits on beverage containers that are refunded upon their
return, collects 85% of aluminum cans. Considerable savings in aluminum
have resulted from the reduction by about one-third of the weight of individ-
ual cans over the last few decades. Aluminum can be recycled endlessly with-
out loss in quality. Globally, recycled aluminum provides about one-third of
the production of the metal. Recycling steel cans saves about two-thirds of the
energy required to produce them from iron ore.
P R O B L E M 16-2
The enthalpy of formation of the principal ore of iron, Fe2O3, is 824 kJ/mol.
Calculate the enthalpy of the reaction in which 1.00 g of metallic iron is
formed from the ore. Given your result, would you expect the price that recy-
cling operators are willing to pay for scrap iron per kilogram to be greater or less
than that for scrap aluminum?
In the case of paper, glass, and plastics, there is no significant change in

the average oxidation number of the principal materials during their transfor-
mation from inexpensive raw material components—wood, sand and lime,
and oil, respectively—to finished products; thus there are no great energy
savings when they are recycled.
Modern, low-polluting, and energy-efficient electric furnaces cannot
handle as high a proportion of used glass as can their more polluting, more
energy-consuming counterparts that use fossil fuels. Consequently, the recy-
cling of too much glass can produce more pollution and use more energy than
would otherwise be the case! In any event, the use of glass containers for bev-
erages has fallen sharply, and their recycling rate dropped from 31% in 1992
to 20% in 2003 in the United States.
The Recycling of Paper

People in developed countries throw away more paper than any of the other
components of municipal solid waste (see Figure 16-1), and it seems an
obvious material to recycle. However, the production of virgin paper, for
example, uses only about one-quarter more energy than the recycling of old
paper. The transportation of waste paper to recycling mills and the de-inking
process itself are heavy consumers of energy. Notwithstanding these consi-
derations, tremendous quantities of paper, especially newsprint, are currently
recycled. Indeed, corrugated paper products are the most intensely recycled
material in North America.
The first step in recycling paper is mechanical dispersal into its compo-
nent fibers in water. Then it is cleaned to remove nonfibrous contaminants,
followed by treatment with sodium hydroxide or sodium carbonate to de-ink it. A
detergent is added to help disperse the pigment, and the ink particles are
removed by washing or flotation on air bubbles, which rise to the top. The
resulting de-inked stock is usually less white than virgin fiber, so the two types
are often blended. If necessary, the whiteness of the recycled stock can be
improved by bleaching, usually with peroxides and hydrosulfites. The used ink,
which is recovered in a sludge with some pulp fibers, is later pressed to remove
water and then can be burned to produce steam for use in mill operations, or
it can be treated to detoxify it. In general, the use and release into the envi-
ronment of materials such as chlorine or other bleaching agents, acids, and
organic solvents are significantly less with the production of recycled paper
than with the creation of the virgin material.
Paper of different types is composed of fibers of very different lengths
(long ones in office paper, short ones in newsprint) that cannot be mixed in
recycling to produce high-quality paper. In addition, there is a limit to the
number of times that paper can be recycled, since with each cycle the pulp
fibers become shorter and so lose some of their integrity. Newsprint can be
recycled back into newsprint about six to eight times. Food boxes and egg car-
tons are usually made from recycled pulp fiber.
From 1985 to 2000, the paper industry in the United States spent almost
$20 billion on the technology and capital investment required to recycle paper;
the ultimate goal was to recycle about half of all paper used in the country.
Indeed, by the mid-2000s, close to half the paper and paperboard products
in North America was being recycled, compared to two-thirds in many
European countries. Recycling rates in the United States in 2003 were 82%
for newspapers, 71% for corrugated boxes, 56% for office paper, 33% for
magazines, and 16% for phone directories.
The issue of whether it is preferable to recycle paper, rather than bury it
in a landfill, is controversial. Since paper is made from wood, which has
grown by extracting carbon dioxide from the atmosphere, landfilling paper
that will never rot is a form of sequestering CO2. Research indicates that
about 70% of the carbon in paper—and more than 97% of that in other wood
products—remains undecomposed in landfills. However, this argument is
negated if any significant fraction of the paper decomposes to emit methane;
nor does it take into account the larger amounts of energy and water required
to produce virgin paper compared to recycled paper.
Perhaps a more clever use of waste paper in the future will be its conver-
sion to fuel ethanol, as discussed in Chapter 8. Paper can be incinerated
directly to recover its energy content, reducing the amount of fossil fuels
burned in power stations. According to an analysis by Britain’s Centre for
Environmental Technology, recycling paper is environmentally superior to
landfilling it but is actually inferior to burning it for its fuel value when all
factors are taken into consideration.
The Recycling of Tires

Another consumer commodity that presents a waste-management headache is
vehicle tires. In North America, about one 10-kg rubber tire per person per
year on average is discarded; thus about one-third of a billion tires are added to
the supply of approximately 3 billion tires presently stored in mountainous
piles, awaiting ultimate disposal! Because the tires are made primarly from oil
and consequently are flammable, tire fires in these huge piles are not uncom-
mon and produce tremendous amounts of smoke, carbon monoxide, and toxins
such as polynuclear aromatic hydrocarbons (PAHs) and dioxins (Chapters 11
and 12). The fires are difficult to extinguish because of air pockets in and
between the tires.
There have been efforts to use tires either as fuel or as a filler for asphalt,
but currently such applications consume only about 10% of the tires that are
discarded annually. Some used tires are also utilized for their rubber content,
to produce landscaping products.
A number of attempts have been made to commercially reprocess shred-
ded scrap tires by pyrolysis—the thermal degradation of a material in the
absence of oxygen. The resulting products are low-grade gaseous and liquid
fuels and a char containing minerals and a low-grade version of the material
called carbon black, which can be further treated and converted into activated
carbon (Chapter 14). It may eventually be possible to convert the liquid com-
ponent into high-grade char, thereby making the process economically prof-
itable. The “rubber” in tires consists of about 62% of a hydrocarbon polymer
and 31% of carbon black—added to strengthen the tires and reduce wear—so
there is a ready market for the latter. Using the liquid component as a fuel is
problematic because of its high content of aromatic hydrocarbons.
The Recycling of Plastics

One of the triumphs of industrial chemistry in the twentieth century was the
development of a wide variety of useful plastics. All plastics are composed at
the molecular level of polymeric organic molecules, very long units of matter
in which a short structural unit is repeated over and over again. All the raw
materials (except chlorine) from which the plastics are currently made are
obtained from crude oil.
Conceptually, the simplest organic polymer is polyethylene (or poly-

ethene), the molecules of which are composed of many thousands of
¬ CH2 ¬ units bonded together:
H H H H H H
9C9C9C9C9C9C9
H H H H H H
This polymer is prepared by combining many molecules of ethylene
(ethene) (hence the name) and is an example of an addition polymer.
Depending on exactly how the polymerization takes place, either low-density
polyethylene (LDPE) (the plastic given the recycling number 4) or high-
density polyethylene (HDPE) (the cloudy white or opaque plastic given the
recycling number 2) is formed.
There are several other addition polymers similar to polyethylene in
which one (or more) of the four hydrogen atoms in each ethylenic
¬ CH2 ¬ CH2 ¬ unit is replaced by a group or atom X, giving the polymer
H H H H
9C9C9C9C9
H X H X
If the X attached to every second carbon atom in each chain is chlorine, then
the clear (or blue-tinted) polymer polyvinyl chloride (PVC) (recycling num-
ber 3) is obtained. If the substituent X is a methyl group, we have polypropylene
(recycling number 5), and if it is a benzene ring we have polystyrene (recycling
number 6). The plastics formed from all these polymers are used extensively in
packaging, as indicated by the original uses listed in Table 16-1.
The other plastic that is commonly recycled (number 1) is the clear plas-
tic poly(ethylene terephthalate) (PET). Its structure is a chain of two CH2
units alternating with a unit of the organic molecule terephthalic acid. PET is
used in the form of film (for magnetic tape as well as photographic film), fiber,
and molded resin (e.g., plastic bottles).
In the last quarter of the twentieth century, plastics became the symbol
of a throwaway society, since much of the product—especially that used in
packaging—was designed to be used once and then discarded. Many environ-
mentalists believed that waste plastic was a major culprit in the garbage cri-
sis. Indeed, molded plastics take up a greater percentage of volume in landfills
than their percentage by mass because their densities are low, although they
are eventually compressed by the weight of the materials piled on them, as
well as by compacting machinery before they are placed in the landfill. Plas-
tics are the second most common constituent of municipal garbage, following
TABLE 16-1 Commonly Recycled Plastics
Plastic Recycling Acronym and Original Use Recycle

Number Name of Plastic Examples Use Examples
1 PET Beverage bottles; food and Carpet fibers; fiber-

Poly(ethylene cleanser bottles; drugstore fill insulation; non-
terephthalate) product containers food containers.
2 HDPE Milk, juice, and water Oil and soap bottles;
High-density bottles; margarine tubs; trash cans; grocery
polyethylene crinkly grocery bags bags; drain pipes
3 PVC (or V) Food, water, and chemical Drainage pipes; floor-
Polyvinyl chloride bottles; food wraps; blister ing tiles; traffic cones
packs; construction material
4 LDPE Flexible bags for trash, milk, Bags for trash and
Low-density and groceries; flexible wraps groceries; irrigation
polyethylene and containers pipes; oil bottles
5 PP Handles, bottle caps, lids, Auto parts; fibers;
Polypropylene wraps, and bottles; food tubs pails; trash containers
6 PS Foam cups and packaging; Insulation; toys; trays;
Polystyrene disposable cutlery; packaging “peanuts”
furniture; appliances
7 Other Various Plastic “timber”:
posts, fencing, and
pallets
paper and cardboard by quite a margin. The per capita annual use of plastics
in North America is approximately 30 kg.
For a number of reasons, including the fact that landfills, especially
throughout Europe, are reaching their capacity and that many citizens in
developed countries are opposed to their incineration, many plastics are now
collected from consumers and recycled. As of the mid-1990s, over 80% of the
mass of plastics recycled in the United States consisted of PET and HDPE, in
approximately equal amounts, with LDPE the only other one of significance.
Some countries, such as Sweden and Germany, have made manufacturers
legally responsible for the collection and recycling of the packaging used in
their products.
There is little doubt that the public in many developed countries has
embraced recyling of plastics. As of the late 1990s, about half the urban
communities in the United States had curbside recycling programs that
included plastics. However, the U.S. recycling rate for PET soda bottles
dropped from a high of 40% in 1995 to only 22% (of the annual total of about
25 billion, corresponding to about 100 per capita) in 2004. As in the case of
aluminum, Sweden achieves a much higher recycling rate (80%) by requiring
refundable deposits on plastic bottles. The majority of recycled PET bottles
are used to make fiber for carpet, strapping, and film, though 14% of it is used
in food and beverage containers. Only a fraction of the demand for PET bottles
is met by the current supply.
HDPE containers have achieved a somewhat higher recycling rate (26%)
than PET ones in the United States, presumably because they are used for
milk and for nonfood products that are primarily found at home. Recycled
HDPE products include nonfood bottles, plastic garden products such as pots,
and plastic lumber.
About 150 polyethylene carrier bags are produced annually for every
man, woman, and child on the planet. About 80% of them are reused at least
once, in kitchens as trash bags or by dog owners. Although they constitute
less than 1% of garbage sent to landfills, and their incineration can recover
the energy of the oil used to make them, they are highly visible forms of pol-
lution when allowed to blow around and collect on streets and beaches. In
addition, plastic bags can have a devastating effect on marine animals such as
turtles and whales, whose stomachs can be blocked if they inadvertently con-
sume the bags. Although plastic bags are collected for recycling in some
locales, countries such as Denmark, Ireland, and Taiwan have imposed a tax
on them in order to discourage their use.
There has been much resistance to plastics recyling in some quarters,
including many in the plastics industry. Their argument is that virgin plas-
tics are a low-cost product that is made from a relatively low-cost raw
material (oil). The input energy for making plastics is very small compared
to that used for making aluminum or steel from its raw materials. The cost
of cleaning used plastic and converting it back into its monomers so that it
can be polymerized again is substantial, compared to the current cost of oil.
Some executives in the plastics industry believe that the best disposal
method for plastics is simply to burn them and use the heat energy pro-
vided, especially given the fact that there is little objection by the public
to simply burning most (over three-quarters) of the oil produced—in vehi-
cles, domestic furnaces, and power plants. In addition, experiments indi-
cate that the presence of plastics makes the other materials in domestic
garbage burn more cleanly and reduces the need for supplemental fossil
fuel to be added. Although plastics account for less than 10% of the mass
of garbage, they make up more than one-third of its energy content.
Environmentalists counter these arguments by pointing out that if envi-
ronmental impacts were to be included in determining the cost of virgin
materials, recycled plastic would be the cheaper choice. Also, the combustion
of some plastics, notably PVC, produces dioxins and furans and releases
hydrogen chloride gas.
Ways of Recycling Plastics

There are four ways to recycle plastics, one physical and three chemical:
1. Reprocess the plastic (a physical process) by remelting or reshaping.
Usually the plastics are washed, shredded, and ground up, so that clean, new
products can then be made.
2. Depolymerize the plastic to its component monomers by a chemical or
thermal process so that it can be polymerized again.
3. Transform the plastic chemically into a low-quality substance from
which other materials can be made.
4. Burn the plastic to obtain energy (energy recycling).
Examples of the reprocessing option include the production of carpet
fibers from recycled PET; of plastic trash cans, grocery bags, etc. from recycled
HDPE; and of CD cases and office accessories such as trays and rulers from
recycled polystyrene. Further examples of reprocessing are listed for each cat-
egory of packaging plastic in the last column of Table 16-1.
The depolymerization option can be employed with PET and other
polymers of the ¬ A ¬ B ¬ A ¬ B ¬ A ¬ B ¬ type, in which units of
types A and B alternate in the structure. These condensation polymers
are produced by combining small molecules that contain A and B units.
During the polymerization process, A and B form the polymer and the
remaining parts of the molecules combine. For example, in the production
of PET, the molecule methanol, CH3OH, is formed from the OH unit of
one component and the CH3 of the other. In the chemical depolymeriza-
tion process, a catalyst and heat are applied to a mixture of methanol and
the plastic to reverse the polymerization process and recover the original
components:
CH3!A! CH3 HO!B! OH CH3!A! CH3 HO!B! OH . . .

polymerization
depolymerization
CH3!A!B!A!B!A . . . !A!B!A!B! OH many CH3OH
For PET, B is ¬ CH2 ¬ CH2 ¬ and A is
O O
9O9C C9O9
Physical recycling of PET is currently more economically viable than chemi-

cal reprocessing.
One of the difficulties in depolymerization of plastics is that the organic
and inorganic compounds that are often added to the original polymer to
modify the physical properties of the plastic, such as its flexibility, must be
removed before the monomers can be reused.
For many addition polymers, it is difficult to devise a process by which
the original monomers can be re-formed. For example, the monomer yield for
the thermal depolymerization of polystyrene is about 40%, but it is close to
zero for polyethylene because the chain will be broken at random positions
and will not exclusively produce two-carbon units.
Examples of the transformation option are:
• Reductive processes such as the production of synthetic crude oil by
hydrogenation of plastics or by heating them to a high temperature to
“crack” the polymer molecules, a process that can be used even with mixed
plastics. The pyrolysis of polyethylene to monomers that can be converted
to lubricants has also been proposed.
• Oxidative processes such as the gasification of plastics by adding oxygen
and steam to produce synthesis gas (a mixture of hydrogen and carbon
monoxide, discussed in Chapter 8).
Green Chemistry: Development

of Recyclable Carpeting
In the United States, 2.3 billion square yards of carpeting were shipped in
2004. This is enough to cover the entire surface area of Washington, D.C.,
11 times, or about 3/4 of the state of Rhode Island. The Carpet America
Recovery Effort (CARE) reports that in 2005, 89% of used carpeting was
disposed of in landfills, 3% was incinerated in cement kilns, and only 7% was
recycled. Carpeting is not biodegradable, takes up valuable and rapidly
declining landfill space, and is ultimately made from petroleum, a nonrenew-
able resource. As landfill fees escalate—estimates indicate they will double
every five years—and the costs of transporting, installing, and replacing
carpeting rise, the demand for an economical and environmentally responsi-
ble alternative to landfilling of this product has increased.
The two major components of carpeting are the backing and the face
fiber. Since the 1970s, PVC has been the material of choice for carpet
backing. Environmental and health concerns about PVC include vinyl
chloride (the monomer used to produce PVC) and phthalate plasticizers.
Vinyl chloride, a known carcinogen, is volatile. Some believe that this
compound outgases from the polymer, whereas others argue that the high
temperatures used to process PVC should eliminate virtually all of the
volatile monomer. Phthalates, which are added to PVC to make it more
flexible, migrate out of the polymer and have become widely dispersed in
the environment. The growing concern over the effects of phthalates on
the human reproductive system was discussed in Chapter 12. In addition, as
also discussed in Chapter 12, when PVC burns, it produces toxic by-products
including dioxins, furans, and hydrochloric acid.
Recycling is now commonplace when it comes to paper, glass, and plastic.
However, most of us do not think of recycling carpeting. In the United
States, only 7% of carpeting is recycled, in part because the PVC backing
interferes with the recycling process. Shaw Industries won a Presidential
Green Chemistry Challenge Award in 2003 for its development of a new
type of carpeting that allows for closed-loop recycling, i.e., recycling of used
carpeting back into carpeting with little loss of material. This new type of
carpeting, known as EcoWorx, employs polyolefin backing and nylon-6 fiber.
In addition to lending itself to recycling, the polyolefin backing has low tox-
icity and eliminates the significant environmental and health concerns
related to PVC.
The process of recycling EcoWorx carpeting begins with grinding the used
carpeting and separating the heavier particles (the polyolefin backing) from
the lighter ones (the nylon-6 fibers) with a stream of air (a process known as
elutriation). The polyolefin particles can then be reused in the extrusion process
to produce new backing. The nylon-6 is depolymerized to its monomer (capro-
lactam) and repolymerized to virgin nylon-6 fibers. The fibers are then used to
form new carpeting, completing the cycle. Both the backing and the fibers of
EcoWorx carpeting can be used again and again to form new carpeting.
There are several additional environmental advantages of EcoWorx, as
well as economic advantages:
• Recycling requires no additional petroleum feedstocks; this benefits not
only the environment but also the economic bottom line.
• Recycling reduces the amount of landfill space needed.
• The polyolefin-backed carpeting is 40% lighter in weight than carpeting
backed with PVC. More carpeting can be shipped by truck within weight
limits, thus lowering fuel consumption, cost, and pollution.
• The use of polyolefins eliminates the energy-intensive heating process
required for PVC. Again, this results in lowering fuel consumption, cost,
and pollution.
• In carpet backing (including PVC backing), significant amounts of
inorganic fillers are used to provide loft and bulk. Traditionally, virgin
calcium carbonate was employed for this purpose. EcoWorx contains
60% class C fly ash (a waste by-product from the burning of lignite or sub-
bituminous coal) as a filler. Using fly ash as a filler utilizes an unwanted
by-product and precludes the use of a virgin chemical.
Returning goods for recycling is often a significant barrier to recycling.
To overcome this difficulty, Shaw developed a system for returning the car-
peting at the end of its useful life, at no cost to the consumer.
Life Cycle Assessments

One technique used in minimizing the production of wastes and in pollution
prevention is the life cycle assessment (or analysis), LCA—an accounting of
all the inputs and outputs in a product’s life, from raw material extraction to final
disposal. This cradle-to-grave analysis for a product (or process) can be used to
identify the types and magnitudes of its environmental impacts, including both
the natural resources used and the pollution produced.
The results of a life cycle assessment can be used in two ways:
• to identify opportunities within the life cycle to minimize the overall
environmental burden of a product, and
• to compare two or more alternative products to determine which is
more environmentally friendly.
An example of the first use is in the production of motor vehicles; the life
cycle and the most important inputs and outputs are illustrated in Figure 16-6.
Energy
Energy
Production of
Energy Natural
maintenance
resources
Crude oil products
production
Fuel
production
Additives
production
Steel
production
Natural
resources Energy Energy
Aluminum
production
Vehicle End of
Use of vehicle
manufacturing vehicle life
Plastics
production
Recycled Waste Reused parts,
materials recycled
Other and waste materials,
materials and waste
production*
*For example, rubber, lead, glass, paints, and coolants.
FIGURE 16-6 Important input and output components in life cycle assessments of motor
vehicles. [Source: M. Freemantle, “Total Life-Cycle Analysis Harnessed to Generate ‘Greener’ Automo-
biles,” Chemical and Engineering News (27 November 1995): 25.]
In designing new cars, life cycle assessments are used to help minimize
pollution while maintaining economic viability. The analysis is particularly
useful for identifying new environmental burdens that would arise if others
are decreased. For example, vehicles could be made much lighter by increased
use of plastics; however, the types of plastics used are difficult to recycle and
would increase the eventual burden of solid waste in landfills.
Soils and Sediments

The contamination of soil by wastes is not solely a phenomenon of modern
times. In Roman times, metal ores were mined and the ores smelted, pollut-
ing the surrounding countryside. The production of materials and chemicals
in Europe even at the start of the Industrial Revolution produced substantial
pollution. However, the extent of contamination and the hazard from dis-
carded materials expanded greatly in the last century, particularly in the
period after World War II.
We begin this section by discussing the nature of soil and of sediments.
Basic Soil Chemistry

Soils are composed roughly equally of solid particles, about 90% of which are
inorganic in nature and the rest organic matter, and of pore space, about half
of which is air and half water. The inorganic particles are residues of weath-
ered rock; chemically they are mainly silicate minerals. At the atomic level,
these minerals consist of polymeric inorganic structures in which the funda-
mental unit is a silicon atom surrounded tetrahedrally by four oxygen atoms.
Since these oxygen atoms are in turn each bonded to another silicon, etc.,
the resulting structure is an extended network. There are many variations on
the silicate structural theme. Some networks have exactly twice as many oxy-
gens (formally, O2) as silicons (formally, Si4) and correspond to electrically
neutral SiO2 polymers. In others, some of the tetrahedral sites are occupied by
aluminum ions, Al3, instead of Si4; the extra negative charge in these net-
works is neutralized by the presence of other cations such as H, Na, K,
Mg2, Ca2, and Fe2. Some common silicon–oxygen structural units are
illustrated in Figure 16-7.
Over time, the weathering of the silicate minerals from rocks can involve
chemical reactions with water and acids in which ion substitution occurs.
Eventually, these reactions yield substances that are important examples of
the class of soil materials known as clay minerals. A mineral having a parti-
cle size less than about 2 ␮m is by definition a component of the clay fraction
of soil.
In addition to clay, there are several other soil types; the definition of
each type depends on particle size, as indicated in Figure 16-8. Notice the
factor-of-10 increase in size with each transition in type: The upper boundary
SiO44– Si2O76– Si3O96– Si6O1812–
End
view
(SiO32–)n (Si4O116–)n
(Si4O104–)n (SiO2)n
FIGURE 16-7 The common structural units in silicate minerals. Dark circles represent silicon atoms; open
circles represent oxygens. [Source: R. W. Raiswell, P. Brimblecombe, D. L. Dent, and P. S. Liss, Environmental Chemistry
(London: Edward Arnold Publishers, 1980).]
Sand
FIGURE 16-8 The soil
Clay Silt Gravel particle size classification
system of the International
Fine Coarse
Society of Soil Science.
[Source: G. W. vanLoon and
2 m 20 m 200 m 2000 m
S. J. Duffy, Environmental
(2.0 mm)
Chemistry (Oxford: Oxford
Soil Nonsoil
for silt is 10 times that for clay, that for fine sand is 10 times that for silt, etc.
Because the particle size of sand is large, it has a relatively low density and
water runs through it easily. In contrast, soils composed of clay are dense and
have poor drainage and aeration, since the clay particles form a sticky mass
when wet, in contrast to sand and silt particles, which do not stick to each
other. The best agricultural soils consist of a combination of soil types. The
range of element content for major and minor elements in the mineral com-
ponent of soil is given in Table 16-2.
Clay particles act as colloids in water. Because the clay particles are much
smaller than those of sand or silt, their total surface area per gram is thou-
sands of times larger. Consequently, most important processes in soil occur on
the surface of colloidal clay particles.
Particles of clay possess an outer layer of cations that are bound electro-
statically to an electrically charged inner layer, as illustrated in Figure 16-9.
The most common cations in soil are H, Na, K, Mg2, and Ca2.
Depending on the concentration of cations in the water surrounding the clay
Element Content of the Mineral Components

TABLE 16-2 of Soils
Major Elements (%) Minor Elements (ppm)
Si 30–45 Zn 10–250
Al 2.4–7.4 Cu 5–15
Fe 1.2–4.3 Ni 20–30
Ti 0.3–0.7 Mn ~400
Ca 0.01–3.9 Co 1–20
Mg 0.01–1.6 Cr 10–50
K 0.2–2.5 Pb 1–50
Na Trace–1.5 As 1–20
Source: G. W. vanLoon and S. J. Duffy, Environmental Chemistry (Oxford: Oxford University
Press, 2000).
Ca2 K
Kⴚ ⴚ ⴚK
ⴚ ⴚ ⴚ Mg2
ⴚ Kⴚ
ⴚ ⴚK
Ca2ⴚ Clay ⴚ Na
K ⴚ Clay ⴚ K
Na ⴚ
K Cl Ca2, Mg2, H,
particle ⴚ H Kⴚ particle ⴚ K
Hⴚ ⴚ

Na , and Cl
ⴚ K ⴚ ⴚ
ⴚ ⴚ 2
ⴚ Ca K ⴚ ⴚ K
Mg2
K K
FIGURE 16-9 Ion-exchange equilibria on the surface of a clay particle. The addition of
K ions to the soil water displaces the exchange equilibria to the right, whereas removal of
K ions from solution displaces it to the left. [Source: R.W. Raiswell, P. Brimblecombe, D. L. Dent,
and P. S. Liss, Environmental Chemistry (London: Edward Arnold Publishers, 1980).]
particle, the cations on the particle are capable of being exchanged for them.
For example, in water rich in potassium ions but poor in other ions, K ions
will displace the ions bound to the surface of the clay particle (see Figure 16-9).
If, on the other hand, the soil is acidic—i.e., rich in H ions—the metal ions
on the surface will be displaced by H ions and the previously bound metal
ions will enter the aqueous phase. Generally, the greater the positive charge
on a cation, the more strongly it binds to the particle. Heavy metals dissolved
in soil water are often bound to the surface of clay particles.
In addition to minerals, the other important components of soil are
organic matter, water, and air. The proportion of each component varies
greatly from one soil type to another. The organic matter (1–6%), which
gives soil its dark color, is primarily a material called humus. Humus is
derived principally from photosynthetic plants, some components of which
(such as cellulose and hemicellulose) have previously been decomposed by
organisms that live in the soil. The undecomposed plant material in humus is
mainly protein and lignin, both polymeric substances that are largely insolu-
ble in water. A significant amount of the carbon in lignin exists in the form
of six-membered aromatic benzene rings connected by chains of carbon and
oxygen atoms (see Figure 11-4). Much of the organic matter in soil also con-
sists of colloidal particles.
As a result of the partial oxidation of some of the lignin, many of the
resulting polymeric strands contain carboxylic acid groups, ¬ COOH. This
dark-colored portion of humus consists of humic and fulvic acids and is
soluble in alkaline solutions due to the presence of the acid groups. By defini-
tion, humic acid is insoluble in acid solution, whereas fulvic acid is soluble.
The humic acid is less soluble in acid than the fulvic not only because its
molecular weight is much greater (100 to 1000 times greater), but also
because its oxygen content is lower, so there are fewer ¬ OH groups per car-
bon to form hydrogen bonds with the water. The acid groups are often
adsorbed onto the surfaces of the clay minerals, to an extent dependent on
the distribution of surface charge on the particles. Humic and fulvic acids
form colloids that are hydrophilic, whereas those of clay are hydrophobic.
Generally speaking, nonpolar organic molecules are more strongly attracted
to the organic matter in soil than to the surfaces of particles derived from
minerals.
Since some of the carbon in the original plant material has been trans-
formed to carbon dioxide and thus lost as a gas to the surroundings, humus
has relatively more nitrogen than the original plants; its other main compo-
nents are carbon, oxygen, and hydrogen. Due to decomposition processes
occurring in the organic component of soil, the O2 content of soil air is often
only 5–10% rather than 20%, and its CO2 concentration is often several
hundred times that in the atmosphere.
P R O B L E M 16-3
The percentage composition of a typical fulvic acid is 50.7% carbon by mass,
45.1% oxygen, and 4.22% hydrogen. Derive the (simplest) empirical formula
for the substance.
The Acidity and Cation-Exchange Capacity of Soil

If the soil at the surface contains minerals with elements in a reduced state,
their oxidation by atmospheric oxygen can produce acid. An example is the
oxidation of sulfur in pyrite, discussed as acid mine drainage in Chapter 13.
Acid rain, of course, provides another source of acidity in certain areas
(Chapter 4).
Quantitatively, the ability to exchange cations is expressed as the soil’s
cation-exchange capacity, CEC, which is defined as the quantity of cations
that are reversibly adsorbed per unit mass of the (dry) material. The quantity
of cations is given as the number of moles of positive charge (usually expressed
as centimoles or millimoles), and the soil mass is usually taken to be 100 g or
1.00 kg. Typical values of the CEC for common clay minerals range from 1 to
150 centimoles per kilogram (cmol/kg). The CEC values are determined in
large part by the surface area per gram of the mineral. CEC values for the
organic component of soil are high, due to the large number of ¬ COOH
groups that can bind to and exchange cations; e.g., the CEC of peat can be as
high as 400 cmol/kg.
P R O B L E M 16-4
The CEC for a soil sample is found to be 20 cmol/kg. What is the CEC value
for this sample in units of millimoles per 100 grams?
Biologically, the exchange of cations by soils is the mechanism by which

the roots of plants take up metal ions such as potassium, calcium, and
magnesium. Although the roots release hydrogen ions to the soil in

exchange for the metal ions, this is not the main reason why soil in which
plants grow is often somewhat acidic. Most of the acidity is due to metabolic
processes involving the roots and microorganisms in the soil, which result in
the production of carbonic acid, H2CO3, and of weak organic acids.
Rainwater that is acidic releases base cations from soil particles by
exchanging them for H ions. The acidity of water flowing through the soil
stays low for this reason. However, once the base cations have been
exhausted, aluminum ions are released, as discussed in Chapter 4. It is now
known that in the past, base cations from dust particles, especially those con-
taining calcium and magnesium carbonates, neutralized some of the acidity in
precipitation; but along with sulfur dioxide, their emission from industrial
sources has been curtailed in recent decades.
The pH of soil can vary over a significant range for a variety of reasons.
For example, soils in areas of low rainfall but high concentrations of the
soluble salt sodium carbonate, Na2CO3, become alkaline due to the (hydro-
lysis) reaction of the carbonate ion, CO32, with water, as discussed in
Chapter 13.
Soils that are too alkaline for agricultural purposes can be remediated
either by the addition of elemental sulfur, which releases hydrogen ions as it
is oxidized by bacteria to sulfate ion, or by the addition of the soluble sulfate
salt of a metal, e.g., iron(III) or aluminum, which reacts with the soil’s water
to extract hydroxide ions and thereby release hydrogen ions:
2 S(s) 3 O2 2 H2O 9: 4 H 2 SO42

Fe3 3 H2O 9: Fe(OH)3(s) 3 H
The pH of water present in the soil is determined by the concentration

of hydrogen and hydroxide ions. However, soil has reserve acidity due to
the large number of hydrogen atoms in the ¬ COOH and ¬ OH groups in
the organic fraction and on the cation-exchange sites on minerals that are
occupied by H ions. In other words, soils act as weak acids, retaining their
H ions in a bound condition until acted upon by bases. Thus the pH of
soil tends to be buffered against large increases in pH, since this bound
hydrogen ion can be slowly released into the aqueous phase. In the process
of liming, which is the addition of salts such as calcium carbonate to soil,
carbonate ions neutralize acids present in the uppermost soil zones, pro-
ducing carbon dioxide and water. Once this process has occurred, calcium
ions can replace hydrogen ions in the organic matter or clays. The addi-
tional carbonate ions that enter the aqueous phase combine with the
newly released H ions, again to produce weakly acidic carbonic acid,
which dissociates into carbon dioxide gas and water. Thus liming is a pro-
cedure by which the pH of a soil can be raised somewhat, and it is the prac-
tical method by which acidic soils can be remediated.
Soil Salinity
In hot, dry climates, salts and alkalinity tend to accumulate in soil since there
is little rainfall to leach ions from it. In contrast to other climates, the net
movement of water in arid climates is upward rather than downward in the
soil: Water evaporation and loss by transpiration of plants exceeds rainfall.
The salts that accompany the upward migration of water remain at or near
the surface when the water has escaped. Salt accumulation at the surface also
occurs in semiarid regions due to the use of poor-quality irrigation water,
whose salt content remains after the water has evaporated.
Ions are also liberated at the surface of soil in the weathering of otherwise
insoluble minerals. A simple example is the reaction of olivine:
Mg2SiO4 4 H2O 9: Si(OH)4 2 Mg2 4 OH
Additional hydroxide ion is produced when the silicate ion, SiO44, produced
by mineral weathering reacts as a strong base with water.
As a general rule, hydrolysis (reaction with water) of silicate minerals at
the surface produces cations and hydroxide ions. In nonarid climates, the
hydroxide is neutralized by acids that are naturally produced in the soil
(see later section), but this does not occur in arid regions. There is very lit-
tle organic matter in the soils of arid areas. The hydroxide reacts with atmo-
spheric carbon dioxide that dissolves in water to produce bicarbonate and
carbonate ions:
OH CO2 9: HCO3
HCO3 9: H CO32
Consequently, bicarbonate and carbonate salts accumulate in arid soils. If
the predominant cations in the soil are calcium and magnesium, most of the
carbonate ion will be locked away as their insoluble carbonate salts. However,
if the predominant cations are sodium and potassium, the soil when moist
will have a high pH, since the carbonate salts of these ions are soluble and the
free CO32 will act as a base:
CO32- + H2O Δ HCO3- + OH-
Increasing soil salinity is a major problem in Australia, especially in
regions where wheat and other shallow-rooted crops have replaced natural,
long-rooted vegetation. This replacement, plus irrigation of crops including
rice and cotton, has resulted in a rise of the water table and, with it, the salt
that was formerly deep in the soil.
Sediments
Sediments are the layers of mineral and organic particles, often fine-grained,
that are found at the bottom of natural water bodies such as lakes, rivers, and
FIGURE 16-10 U.S. water-

sheds where contaminated
sediments may pose envi-
ronmental risks. [Source:
U.S. EPA, in B. Hileman, “EPA
Finds 7% of Watersheds Have
Polluted Sediments,” Chemical
and Engineering News
(26 January 1998): 27.]
oceans. The ratio of minerals to organic matter in sediments varies consider-

ably, depending on location. Sediments are of great environmental impor-
tance because they are sinks for many chemicals, especially heavy metals and
organic compounds such as PAHs and pesticides, from which they can be
transferred to organisms that inhabit this region. Thus the protection of
sediment quality is a component of overall water management.
The map in Figure 16-10 shows watersheds in the continental United
States where sediments are sufficiently contaminated to pose environmental
risks. According to a U.S. EPA report, 7% of all watersheds pose a risk to peo-
ple who eat fish from them and to the fish and wildlife themselves. The two
pollutants found at high levels most frequently at contaminated sites are
PCBs and mercury, although DDT (and its metabolites) and PAHs were also
found at high concentrations at many sampling stations.
The transfer of hydrophobic organic pollutants to organisms may proceed
by intermediate transfer to pore water, which is the water present in the
microscopic pores that exist within the sediment material. Organic chemicals
equilibrate between being adsorbed on the solid particles and being dissolved
in the pore water. For this reason, pore water is often tested for toxicity in
determining sediment contamination levels.
The Binding of Heavy Metals to Soils and Sediments

The ultimate sink for heavy metals, and for many toxic organic compounds as
well, is deposition and burial in soils and sediments. Heavy metals often accu-
mulate in the top layer of the soil and are therefore accessible for uptake by
the roots of crops. For these reasons, it is important to know the nature of
these systems and how they function.
Humic materials have a great affinity for heavy-metal cations and extract
them from the water that passes through by the process of ion exchange. The
binding of metal cations occurs largely by the formation of complexes with the
metal ions by ¬ COOH groups in the humic and fulvic acids. For example, for
fulvic acids the most important interactions probably involve a ¬ COOH
group and an ¬ OH group on adjacent carbons of a benzene ring in the polymer
structure, where the heavy-metal M2 ion replaces two H ions:
O
C
O
M heavy metal
M
O
Humic acids normally yield water-insoluble complexes, whereas those of
smaller fulvic acids are water-soluble.
P R O B L E M 16-5
Draw the structure that would be expected if a dipositive metal ion M2 were
to be bound to two ¬ COO- groups on adjacent carbons in a benzene ring.
Heavy metals (Chapter 15) are retained by soil in three ways:

• by adsorption onto the surfaces of mineral particles,
• by complexation by humic substances in organic particles, and
• by precipitation reactions.
The precipitation processes for mercury and cadmium ions involve the for-
mation of the insoluble sulfides HgS and CdS when the free ions in solution
encounter sulfide ion, S2. Significant concentrations of aqueous sulfide ion
occur near lake bottoms in summer months when the water is usually oxygen-
depleted, as discussed in Chapter 13. However, the total concentration of mer-
cury in soil water can exceed the limits set by the solubility product of HgS
because some of the mercury will take the form of the moderately soluble
molecular compound Hg(OH)2 and does not participate in the equilibrium
with the sulfide.
In acidic soils the concentration of Cd2 can be substantial, since this
ion adsorbs only weakly onto clays and other particulate materials. Above
a pH of 7, however, Cd2 precipitates as the sulfide, carbonate, or phosphate,
since the concentration of these ions increases with increasing hydroxide ion
levels. Thus the liming of soil to increase its pH is an effective way of tying up
cadmium ion and thereby preventing its uptake by plants.
Like many other chemicals, heavy-metal ions are often adsorbed onto
the surfaces of particulates, especially organic ones that are suspended
in water, rather than simply being dissolved in water as free ions or as
complexes with soluble biomolecules such as fulvic acids. The particles
eventually settle to the bottom of lakes and are buried when other sediments
accumulate on top of them. This burial represents an important sink for
many water pollutants and is a mechanism by which the water is cleansed.
Before they are covered by subsequent layers of sediments, however, freshly
deposited matter at the bottom of a body of water can recontaminate the
water above it by desorption of the chemicals, since adsorption and desorption
establish an equilibrium. Furthermore, the adsorbed pollutants can enter the
food web if the particles are consumed by bottom-growing and -feeding
organisms.
Just as the total concentration of organic material in sediments may not
be a good measure of the amounts that are biologically available, the same is
true for the levels of heavy-metal ions present. Different sediments with the
same total concentration of the ions of a heavy metal can vary by a factor of
at least 10 in terms of the toxicities to organisms arising from the metal.
This variation occurs principally because sulfides in the sediments control the
availability of the metals. If the concentration of sulfide ions exceeds the total
of that of the metals, virtually all the metal ions will be tied up as insoluble
sulfide salts such as HgS, CdS, etc. and will be unavailable biologically at
normal pH values. However, if the sulfide concentration is less than that of
the metals, the difference is biologically available. The sulfide ion that is
available to complex with metals is the amount that will dissolve in cold
aqueous acid and is termed acid volatile sulfide, AVS. Industrially polluted
sediments may have AVS concentrations of hundreds of micromoles of sulfur
per gram, whereas uncontaminated sediments from oxidizing environments
can have values as low as 0.01 ␮mol/g.
Although mercury in the form of Hg2 is firmly bound to sediments and
does not readily redissolve into water, environmental problems have arisen
in several bodies of water due to the conversion of the metal into methyl-
mercury and its subsequent release into the aquatic food web. The overall
cycling of mercury species among air, water, and sediments was illustrated in
Figure 15-1.
As previously discussed, anaerobic bacteria methylate the mercuric ion to
form Hg(CH3)2 and CH3HgX, which then rapidly desorb from sediment
particles and dissolve in water, thereby entering the food web. Although the
levels of methylmercury dissolved in water can be extremely low (of the
order of hundredths of a part per trillion), a biomagnification factor of 108
results in ppm-range concentrations in the flesh of some fish. The devastating
Lead (ppm)
0 100 100 200 200 300 400
0 1980
1960
10 Lead 1940
Mercury 1920
20 1900
1880/1860
30 1840
Depth (cm)
1820
40
50
FIGURE 16-11 Lead and
60 mercury concentrations
in the sediments of Halifax
70 Harbor versus depth (and
therefore year of deposit).
80 [Source: D. E. Buckley,
0 0.5 1.0 1.5
“Environmental Geochemistry
Mercury (ppm) in Halifax Harbour,” WAT on
Earth (1992): 5.]
consequences of methylmercury poisoning have already been described

(Chapter 15).
Excavation and analysis of the sediments at the bottom of a body of
water can yield a historical record of contamination by various substances.
For example, the curves in Figure 16-11 show the levels of mercury and of
lead in the sediments of the harbor in Halifax, Nova Scotia, as a function
of depth and therefore of year. For decades raw sewage has been dumped into
this harbor; consequently, its sediments are a historical record of the levels
of pollutants in sewage. The metal pollution peaked about 1970, having
begun to increase dramatically about 1900. These trends are also typical of
heavy-metal levels in other water bodies, such as the Great Lakes; the char-
acteristic decreases of the past few decades are due to the imposition of
pollution controls.
In summary, then, both soils and sediments act as vast sinks and reser-
voirs in the containment of heavy metals.
Mine Tailings
In modern times, many minerals (and in some cases fossil fuels) are
extracted from much, much larger quantities of rock (or sand, etc.) than in
the past, since the remaining supplies of the minerals occur in dilute form.
This practice produces huge quantities of unwanted crushed rock in the
form of dry, coarse-grained waste that must be disposed of, usually in slag
heaps or landfills close to the mine. Eventually these waste piles are cov-
ered with soil and vegetation.
A more important environmental problem arises from disposal of the
tailings of mining processing—fine-grained slurries that are more mineral-
rich and often contain chemicals such as cyanide (Chapter 14) that were used
to extract or process the ore. The toxic components of tailings are a potential
source of pollution to local surface water, groundwater, and soil.
To prevent their dispersal into the environment, tailings are usually
deposited as slurries in dams constructed on-site for the purpose. To prevent
leakage into the soil, a clay or geomembranic liner is usually incorporated at
the dam’s base. Over time, the solid settles to the bottom of the dam and the
water evaporates or is drained off, i.e., the tailings become dewatered,
although this can take a long time to achieve. In some cases, toxic materials
such as heavy metals, nitrates, or excess acidity is removed by treatment of
the tailings. Eventually, to establish a vegetated cover, organic matter and fer-
tilizer must be added, since the dried tailings themselves contain little or no
organic matter and consequently are sterile as well as hostile to plants.
If the crushed rock or tailings contain iron pyrites, exposure to oxygen will
produce sulfuric acid by the series of reactions discussed as acid mine drainage
in Chapter 13. The acidity can be neutralized by the continuous addition of
limestone.
The most important environmental problem associated with a tailings
dam is its potential failure, resulting in a catastrophic discharge of the tailings
into a waterway and/or onto land. The failure might be due to flood, earth-
quake, or simply the loss of stability of the dam to pressure over time. A num-
ber of such incidents have occurred within the last decade—e.g., in
Spain—with devastating results to wildlife, fish, and, in some cases, agricul-
tural land.
An alternative to the storage of tailings on land is disposal in the deep
ocean by using pipelines reaching down 100 m or more. Lack of oxygen there
will slow the process of oxidation, and within a few years the tailings will be
covered by other debris. Some biologists are dubious about this plan, because
the environment for bottom-dwelling organisms will suffer. Heavy-metal
contamination of fish has occurred in areas where this means of disposal is
practiced. Due to the fine-grained nature of the tailings, dispersal over wide
areas of the ocean floor occurs.
The Remediation of Contaminated Soil

Even areas thought to be rather pristine can have localized areas of contami-
nated soil. For example, the large-scale forestry industry in New Zealand has
resulted in the contamination of several hundred sites where lumber is
treated with the preservative pentachlorophenol, PCP (Chapter 11). Furan and
dioxin contaminants of the PCP are also found in the soils. All three con-
taminant types have now leached into the groundwater at some of the sites
and have begun to bioacccumulate in the food chain.
Contaminated soil is found most often not only near waste disposal sites
and chemical plants, but also near pipelines and gasoline stations. The three
main types of technologies currently available for the remediation of con-
taminated sites are
• containment or immobilization,
• mobilization, and
• destruction.
In general, the technologies can be applied in situ, i.e., in the place of con-
tamination, or ex situ, i.e., after removing the contaminated matter to
another location. Owing to the costs and risks, e.g., air pollution arising from
excavation, in situ processes are usually preferred.
Among the techniques associated with in situ containment (i.e., the iso-
lation of wastes from the environment) are capping of the contaminated
site, especially with clay, and/or the imposition of cut-off walls of low perme-
ability that prevent the lateral spread of contaminants. Ex situ containment
would consist of the placing of the excavated soil in a special landfill. Immo-
bilization techniques, including solidification and stabilization, are espe-
cially useful for inorganic wastes, which tend to be difficult to treat by other
methods. Stabilization can often be achieved by adding a substance to con-
vert a heavy-metal ion into one of its insoluble salts, such as the sulfide in
the case of mercury and lead, or the oxide in the case of chromium. A con-
centrated waste can be solidified by reaction with portland cement, for
example, or by entombing the wastes in molten glass in the process of vitri-
fication. By these techniques, the solubility and mobility of the contami-
nants are reduced.
Mobilization techniques are mainly accomplished in situ and include soil
washing and the extraction of contaminant vapor from soil for highly
volatile, water-insoluble contaminants such as gasoline. Heating of the soil to
increase the rate of evaporation and air injection wells are sometimes used in
conjunction with soil vapor extraction, in which the contaminants are
removed by drilling wells in the soil and applying vacuum extraction. As
indicated in Table 16-3, this technique is the most frequently used innovative
technology at Superfund sites (Box 16-1) in the United States. A related
technology is thermal desorption, in which wastes are heated to cause
volatile organic compounds to vaporize. Both soil vapor extraction and
thermal desorption are useful to remediate both volatile and semivolatile
organic compounds, the latter including many PAHs.
Common Innovative Remediation Technologies

TABLE 16-3 in Projects at U.S. Superfund Sites (as of 1996)
Sites in Design Sites Operational

Technology or Installation or Completed Total Number
Soil vapor extraction 69 70 139

Thermal desorption 22 28 50
Bioremediation (ex situ) 24 19 43
Bioremediation (in situ) 14 12 26
In situ flushing 9 7 16
Soil washing 8 1 9
Solvent extraction 4 1 5
Source of data: U.S. EPA, Innovative Treatment Technologies: Annual Status Report, 8th ed., 1996.
BOX 16-1 The Superfund Program
n 1980 the federal government of the having such serious potential to cause harm to
I United States established a program now
known as Superfund to clean up abandoned
humans and the environment that they have
been placed on a National Priorities List. New
and illegal toxic waste dumps, since dangerous Jersey, Pennsylvania, and California have the
chemicals from many such sites were polluting greatest number of priority sites.
groundwater. The cleanup costs are shared by By the late 1990s, the EPA had finished
chemical companies, the current and past cleanup work at 300 sites, begun work at more
owners of the sites, and the government. than 700 others, and conducted emergency
Many billions of dollars have already been removal of materials at more than 3000 addi-
spent on remediation, and many billions more tional locations. The rate at which cleanup
will eventually be required. Progress in the work was completed at additional sites slowed
cleanups has been rather slow on account of appreciably in the mid-2000s. In all, over
the litigation involved and the huge amounts 30,000 sites have been identified as potentially
of money at stake. Many decades will pass in need of cleanup.
before even the highest-priority sites are all The most common contaminants at the
cleaned up. Superfund sites are the heavy metals lead,
The Superfund program is administered cadmium, and mercury, and the organic
by the Environmental Protection Agency, compounds benzene, toluene, ethylbenzene,
which has identified nearly 1,300 waste sites and trichloroethylene.
In situ soil washing is accomplished by injecting fluids through wells into

subsurface soil and collecting them in other wells. The fluid can simply be
water, which will remove water-soluble constituents, or an aqueous solution
that is acidic or basic in order to remove basic and acidic contaminants,
respectively. Other options in soil washing include the use of solutions con-
taining chelating agents such as EDTA (see Chapter 15) to remove metals
and of oxidizing agents to oxidize and thereby solubilize previously insoluble
species. The solvents used to extract the metal–organic complex from the
aqueous environment of the soil include hydrocarbons and supercritical car-
bon dioxide (a substance described later in this chapter). In order for the
resulting complex to be electrically neutral and therefore preferentially
soluble in the organic phase, a chelating agent with acidic hydrogens that are
substituted by the metal is usually employed. If the metal exists as an oxyan-
ion, e.g., chromium as Cr(VI), it may first have to be reduced in oxidation
number before it will bind to a chelating agent.
Sometimes the washing solution uses surfactants, surface-active agents.
These are substances such as detergents that possess both hydrophobic and
hydrophilic components within the same molecule and therefore can
increase the mobilization of hydrophobic contaminants into the aqueous
phase. Biosurfactants produced by microbes have recently been discovered
that can selectively remove certain heavy metals such as cadmium from soil.
Currently, soil washing and flushing are the most common innovative tech-
nologies used to remove metals at Superfund sites.
The containment, mobilization, and immobilization techniques by them-
selves do not result in the elimination of the hazardous contaminants.
Destruction techniques, principally incineration and bioremediation, do
result in permanent elimination because they chemically or biochemically
transform the contaminants. Organic contaminants in soil can be oxidized
(mineralized) by feeding the excavated soil into the combustion chamber of
an incinerator or by using incineration or one of the specialty oxidation tech-
niques, to be discussed later, to treat the substances that have been extracted
from the soil. Bioremediation uses the metabolic activities of microorganisms
to destroy toxic contaminants and is also discussed in detail later.
Electrochemical techniques are sometimes used to remediate soil. Plac-
ing electrodes in the contaminated ground and applying a dc voltage between
them results in ion transport within the soil: The ions travel within the
groundwater electrolyte. If heavy-metal ions are dissolved in the electrolyte
water, they will eventually move to the (negatively charged) cathode and be
deposited on it. Indeed, other metal ions tend to be desorbed from their posi-
tions on negatively charged clay surfaces in the process, since hydrogen ion is
released at the anode (as water is electrolyzed) and subsequently migrates in
the groundwater toward the cathode (see Figure 16-12). Recall that heavy-
metal ions are much more soluble in an acidic than in a neutral or alkaline
environment.
In some applications of such electro-

e– e–
dc kinetic methods, the process is stopped
source before the metals are deposited on the
cathode but after they have migrated most
of the distance toward it. The flow of
+ –
– ne – hydroxide ion from the cathode (see Fig-
2e Mn+
ure 16-12) precipitates many metals in any
+ ions – event. The metal-rich soil surrounding
H2O 2 e
– ions the electrode is then excavated and
Anode H+ +
cleansed by washing it or by other tech-
H2O Cathode
1/2 O
niques. By repeating this procedure and
2
inserting the electrodes at different loca-
OH– + tions in the soil, more efficient extraction
Soil 1/2 H
(with groundwater)
2 of the heavy metals is possible. The elec-
trokinetic technique has been used suc-
cessfully for copper, lead, cadmium,
FIGURE 16-12 Electro- mercury, chromium, and some radioactive metals. The method is high in
chemical remediation of energy demand, and hence in cost, because so much of the applied electrical
metal-contaminated soil.
potential is lost by the electrolysis of soil water.
In situ chemical oxidation can often be used to remediate soils (and
groundwater) contaminated with chlorinated solvents and/or with BTEX
(Chapter 14). The oxidizing agent is injected directly by means of a well into
the underground waste and may or may not be extracted at the other side of
the contaminated zone. Typically, a salt of permanganate ion, MnO4, is used
for TCE, PCE, and MTBE deposits, whereas ozone or hydrogen peroxide is
used for BTEX and PAHs or, in some cases, for the C2 chlorinated solvents as
well. The MnO2 product of oxidation by permanganate is a natural con-
stituent of soil. Hydrogen peroxide is often supplemented with ferrous salts
(together called Fenton’s Reagent) to create hydroxyl radical by a reaction
described in Chapter 14.
The Analysis and Remediation

of Contaminated Sediments
We now realize that many river and lake sediments are highly contaminated
by heavy metals and/or toxic organic compounds and that such sediments act
as sources to recontaminate the water that flows above them.
One way to determine the extent of contamination of a sediment is to
analyze a sample of it for the total amounts of lead, mercury, and other heavy
metals that are present. However, this technique fails to distinguish between
toxic materials already present in either their toxic form or in a form that can be
resolubilized into the water and those that are firmly bound to sediment particles
and unlikely to become resolubilized. Thus a more meaningful test involves
extracting from a sediment sample the substances that are soluble in water or
in a weakly acidic solution and analyzing the resulting liquid. In this way, the
permanently bound and therefore inactive toxic agents can be left out of the
account. Finally, the effect of sediments on organisms that usually dwell in or on
them can be determined by adding the organisms to a sediment sample and
observing whether they survive and reproduce normally.
Several types of remediation have been used for highly contaminated
sediments. The simplest solution is often to simply cover the contaminated
sediments with clean soil or sediment, thereby placing a barrier between the
contaminants and the water system. In other instances, the contaminated
sediments are dredged from the bottom of the water body to a depth below
which the contaminant concentration is acceptable. If the sediments are
high in organic content and inorganic nutrients, they are often used to
enhance soil used for nonagricultural purposes. In some cases, the sediment
can be used for cropland provided that its heavy metals and other contami-
nants will not enter the growing food. Cadmium is usually the heavy metal
of greatest concern in such sediments; if the pH of the resulting soil is 6.5 or
greater, most of the cadmium will not be soluble, so a higher total concen-
tration is often tolerated.
Several chemical and biological methods of decontaminating sediments
are in use. For example, treatment with calcium carbonate or lime increases
the pH of the sediments and thereby immobilizes the heavy metals. In some
situations, contaminated sediments are simply covered with a chemically
active solid, such as limestone (calcium carbonate), gypsum (calcium sulfate),
iron(III) sulfate, or activated carbon, that gradually detoxifies the sediments. In
other cases, the sediments are first dredged from the bottom of the water body
and then treated. Heavy metals are often removed by acidifying the sedi-
ments or treating them with a chelating agent; in both cases, the heavy met-
als become water-soluble and leach from the solid. For organic contaminants,
extraction of toxic substances using solvents and destruction by either heat
treatment of the solid or the introduction of microorganisms that consume
them are the main options. The cleaned sediments can then be returned to
the water body or spread on land. These techniques for removing metals and
organics from sediments are also often useful on contaminated soils.
Bioremediation of Wastes and Soil

Recall from Chapter 14 that bioremediation involves the use of living organ-
isms, especially microorganisms, to degrade environmental wastes. It is a rap-
idly growing technology, especially in collaboration with genetic engineering,
which is used to develop strains of microbes with the ability to deal with spe-
cific pollutants. Bioremediation is used particularly for the remediation of
waste sites and soils contaminated with semivolatile organic compounds such
as PAHs. It is a popular method for use at Superfund sites (see Table 16-3).
Bioremediation exploits the ability of microorganisms, especially bacte-
ria and fungi, to degrade many types of wastes, usually to simpler and less
toxic substances. Indeed, for many years it was thought that microorganisms
could and would eventually biodegrade all organic substances, including all
pollutants, that entered natural waters or the soil. The discovery that some
compounds, chloroorganics especially, were resistant to rapid biodegradation
was responsible for correcting that misconception. Substances resistant to
biodegradation are termed recalcitrant or biorefractory. In addition, other
substances, including many organic compounds, biodegrade only partially;
they are transformed instead into other organic compounds, some of which
may be biorefractory and/or even more toxic than the original substances. An
example of the latter phenomenon is the potential conversion of the once
widely used solvent 1,1,1-trichloroethane (methyl chloroform, now banned as
an ozone-depleting substance, as discussed in Chapter 2) into carcinogenic
vinyl chloride, CHCl “ CH2, by a combination of abiotic and microbial steps.
If a bioremediation technique is to operate effectively, several conditions
must be fulfilled:
• The waste must be susceptible to biological degradation and in a physi-
cal form that is susceptible to microbes.
• The appropriate microbes must be available.
• The environmental conditions, such as pH, temperature, and oxygen
level, must be appropriate.
An example of biodegradation is the degradation of aromatic hydrocar-
bons by soil microorganisms when land is contaminated by gasoline or oil. The
largest bioremediation project in history was the treatment of some of the oil
spilled by the Exxon Valdez tanker in Alaska in 1989. The bioremediation
consisted of adding nitrogen-containing fertilizer to more than 100 km of the
shoreline that had been contaminated, thereby stimulating the growth of
indigenous microorganisms, including those that could degrade hydrocar-
bons. Both surface and subsurface oil was biodegraded in this operation.
Some of the aromatic components in crude oil in marine spills become more
susceptible to biodegradation once they are photooxidized by sunlight into
more polar molecules.
In contexts such as contaminated soils, the biodegradation of PAHs is
slow since they are strongly adsorbed onto soil particles and are not readily
released into the aqueous phase, where biodegradation could occur. PAH-
contaminated soils are especially prevalent at gasworks sites used in the
1850–1950 period for the production of “town gas” from coal or oil. The pol-
lution is mainly in the form of deposits of tars, which are waste products that
are high-molecular-weight organic liquids denser than water that are mixed
with the soil and contain high levels of both BTEX and PAHs. Unfortu-
nately, groundwater that comes into contact with the tar can become con-
taminated if some of its more soluble constituents such as benzene and
naphthalene dissolve, although most of the tar is insoluble in water. The
other common soil contaminants at gasworks sites are phenols and cyanide.
Bioremediation processes can take place under either aerobic or anaer-

obic conditions. In the aerobic treatment of wastes, aerobic bacteria and
fungi that utilize oxygen are employed; chemically, the processes are oxida-
tions, as the microorganisms use the wastes as food sources. In some of the
bioremediation procedures used for aerobic soil, oxygen-saturated water is
pumped through the solid to ensure that O2 availability remains high. For
example, about 85,000 tonnes of soil contaminated by gasoline, oil, and
grease from a fuel plant in Toronto were decontaminated by first enclosing
it in plastic and then pumping air, water, and fertilizer into it to encourage
the population of aerobic bacteria to multiply and devour the hydrocarbon
pollutants. The bioremediation process took only three months.
There are many examples of wastes that can be degraded by anaerobic
microorganisms, although usually the most rapid and complete biodegrada-
tions are obtained with aerobic microorganisms. The anaerobic process
usually works best when there are some oxygen atoms in the organic wastes
themselves. In general, the process corresponds to the fermentation discussed
in Chapter 13, in which biomass with an approximate empirical formula of
CH2O decomposes ultimately to methane and carbon dioxide:
2 CH2O 9: CH4 CO2
An advantage of anaerobic biodegradation is its production of hydrogen sul-
fide, which in situ precipitates heavy-metal ions as the corresponding sulfides.
Several strategies used in bioremediation are based on the fact that
microorganisms evolve quickly—due to their short reproductive cycle—and
they develop the ability to use the food source at hand, even if it is chemical
wastes. One remediation strategy is to isolate the most efficient degrading
biomicroorgansims flourishing at a contaminated site, grow a large popula-
tion of them in the laboratory, and finally return the enhanced population to
the site. Another strategy is to introduce microorganisms that were found to
be useful at other sites in degrading a particular type of waste, rather than
waiting for them to evolve. Unfortunately, microorganisms adapted to one
environment may not be capable of surviving in another if additional hostile
contaminants are present. A third strategy is to encourage an increase in the
population of indigenous microorganisms at the site by adding nutrients to
the wastes and ensuring that the acidity and moisture levels are optimum.
Rather than waiting for microorganisms to evolve spontaneously, an
alternative strategy is to use genetic engineering to develop microbes specifi-
cally designed to attack common organic pollutants. However, regulatory
authorities have thus far been reluctant to allow genetically modified organ-
isms to be released into the environment, since public opposition to such
a move would be substantial.
In addition to bacteria, white-rot fungi can be used in biodegradation.
This species protects itself from pollutants by degrading them outside its cell
wall by secreting enzymes there that catalyze the production of hydroxyl
Clx Clx Clx Clx
OH OH C
H HO O
OH
H OH
FIGURE 16-13 Example other
of the aerobic degradation acyclic
of PCB molecules. products
radicals and other reactive chemicals. Since hydroxyl radical in particular is

quite nonspecific about which substances it oxidizes, the fungi are useful in
degrading mixtures of waste, including various chlorinated substances such
as DDT and 2,4,5-T, as well as PAHs.
Bioremediation of Organochlorine Contamination

It has been discovered that PCBs (Chapter 11) in sediments undergo some
biodegradation. PCB molecules with relatively few chlorine atoms undergo
oxidative aerobic biodegradation by a variety of microorganisms. For the
reaction to begin, a pair of nonsubstituted carbons—one ortho to the point of
connection between the rings and one meta site next to it—must be available
on one of the benzene rings. After 2,3 hydroxylation at these two sites, the
1,2 carbon–carbon bonds to the ortho carbons split in sequence, thereby
destroying the second ring and producing compounds that readily degrade
(see Figure 16-13).
P R O B L E M 16-6
Deduce the chlorine substitution positions on the benzene ring in the benzoic
acid that results from the aerobic degradation of 2,3
,5-trichlorobiphenyl.
Although PCB molecules that are heavily substituted by chlorines will

not undergo this process, since they are unlikely to have adjacent unsubsti-
tuted carbons, they will instead undergo anaerobic degradation, as will per-
chlorinated organic compounds such as TCE and HCB (Chapter 10). In the
absence of oxygen, anaerobic microorganisms facilitate the removal of chlo-
rine atoms and their replacement by hydrogen atoms, apparently by a reduc-
tive dechlorination mechanism that initially involves the addition of an
electron to the molecule. In the case of PCBs, this reductive dechlorination
occurs most readily with meta and para chlorines. Apparently, steric effects
block the ortho position from being attacked in most anaerobic mechanisms.
47
37 48
31 46
Aroclor 1242
5
8
2 7
in sediments
FIGURE 16-14 Concentration profiles (chromatograms) for various PCB congeners

of commercial Aroclor 1242 before and after biodegradation (different scales) in a
sediment. The major components of the peaks correspond to the following positions of
chlorine substitution: 2 2-chlorobiphenyl; 5 2,2
and some 2,6; 7 2,3
; 8 2,4
and some 2,3; 31 2,2

, 5,5
; 46 2,4,4
, 5; 47 2,3
, 4
,5; 48 2,3
, 4,4
. Notice
that biodegradation produces ortho-substituted congeners that are present in low
concentrations or absent in the original sample. [Source: D. A. Abramowicz and D. R. Olson,
CHEMTECH (July 1995): 36–40.]
Thus the products of anaerobic treatment here are ortho-substituted con-

geners, ultimately 2-chlorobiphenyl and 2,2
-dichlorobiphenyl especially.
Cl
anaerobic
conditions
Cl
Cl Cl Cl Cl
Since dioxin-like toxicity of PCBs requires several meta and para chlorines
(see Chapter 11), the anaerobic degradation process significantly reduces the
health risk from PCB contamination. Of course, once adjacent ortho and meta
sites without chlorine are available, aerobic microorganisms—if available—
could degrade the biphenyl structure, as already discussed. Figure 16-14
illustrates the change in composition of a commercial PCB sample after it has
resided for some time in sediment that contains anaerobic bacteria.
Phytoremediation of Soils and Sediments

The technique of phytoremediation, the use of vegetation for the in situ
decontamination of soils and sediments of heavy metals and organic
O2 Some pollutants
H2O
CO2
Some forms of contaminants

are trapped in fibrous parts Enzymes in fungi and
of the tree or other plant. microbes released from the
plant react with pollutants
and break them down.
Other pollutants are Some pollutants in the

FIGURE 16-15 absorbed into the tree soil are broken down
Mechanisms of from the roots. by oxygen and enzymes
phytoremediation by O2, enzymes emitted from the roots.
a plant.
pollutants, is an emerging technology. As illustrated in Figure 16-15, plants

can remediate pollutants by three mechanisms:
• the direct uptake of contaminants and their accumulation in the plant
tissue (phytoextraction),
• the release into the soil of oxygen and biochemical substances such as
enzymes that stimulate the biodegradation of pollutants, and
• the enhancement of biodegradation by fungi and microbes located at
the root–soil interface.
Advantages of phytoremediation include its relatively low cost, aesthetic
benefits, and nonobtrusive nature.
Certain plants are hyperaccumulators of metals, i.e., they are able to

absorb through their roots much higher than average levels of these contam-
inants (by a factor of at least 10–100, to yield a contaminant concentration
of 0.1% or more) and to concentrate them much more than do normal plants.
This ability probably evolved over long periods of time as the plants grew on
natural soils that contained high concentrations of pollutants, especially
heavy metals. In bioremediation, these plants are deliberately planted on
contaminated sites and then harvested and burned. In some instances, the
resulting ash is so concentrated in metal that it can be mined!
Phytoremediation is an attractive technique because metals are often
difficult to extract with other technologies since their concentration is
usually so small. For example, the shrub called the Alpine pennycress has the
ability to hyperaccumulate cadmium, zinc, and nickel. Phytoremediation has
been successfully used for extraction, e.g., of cadmium by both water
hyacinths and various grasses; of lead and copper by alfalfa; and of chromium
by Indian mustard, sunflowers, and buckwheat. In some cases, a chelating
agent is added to the soil to enhance the accumulation of metals by the plant.
Scientists are experimenting with various types of plants that can extract
lead from soils. One difficulty with phytoremediation is that hyperaccumu-
lators are usually plants that are slow to grow and therefore slow to accumu-
late metals. However, fast-growing poplar trees show promise of being
efficient phytoremediators. One recently developed type of hybrid poplar
efficiently absorbs TCE from hazardous waste sites and from groundwater. In
general, there is a need to harvest the plants before they lose their leaves or
begin to decay, so that contaminants do not become dispersed or return to
the soil.
Plants can efficiently take up organic substances that are moderately
hydrophobic, with log Kow values (Chapter 10) from about 0.5 to 3, a range
that includes BTEX components and some chlorinated solvents. Substances
that are more hydrophobic than the upper limit of this range bind so strongly
to roots that they are not easily taken up within the plant. Once taken up, the
plant may store the substance by transformation within its lignin component
or it may metabolize it and release the products into the air.
Substances that plants release into the soil include chelating ligands and
enzymes; by complexing a metal, the former can decrease its toxicity, and the
latter in some cases can biodegrade pollutants. For example, it has been found
that the plant-derived enzyme dehalogenase can degrade TCE. Plants also
release oxygen at the roots, thereby facilitating aerobic transformations. As
previously discussed, the fungi that exist in symbiotic association with a plant
also have enzymes that can assist in the degradation of organic contaminants
in soil.
Bioremediation in general and phytoremediation in particular are rapidly
emerging technologies. The long-term potential for these techniques to be
used at many sites that require decontamination is apparent. Experiments at
several test sites have shown that phytoremediation can be used successfully
to degrade petroleum products in soils. The number of Superfund sites apply-

ing bioremediation technology is shown in Table 16-3.
Hazardous Wastes
In this section, we consider the nature of various types of hazardous wastes
and discuss how individual samples of such wastes can be destroyed as an
alternative to simply dumping them and thereby deferring the problem to
a later date.
Currently there are more than 50,000 hazardous waste sites and perhaps
300,000 leaking underground storage tanks in the United States alone. The
Superfund program of the U.S. EPA was created to remediate waste sites;
its eventual cost is estimated to be $31 billion (see Box 16-1).
The Nature of Hazardous Wastes

A substance can be said to be a hazard if it poses a danger to the environment,
especially to living things. Thus hazardous wastes are substances that have
been discarded or designated as waste and that pose a danger. Most of the haz-
ardous wastes with which we shall deal are commercial chemical substances
or by-products from their manufacture; biological materials are not consid-
ered here.
In Chapter 10, we paid a great deal of attention to substances that were
toxic, i.e., they threaten the health of an organism when they enter its body.
Other common types of hazardous materials include those that are
• ignitable and burn readily and easily;
• corrosive because their acid or base character allows them to easily
corrode other materials;
• reactive in senses not covered by ignition or corrosion, i.e., by
explosion; and
• radioactive.
Some waste materials are hazardous in more than a single category.
The Management of Hazardous Wastes

There are four strategies in the management of hazardous waste. In order of
decreasing preference, they are:
• Source reduction: The deliberate minimization, through process
planning, of hazardous waste generation in the first place. The green
chemistry cases presented throughout this text provide many examples of
this strategy.
• Recycling and reuse: The use in a different process as raw materials,

whether by the same company or a different one, of hazardous wastes
generated in a process.
• Treatment: The use of any physical, chemical, biological, or thermal
process—including incineration—that reduces or eliminates the hazard from
the waste. Examples of such technology are discussed in subsequent sections.
• Disposal: Burial of the nonliquid waste in a properly designed landfill.
In the past, liquid hazardous wastes were often injected into deep
underground wells.
Landfills that are specially designed to accommodate hazardous wastes
have several characteristics in addition to those discussed for sanitary landfills.
The locations of such landfills should be
• in an area with clay or silt soil, to provide an additional barrier to
leachate dispersal, and
• away from groundwater sources.
Often the hazardous wastes in such landfills are grouped according to their
physical and chemical characteristics so that incompatible materials are not
placed near each other.
Toxic Substances
As mentioned, toxic wastes are those that can cause a deterioration in the
health of humans or other organisms when they enter a living body. Their char-
acteristics, as well as many examples, were discussed in Chapters 10–12 and
15 particularly and so will not be reviewed in detail here. Those of main con-
cern are heavy metals, organochlorine pesticides, organic solvents, and PCBs.
As an example of the magnitude of the problem of toxic substance waste
management, consider the PCBs that are still used in the capacitors in the
ballast tubes of fluorescent light fixtures. Within the sealed capacitor con-
tainer is a thick, gel-like liquid of concentrated PCB oil that is absorbed in
several layers of paper. A typical capacitor contains about 20 g—about a
tablespoon—of liquid PCB. Although each ballast does not contain much
PCB, the number of these lighting fixtures in use in the developed world is
huge. Thus the ultimate collection and disposal of PCBs from these sources
will be a task requiring many years and many dollars. Disposal methods for
toxic organic compounds are discussed later in this chapter.
Incineration of Toxic Waste

Incinerators that deal with hazardous waste are often more elaborate than
those that burn municipal waste because it is important that the material be
more completely destroyed and that emissions be more tightly controlled.
In some cases, the waste (e.g., PCBs) will not ignite on its own and must be
added to an existing fire fueled by other wastes or by supplemental fuel such
as natural gas or petroleum liquids. Modern facilities employ very hot flames,
ensure that there is sufficient oxygen in the combustion zone, and keep the
waste compounds in the combustion region long enough to ensure that their
destruction and removal efficiency, DRE, is essentially complete, i.e.,
99.9999%, called “six nines.” The presence of carbon monoxide at a con-
centration greater than 100 ppm in the gaseous emissions is often used as an
indicator of incomplete combustion.
About 3 million tonnes of hazardous wastes are burned annually in the
United States, although this is only 2% of the amount generated. Three-
quarters of the hazardous waste is dealt with by aqueous treatment, and 12%
is disposed of on land or injected into deep wells.
The two most common forms of toxic waste incinerators are the rotary
kiln and the liquid injection types. The rotary kiln incinerator can accept
wastes of all types, including inert solids such as soil and sludges. The wastes
are fed into a long ( 20 m) cylinder that is inclined at a slight angle (about
5° from the horizontal) away from the entrance end and slowly rotates so that
unburned material is continually exposed to the oxidizing conditions
of 650–1100°C; see Figure 16-16. Over a period of about an hour, the waste
makes its way down the cylinder and is largely combusted. The hot exit gases
from the kiln are sent to a secondary (nonrotating) combustion chamber
equipped with a burner in which the temperature is 950–1200°C. The
gas stays in the chamber for at least two seconds so that destruction of organic
molecules is essentially complete. In some installations, liquid wastes can be
fed directly into this chamber as the fuel. The gases exiting the secondary
chamber are rapidly cooled to about 230°C by an evaporating water spray (in
some cases with heat recovery), since they would otherwise destroy the air
pollution equipment that they next enter.
Liquid Water
wastes spray
and air
Waste
+ Other air Gases
air pollution to air
control
Rotary kiln Secondary equipment
incinerator combustion
chamber
FIGURE 16-16 Schematic
diagram of the components Ash Solid ash
of a rotary kiln incinerator, +
including air pollution wastewater
equipment.
Rotary kiln and other types of incinerators usually employ the same series
of steps to purify the exhaust of particulates and of acid gases before it is
released into the air, as do garbage incinerators, e.g., a gas scrubber and a bag-
house filter.
Cement kilns are a special type of large rotary kiln used to prepare
cement from limestone, sand, clay, and shale. Very high temperatures of
1700°C or more are generated in cement kilns in order to drive off the carbon
dioxide from limestone, CaCO3, in the formation of lime, CaO. In addition
to hotter combustion temperatures (compared to incinerators), wastes in
cement kilns are burned with the fuel right in the flame; the residence time
of the material in the kiln is also longer. Liquid hazardous wastes are some-
times used as part of the fuel (up to 40%) for these units, the remainder being
a fossil fuel, usually coal. Recently, techniques have been developed that
allow kilns to handle sludges and solids. Cement kilns burn more hazardous
waste (about a million tonnes a year) than do commercial incinerators in the
United States, although even more waste is incinerated on-site by chemical
industries.
In the liquid injection incinerator—a vertical or horizontal cylinder—
pumpable liquid wastes are first dispersed into a fine mist of small droplets.
The finer these droplets, the more complete their subsequent combustion,
which occurs at about 1600°C with a waste residence time of a second or two.
A fuel or some “rich” (easily combustible) waste is used to produce the high
temperatures of the combustion. In contrast to the rotary kiln, only a single
combustion chamber is used, although in some modern versions a secondary
input of air is introduced to improve oxygen distribution and generate more
complete combustion. The exit gases can be passed through a spray dryer to
neutralize and remove acid gases, followed by a baghouse filter to remove par-
ticulates, before being released into the outside air.
The incineration of hazardous waste has garnered much attention from
environmentalists and some of the general public because of the potential
release of toxic substances—particularly from the stack into the air—
resulting from the operation of these units. Of special concern are the
organic products of incomplete combustion, PICs, that have been found
both in gases and adsorbed on particles emitted from incinerators. The PICs
must be formed in the post-flame region because they could not survive the
temperatures of the flame. Some of the most prevalent PICs are methane
and benzene.
In their research to understand the production of these pollutants, scien-
tists and engineers have discovered that reactions can occur downstream of
the flame in “quench” zones and in pollution control devices, where tempera-
tures fall below 600°C. Both gas-phase and surface-catalyzed processes appar-
ently occur. For example, trace amounts of various dioxins and furans form at
200–400°C on fly ash and soot surfaces where the processes may be catalyzed
by transition metal ions. A temperature of about 400°C is optimal for dioxin
formation; below this the formation reaction is slow and above it they are
quickly decomposed. It has not been established whether the dioxins and furans
result from the coupling on surfaces of precursor compounds such as chloroben-
zenes and chlorophenols, or from the so-called de novo synthesis involving
chlorine-free furan- or dioxin-like structures reacting with inorganic chlorides.
Concern has also been expressed about increased emissions that could
occur when the incinerator is being closed down and during accidents or
power failures, when lower temperatures would result for some time, since
much greater quantities of dioxins and furans could presumably form under
such conditions. Fugitive emissions, which include emissions from valves,
minor ruptures, incidental spills, etc. are also a concern. The dust emitted
from cement kiln incinerators has been found to contain toxic metals and
some PICs. In fact, the health risk from toxic metal ion emissions (usually as
oxides or chlorides) from the hazardous waste incinerators is found to exceed
that from the toxic organics. As in the case of municipal incinerators, the
solid residue from hazardous waste units can amount to one-third of the orig-
inal waste volume and contains traces of toxic materials, as does the waste-
water from the scrubber units.
Concerns about incineration have spurred the development of other
technologies for disposing of hazardous waste. In molten salt combustion,
wastes are heated to about 900°C and destroyed by being mixed with molten
sodium carbonate. The spent carbonate salt contains NaCl, NaOH, and var-
ious metals from the combusted waste, which can be recovered so that the
Na2CO3 can be reused. No acidic gas is evolved, since it reacts within the
salt. In fluidized-bed incinerators, a solid material such as limestone, sand, or
alumina is suspended in air (fluidized) by means of a jet of air, and the wastes
are combusted in the fluid at about 900°C. A secondary combustion chamber
completes the oxidation of the exhaust gases. Plasma incinerators can
achieve temperatures of 10,000°C by passing a strong electrical current
through an inert gas such as argon. The plasma consists of a mixture of elec-
trons and positive ions, including nuclei, and can successfully decompose
compounds, producing much lower emissions than traditional incinerators.
In such a thermal or hot plasma, all the particles travel at high speeds and are
thermally hot. In a variant that is used to treat municipal solid waste, plasma
is first created in air, which is then used to heat a mixture of waste, coke, and
limestone to 1500°C or more in a second, oxygen-starved chamber. The inor-
ganic compounds are converted into a slag that is innocuous enough to be
used as a construction material. The organic compounds are broken down
into syngas, the combination of carbon monoxide and hydrogen discussed in
Chapter 8, which is then used as a fuel.
Supercritical Fluids
The use of supercritical fluids is another modern alternative to incineration.
The supercritical state of matter is produced when gases or liquids are
subjected to very high pressures and, in

some cases, to elevated temperatures. At Supercritical
pressures and temperatures at or beyond Critical point fluid
218
Pressure (atmospheres)
the critical point, separate gaseous and
liquid phases of a substance no longer
exist. Under these conditions, only the Liquid
supercritical state, with properties that lie Solid
between those of a gas and those of a
liquid, exists. For example, for water, the 1
critical pressure is 218 atm (22.1 megapas- 0.006
cals) and the critical temperature is Vapor
374°C, as illustrated in the phase diagram
in Figure 16-17. Depending on exactly
how much pressure is applied, the physical
properties of the supercritical fluid vary 0.01 100 374
between those of a gas (at relatively lower Temperature (ºC)
pressures) and those of a liquid (at higher
pressures); the variation of properties with
FIGURE 16-17 Phase
changes in pressure or temperature is particularly acute near the critical diagram for water (not
point. Thus the density of supercritical water can vary over a considerable to scale). Notice the region
range, depending upon how much pressure (beyond 218 atm) is applied. for the supercritical state
Other substances that readily form useful supercritical fluids are carbon diox- (shaded light green), which
ide (see Chapters 6 and 7; it is used for many extractions in the food industry, exists at temperatures and
pressures beyond the
including the decaffeination of coffee beans), xenon, and argon. See Table critical point.
16-4 for their critical temperatures and pressures.
One rapidly developing innovative technology for destruction of organic
wastes and hazardous materials such as phenols is supercritical water oxida-
tion (SCWO). Initially, the organic wastes to be destroyed are either dis-
solved in aqueous solution or suspended in water. The liquid is then subjected
to very high pressure and a temperature in the 400–600°C range so that the
water lies beyond its critical conditions and so is a supercritical fluid. The
solubility characteristics of supercritical water differ markedly from those of
normal liquid water: Most organic substances become much more soluble, and
TABLE 16-4 Supercritical Fluid Characteristics
Substance Critical Temperature (°C) Critical Pressure (atm)
Water 374.1 217.7

Carbon dioxide 31.3 72.9
Argon 150.9 48.0
Xenon 16.6 58.4
many ionic substances become much less soluble. Similarly, and also because
very high pressures are applied, O2 is much more soluble in supercritical than
in liquid water.
At the elevated temperatures associated with supercritical water, the dis-
solved organic materials are readily oxidized by the ample amounts of O2 that
are pumped into and dissolve in the fluid. Hydrogen peroxide may be added
to generate hydroxyl radicals, which initiate even faster oxidation. Because
materials diffuse much more rapidly in the supercritical state than in liquids,
the reaction is generally complete within seconds or minutes. One practical
problem with the SCWO method is that insoluble inorganic salts that are
formed in the reactions can corrode the high-pressure equipment used in the
process and so shorten its lifetime; this problem can be solved by designing
the reactor so that there are no zones where salts can build up.
The advantages of the SCWO technology include the rapidity of the
destruction reactions and the lack of the gaseous NOX by-products that are
characteristic of gas-phase combustion. The required pressure and tempera-
ture conditions are readily accessible with available high-pressure equipment.
However, some intermediate products of oxidation—mainly organic acids
and alcohols, and perhaps also some dioxins and furans—are formed with the
SCWO method, which raises concerns about the toxicity of the effluent from
the process. In the variant of this technology in which a catalyst is used, the
percentage conversion to fully oxidized products is increased and the amount
of intermediates that persist is decreased.
In the wet air oxidation process, temperatures (typically 120–320°C)
and pressures lower than those required to achieve supercritical conditions
for water are used to efficiently oxidize aqueous wastes (often catalytically).
The oxidation is efficient because the amount of oxygen that dissolves at the
enhanced pressures favors the reaction. The process is generally much slower
than in supercritical water, requiring about an hour. The method is cheaper
to operate, however, than the relatively expensive SCWO technology.
Supercritical carbon dioxide has been used to extract organic contami-
nants such as the gasoline additive MTBE from polluted water. After extrac-
tion, the pressure can be lowered, at which point the carbon dioxide becomes
a gas, leaving behind the liquid contaminants to be incinerated or otherwise
oxidized. Similarly, supercritical fluids could be used to extract contaminants
such as PCBs and DDT from soils and sediments.
Nonoxidative Processes
All the processes just described employ oxidation as the means of destroying
the hazardous wastes. However, a closed-loop chemical reduction process
has been devised that has no uncontrolled emissions, using a reducing rather
than an oxidizing atmosphere to destroy hazardous wastes. One advantage to
the absence of oxygen is that there is no opportunity for the incidental forma-
tion of dioxins and furans. The reducing atmosphere is achieved by using
hydrogen gas at about 850°C as the substance with which the preheated mist
of wastes reacts. The carbon in the wastes is converted to methane (and some
transiently to other hydrocarbons such as benzene, which are subsequently
hydrogenated to produce additional methane). The oxygen, nitrogen, sulfur,
and chlorine are converted into their hydrides. The process is actually
enhanced by the presence of water, which under these reaction conditions
can act as a reducing agent and form additional hydrogen by the water-gas
shift reaction with methane (see Chapter 8). PAH formation, which is char-
acteristic of other processes at high temperatures in the absence of air, is sup-
pressed by maintaining the hydrogen level at more than 50%. The gas output
is cooled and scrubbed to remove particulates. The hydrocarbon output from
the process is subsequently burned to provide heat for the system; thus there
are no direct emissions to the atmosphere.
P R O B L E M 16-7
Construct and balance chemical equations for the destruction of the PCB
molecule with the formula C12H6Cl4 (a) by combustion with oxygen to yield
CO2, H2O, and HCl and (b) by hydrogenation to yield methane and HCl.
Chemical dechlorination methods for the treatment of chlorine-

containing organic wastes, especially PCBs from transformers, have been
developed and used in various parts of the world, though they are rather
expensive to operate. The basic idea is to substitute a hydrogen atom or some
other nonhalogen group for the covalently bound chlorine atoms on the mol-
ecules, thereby detoxifying them. The mostly dechlorinated wastes can then
be incinerated or disposed of in landfills. The commonly used reagent for this
purpose is MOR, the alkali metal (M sodium or potassium) salt of a poly-
meric alcohol. In the reaction, an ¬ OR group replaces each of the chlorines,
which depart as the salt MCl:
Cl Cl RO OR
5 MOR 5 MCl
Cl Cl Cl RO OR OR
The process is carried out at temperatures above 120°C in the presence of

potassium hydroxide, KOH, and occurs most efficiently for highly chlorinated
PCBs. An alternative dechlorination method is the reaction of the PCBs
with dispersions of metallic sodium to give sodium chloride and a polymer
containing many biphenyl units joined together.
Review Questions
1. Define the term solid waste and name its five 15. What is meant by a soil’s cation-exchange
largest categories for developed countries. capacity? What are its common units?
2. Describe the components and steps in the 16. What is meant by a soil’s reserve acidity? How
creation of a sanitary landfill. does it arise?
3. Describe the three stages of waste decomposi- 17. Describe several methods, including chemical
tion that occur in a sanitary landfill, including the equations, by which soils that are too acid or too
products of each stage. Are all stages equal in alkaline can be treated.
production or consumption of acidity? 18. Describe the processes by which soil in arid
4. Define the term leachate, explain how this areas becomes salty and alkaline.
substance arises, and list several of its common 19. What do the terms sediments and pore water
components. How can leachate be controlled and mean?
how is it treated?
20. By what three ways are heavy metals bound to
5. Explain the difference between the two sediments?
common types of MSW incinerators.
21. How can mercury stored in sediments be
6. What is the difference between bottom ash and solubilized and enter the food chain?
fly ash in an incinerator? Describe some of the air
pollution control devices found on incinerators. 22. Describe how mine tailings are usually stored
and how this represents a potential environmental
7. What is meant by the four Rs in waste man- problem.
agement?
23. How can sediments contaminated by heavy
8. Why can the recycling of metals often be metals be remediated so they can be used on
justified by economics alone? agricultural fields?
9. Describe the processes by which paper and 24. Describe two ways by which contaminated
rubber tires can be recycled. sediments can be treated without removing the
10. What are the common types of consumer sediments themselves.
packaging plastics that can be recycled? What four 25. List the three categories of technologies com-
ways are used to recycle plastics? monly used to remediate contaminated soils. Give
11. What are some of the arguments for and examples of each.
against the recycling of plastics? 26. List three conditions that must be fulfilled
12. What is meant by a life cycle assessment and if bioremediation of soil is to be successful.
what are the two main uses for LCAs? 27. Describe the two ways in which PCBs in
13. Describe the main inorganic constituents sediments are bioremediated.
of soil. How do clay, sand, and silt particles differ 28. Define phytoremediation and list the three
in size? mechanisms by which it can operate. What are
hyperaccumulators?
14. What are the names and origins of the
principal organic constituents of soil? Are both 29. Define the term hazardous waste. What are the
types of acids soluble in base? In acid? five common types?
30. List, in order of decreasing desirability, 33. Explain the advantages and disadvantages
the four strategies used in the management of of supercritical water oxidation for the destruction
hazardous waste. of hazardous wastes.
31. Name and describe the three common types 34. How is the chemical reduction process carried
of incinerators used to destroy hazardous waste. out? What advantages does it have over oxidation
What does DRE stand for and how is it defined? methods?
32. Define the term PICs and describe how they
are formed.

See the discussion of focus areas and the principles 3. The development of recyclable carpeting by
of green chemistry in the Introduction before Shaw Industries won a Presidential Green
attempting these questions. Chemistry Challenge Award.
1. What are the environmental advantages of (a) Into which of the three focus areas for these
using polyaspartate as an antiscalant/dispersant awards does this award best fit?
versus polyacrylate? (b) List three of the twelve principles of green
chemistry that are addressed by the chemistry
2. The synthesis of polyaspartate as developed developed by Shaw Industries.
by Donlar won a Presidential Green Chemistry
Challenge Award. 4. What are the environmental advantages
(a) Into which of the three focus areas for these of using polyolefin-backed nylon fiber carpeting
awards does this award best fit? in place of PVC-backed carpeting?
(b) List at least three of the twelve principles of
green chemistry that are addressed by the chemistry
developed by Donlar Corporation.
Additional Problems
1. Consider a small city of 300,000 people in the 2. By reference to the general solubility rules for
northern United States, southern Canada, or sulfides found in introductory chemistry textbooks,
central Europe, and suppose that its residents on deduce which metals would not have their sedi-
average produce 2 kg/day of MSW, about one- ment availabilities determined by AVS. Which of
quarter of which will decompose anaerobically to these metals would occur in the form of insoluble
release methane and carbon dioxide evenly over a carbonates instead and thus be biologically
10-year period. Calculate how many homes could unavailable in marine environments?
be heated by burning the methane from the land-
fill, given that residential requirements are about 3. The acid volatile sulfide concentration in a sedi-
108 kJ/year in that climate zone. Consult Chapter 7 ment is found to be 10 ␮mol/g. The majority of the
for data on methane combustion energetics. sulfide is present in the form of insoluble FeS, since
the Fe2 concentration in the sediment is done is to first perform an acid hydrolysis of the
450 ␮g/g. What mass of mercury in the form of cellulose to convert it into glucose. This is then
Hg2 can be tied up by the remaining sulfide in followed by fermentation of the glucose to produce
1 tonne of such sediment? Assume that a negligible ethanol. Write a balanced equation for the
amount of iron is not tied up as FeS. fermentation of glucose, C6H12O6, into ethanol,
C2H5OH. Given that the pyranose monomer
4. For the PCB congener 2,4,4
,5-tetrachloro- unit in cellulose has the formula C6H10O5 (i.e.,
biphenyl, deduce (a) the chlorine substitution glucose H2O), determine the volume of ethanol
pattern on the benzoic acid that results from its that could be produced in this way from 1.00 tonne
aerobic degradation and (b) the various PCB of hardwood scraps (46% cellulose), assuming
congeners with one or two chlorines that could 100% conversion in both steps. Ethanol’s density is
result from its anaerobic degradation. 0.789 g/mL.
5. Generate lists of the aspects of production, 7. One way to reduce the lifetime of plastic wastes
distribution, and disposal that you would employ is to make them photodegradable, so that some of
in a life cycle assessment to decide which is the the bonds in the polymers will break on absorption
more environmentally friendly container for beer: of light. When designing a photodegradable plastic,
glass bottles or aluminum cans. Do you think the what range of sunlight wavelengths would it be best
conclusions of such an analysis would depend for the plastic to absorb? What is the main limita-
significantly on the extent of recycling of the tion of the breakdown of these plastics? If you were
containers? to design a photodegradable plastic that would
6. Waste having a high cellulose content, such as break down on absorption of 300-nm light, what
paper, wood scraps, and corn husks, can be converted would be the maximum bond energy of the bonds to
to ethanol for use as a fuel. One way this can be be cleaved?
Further Readings
1. M. B. McBride, Environmental Chemistry of Soils 6. T. E. McKone and S. K. Hammond, “Managing
(New York: Oxford University Press, 1994). the Health Impacts of Waste Incineration,”
Environmental Science and Technology (1 September
2. P. S. Phillips and N. P. Freestone, “Managing
2000): 380A.
Waste—The Role of Landfill,” Education in Chem-
istry (January 1997): 11. 7. R. Brown et al., “Bioremediation,” Pollution
Engineering (October 1999): 26.
3. F. Pearce, “Burn Me,” New Scientist
(22 November 1997): 31. 8. M. E. Watanabe, “Phytoremediation on the
Brink of Commercialization,” Environmental
4. B. Piasecki et al., “Is Combustion of Plastics
Science and Technology 31 (1997): 182A.
Desirable?” American Scientist 86 (1998): 364.
9. P. B. A. Kumar et al., “Phytoextraction:
5. K. Tuppurainen et al., “Formation of PCDDs
The Use of Plants to Remove Heavy Metals from
and PCDFs in Municipal Waste Incineration and
Soils,” Environmental Science and Technology 29
Its Inhibition Mechanisms: A Review,” Chemo-
(1995): 1232.
sphere 36 (1998): 1493.
10. D. A. Wolfe et al., “The Fate of the Oil Spilled 14. D. Amarante, “Applying in Situ Chemical
from the Exxon Valdez,” Environmental Science and Oxidation,” Pollution Engineering (February
Technology 28 (1994): 561A–568A. 2000): 40.
11. F. Pearce, “Tails of Woe,” New Scientist 15. H. Black, “The Hottest Thing in Remedia-
(11 November 2000): 46. tion,” Environmental Health Perspectives 110
(2002): A146.
12. M. L. Hitchman et al., “Disposal Methods for
Chlorinated Aromatic Waste,” Chemical Society 16. D. M. Roundhill, “Novel Strategies for the
Review (1995): 423. Removal of Toxic Metals from Soils and Waters,”
Journal of Chemical Education 81 (2004): 275.
13. D. Simonsson, “Electrochemistry for a
Cleaner Environment,” Chemical Society Reviews
26 (1997): 181.
770 Environmental Instrumental Analysis VI
Environmental Inductively Coupled Plasma

Instrumental
Analysis VI
Determination of Lead
The analysis of heavy metals in environmental these excited-state electrons will relax by
samples is now routinely accomplished by the returning to the ground state; but that return is
spectroscopic method discussed in this box. accompanied by the emission of a photon
whose energy corresponds to the difference
s discussed in the text, anthropogenic between the excited-state and ground-state
A lead contamination in the environment
in North America and Europe has been
energy levels. And just as the energy of the
promotion is well defined, meaning that
decreasing since tetraethyllead and tetra- only specific energies can be absorbed by a
methyllead were phased out of gasolines in the particular atom, the energy released by this
1970s and 1980s. Presently, major sources of relaxation—and the emitted photon contain-
environmental Pb are residual lead in aerosol ing that energy—is very specific to the atom.
particles and dust near roadways (sometimes Since photon energy is related to wavelength
originating in decaying structures originally (Chapter 1), a means of elemental detection
painted with lead-based paints), smelting ash, can be based on detecting the light emitted
and lead pipes in plumbing (plumbum is Latin from a sample after the atoms in it are excited
for “lead”). Other sources include automobile by some means: That light is characteristic of
battery manufacture and disposal as well as the atoms excited in the sample.
cigarette smoke. In the developed countries, In the case of ICP, the excitation source is a
exposure to lead is dropping, but in developing very-high-temperature plasma (see Chapter 16
countries this exposure is increasing (Ahmed for a definition of plasmas). Light emitted by
and Ishiga, 2006). sample atoms injected into the plasma is col-
Like some of the other toxic metals dis- lected via lenses and mirrors and focused onto
cussed in this book, lead concentrations can a diffraction grating. This grating separates
be determined quickly and accurately using an individual wavelengths in space and focuses
atomic emission technique called inductively the light on a photomultiplier tube (PMT) or
coupled plasma spectroscopy (ICP). other detector that converts light into elec-
Each chemical element has a unique tronic signals. The wavelength of the light
atomic structure with electrons in well-defined identifies the elements in the sample that
(quantized) energy levels. The movement of emitted the photons, and the intensity of the
electrons between these levels, which requires light as measured by the PMT specifies the
the absorption or emission of energy, is also concentration of that element in the sample.
well defined, and therein lies the key to Atomic identity and amount are the two
atomic emission spectroscopy. If the atoms in a parameters determined by emission spectrom-
sample are excited using a very-high-energy etry that enable it to be used as an analytical
source—such as a flame, spark, or plasma— tool in environmental analysis.
many of the atoms’ electrons will be excited to The specific components of an ICP spec-
higher energy levels. Almost immediately, trometer depend on which of two basic designs
Inductively Coupled Plasma Determination of Lead 771
is used. The first type is called a sequential modest compared to the second, more power-
spectrometer and the second a simultaneous ful spectrometer design, the simultaneous ICP
spectrometer. The sequential spectrometer uses spectrometer.
only one PMT (detector) and requires a Simultaneous spectrometers have a simi-
process of scanning through the emission lar configuration to the simpler sequential
wavelengths to determine multiple elements instruments—they both have a plasma source
in one sample. This scanning process is usually (also called a torch) and a monochromator to
accomplished by very exacting rotation of the separate the light into individual wavelength
diffraction grating, which separates the light components. However, in the simultaneous
emissions. This rotation is carefully controlled instrument the spatially separated wavelength
by a computer so that the signal generated by beams are simultaneously dispersed onto a
the PMT can be correlated with the wave- plane, by a grating and a prism, and focused on
length of light that falls on it; i.e., the com- a detector similar to that of a digital camera.
puter knows by the grating position—which it This detector, called a charge-coupled device
is controlling—which wavelength is striking (CCD), can simultaneously record the inten-
the PMT. Sequential ICPs require time to scan sities of each of the different wavelengths
and sample the light for each element’s emis- for all of the elements emitting in the hot
sion, but the cost of a sequential instrument is environment of the plasma. In this way, many
Plasma
torch Emission from plasma
Slit Mirror
Charge-coupled device
Sample
input
Grating Prism
Two dispersion elements Different element emissions
strike different CCD locations.
Signals to
computer
772 Environmental Instrumental Analysis VI
Environmental Inductively Coupled Plasma

Instrumental
Analysis VI
Determination of Lead (continued)
elemental emission wavelengths can be atomized (converted to elemental Pb) and

detected individually—but all at one time— vaporized by the high temperature, a source
without having to scan between them; there- lamp with a specific wavelength is shone
fore, many chemical elements can be deter- through the vaporized atoms. Since only spe-
mined in the same sample simultaneously. cific energies can be absorbed by Pb atoms
Once again, the wavelength identifies the ele- (since the gaps between the atomic energy
ment emitting it, and the light’s intensity levels are quantized and specific to that ele-
conveys the concentration of that element in ment), the amount of absorption of the source
the sample injected into the plasma. lamp’s light can be used as a measure of the
Street dust is a measure, to some degree, amount of lead in the beam. A PMT on
of the amount of lead to which people in the opposite side of the sample atoms from the
cities become exposed via inhalation. It is source lamp records a decrease in source-lamp
thought that most of the lead in urban dust light intensity when the sample is introduced.
originated in the past from the particulates The larger the absorption, the more lead
released by the combustion of leaded gasoline. atoms are present in the sample. AAS there-
With that in mind, a comparison has been fore significantly differs from ICP: One is an
made of the lead determined in dust samples absorbance method and the other depends on
taken from the streets of Manchester, England, emission.
over time (Nageotte and Day, 1998). Samples The following table shows abridged results
of dust, dirt, and soil were scraped off streets from both the English studies, in 1975 and
with a spatula and analyzed by atomic absorp- 1997. Lead amounts are reported for three dif-
tion spectrometry (AAS) and by a modified ferent sampling categories: high-traffic areas,
ICP technique. In AAS, a high-temperature low-traffic areas, and areas where children
flame or hot carbon tube is used to atomize played (Nageotte and Day, 1998). The signifi-
the element of interest (lead, in our case) in cant improvement in lowered lead levels from
a dust sample that has been dissolved in an 1975 to 1997 certainly seems to stem from
acid solution. Once the lead ions have been England’s phase-out of leaded gasoline.
ppm Pb (number of samples)

Category
1975 1997
> 100 cars/hour 1001 ; 40 (180) 577 ; 53 (17)
< 10 cars/hour 993 ; 186 (53) 536 ; 93 (13)
Playgrounds, parks, gardens 1014 ; 206 (49) 572 ; 77 (47)

Inductively Coupled Plasma Determination of Lead 773
Childrens’ blood lead levels are also a References: F. Ahmed and H. Ishiga, “Trace Metal
measure of exposure to this toxic metal. The Concentrations in Street Dusts of Dhaka City,
Bangladesh,” Atmospheric Environment 40 (2006):
U.S. Centers for Disease Control (2006) notes 3835–3844.
that lead-associated intellectual deficits are
Chemistry-Based Animations, 2006: http://www.shsu
found in children with less than 100 ␮g/L .edu/~chm_tgc/sounds/sound.html.
of lead in their blood. In many developing S. M. Nageotte and J. P. Day, “Lead Concentration
countries, leaded gasoline and paint are still and Isotope Ratios in Street Dust Determined by
common. A meta-study incorporating 315 Electrochemical Atomic Absorption Spectrometry
published papers and involving 11,272 chil- and Inductively Coupled Plasma Mass Spectrometry,”
dren in provinces all over China (in the Analyst 123 (1998): 59–62.
period 1994–2004) reported a weighted mean U.S. Centers for Disease Control (2006), www.cdc.
of 92.9 ␮g Pb/L of blood in children of ages 1 gov/nceh/ lead.
to 12 years. Blood concentration levels of lead S. Wang and J. Zhang, “Blood Lead Levels in Children,
China,” Environmental Research 101 (2006): 412–418.
in children living in industrial areas were sig-
nificantly higher than those in suburban or
rural areas (Wang and Zhang, 2006).
news
SCAN
ENVIRONMENT
Mapping Mercury
HOT-SPOT UNKNOWNS COMPLICATE MERCURY REGULATIONS BY REBECCA RENNER
n issuing the Clean Air Mercury Rule a “cap and trade” approach to reduce
I this past March, the Bush adminis-

tration hoped to ease health con-
cerns about mercury from coal-fired
emissions of the element nationwide by
about 20 percent in five years and 70
percent by 2018. In formulating its
rule, the administration noted that
power plants. The White House enacted
power plants emit only 48 tons of the
metal every year—just a small fraction
of the total amount of mercury in the
atmosphere. Mandating further emis-
sion cuts, it argued, would not solve
the problem of human exposure to the
neurotoxin.
Eleven states and four public health
groups are challenging this approach,
arguing that cap-and-trade does not
address areas particularly vulnerable to
mercury pollution. Not so, says the
Environmental Protection Agency. When
the cap-and-trade proposals were
announced, the EPA’s head of air regula-
tions, Jeffrey Holmstead, said, “We don’t
think there will be any hot spots.” The
METALLIC SPREAD: Distinct environmental conditions help to amplify local
hot-spot standoff arises from big gaps
concentrations of methyl mercury, leading to health warnings such as this one in the
Florida Everglades. in mercury science, according to envi-
ronmental researchers, and the lack of
Rebecca Renner, “Mapping Mercury,” Scientific American,
September 2005, 20–22.
Mapping Mercury
news comprehensive data on mercury deposition than the Northeast, but both regions
SCAN tion means that a consensus about emis-
sions control will not likely emerge soon.
have serious methyl mercury problems.
A partial explanation for this dichoto-
Theoretically, mercury should prefer- my is the process by which elemental mer-
MERCURY’S entially rain down in areas near to power cury becomes methyl mercury. For mer-
TIME TO FALL plants. But attempts to determine the cury to get methylated and enter the food
fallout have proved incomplete. For web, it must be processed by bacteria that
The Bush administration instance, the Mercury Deposition thrive on sulfate, a sulfur compound. This
argues that mercury from means that dissolved organic matter and
power plants is a small sulfur enhance methylation, as do acidic
Percent of Total Mercury as Methyl Mercury
fraction of that already in the
atmosphere. The comparison Greater than 8 Less than 8 but greater than 4 waters such as those in the Northeast. The
Less than 4 but greater than 2 Less than 2 methylation process changes the conclu-
is misleading, argues Praveen
Amar, science director for sions drawn simply from examining mer-
NESCAUM, an association of cury fallout. For instance, Krabbenhoft
air-quality regulators in the recently completed a study of New
northeastern states. That’s
because most of the England lakes from locations near Boston
mercury in the atmosphere is and up to Maine. Mercury emissions and
in a gaseous elemental state deposition are highest in the urban area,
that remains there for about a but methyl mercury in fish is low. The fish
year and should not be a problems occur in Vermont and New
major contributor to rapid
changes in mercury Hampshire, where the conditions are right
deposition. On the other hand, for methylation. “What do we want to
HOT SPOTTING: Measurements reveal areas that
about 50 percent of the mer- protect?” he asks. “If it’s beautiful fishing
readily convert mercury to methyl mercury.
cury emitted by power plants spots like these lakes, then we need to look
is oxidized mercury that rains at more than deposition.”
down within a few days,
he says. Network, which measures the metal in Scientists finally understand methy-
rainwater in many parts of the country, lation well enough to map out vulnera-
Many mercury scientists does not account for mercury particulates ble areas at a national level, according to
agree, but it is hard to prove. that settle dry onto vegetation, a form of Krabbenhoft, who is currently working
The best evidence comes deposition that could be equal to the wet on such a map for the EPA. The work
from recent EPA monitoring of
Ohio Valley power plants. It variety, according to Oak Ridge National should, for the first time, combine depo-
showed that the depositions Laboratory scientist Steve Lindberg. sition and vulnerability to identify
of oxidized mercury and And just because a region receives unambiguous hot spots—regions where
sulfur dioxide, a tracer for above-average deposition doesn’t mean that it makes the most sense to take action to
combustion, increase together, it will have high levels of methyl mercury, limit the effects of mercury. Scientists
and back trajectories based
on meteorological data the form that builds up in long-lived preda- hope that this information and other
implicate the plants. tory fish such as trout, pike, tuna and advances may resolve the hot-spot
swordfish. “The areas with the most prob- debate and demonstrate the wisdom or
lems may not have the highest levels of dep- folly of the administration’s approach to
osition,” explains mercury expert David mercury regulation.
Krabbenhoft of the U.S. Geological Survey
branch office in Middleton, Wis. Indeed, Rebecca Renner is a writer based in
the Southeast has greater measured deposi- Williamsport, Pa.
776
APPENDIX
Background Organic Chemistry
In Chapters 10–12, the most important environmental problems caused by
toxic organic chemicals are discussed in detail. In this appendix, we provide
some necessary background in organic chemistry for those students whose
previous education has not included this subject.
The organic compounds of interest environmentally are mostly electri-
cally neutral molecules containing covalent bonds. Stable compounds of this
type inevitably involve the formation of four bonds by carbon; in carbon-
centered free radicals, they form three bonds. Conceptually at least, chemists
view all organic chemicals as “derived” from those simple organic compounds
that contain only carbon and hydrogen, i.e., hydrocarbons. We shall follow
this convention and divide our discussion into several sections, most of which
deal with specific types of hydrocarbons.
Alkanes
The simplest hydrocarbons are those that contain strings of carbon atoms,
each one singly bonded to its closest neighboring carbon atom(s) and to
several hydrogen atoms. Such hydrocarbons are called alkanes, of which the
simplest are methane, CH4; ethane, C2H6; and propane, C3H8. Commercial
supplies of all three are readily available from natural gas wells. Structural
formulas for these three alkanes are:
H H H H H H
H9C9H H9C9C9H H9C9C9C9H
H H H H H H
methane ethane propane
For convenience, chemists often write the formulas for such species by gath-
ering together in one unit all the hydrogens bonded to a given carbon and
displaying only the carbon – carbon bonds; thus ethane is represented as
CH3 ¬ CH3 and propane as CH3 ¬ CH2 ¬ CH3. In another common
representation, called a condensed formula, the C ¬ C single bonds are not
shown; rather the formula lists each carbon and the atoms attached to it. For
example, the condensed formula for ethane is CH3CH3. Each carbon atom in
an alkane molecule forms four equiangular single bonds, so the geometry
about each carbon is tetrahedral. Thus all alkanes are three-dimensional,
nonplanar molecules, even though, for the sake of clarity, their structural
AP-1
AP-2 Appendix Background Organic Chemistry
TABLE 1 Some of the Simple Unbranched Alkanes
Molecular Condensed Boiling

Formula Name Formula Point (°C)
CH4 Methane CH4 164

C2H6 Ethane CH3CH3 89
C3H8 Propane CH3CH2CH3 42
C4H10 Butane CH3CH2CH2CH3 0.5
C5H12 Pentane CH3(CH2)3CH3 36
C6H14 Hexane CH3(CH2)4CH3 69
C7H16 Heptane CH3(CH2)5CH3 98
C8H18 Octane CH3(CH2)6CH3 126
C9H20 Nonane CH3(CH2)7CH3 151
C10H22 Decane CH3(CH2)8CH3 174
C11H24 Undecane CH3(CH2)9CH3 196
C12H26 Dodecane CH3(CH2)10CH3 216
formulas seem to represent them as planar molecules involving bond angles

of 90° and 180°.
Table 1 lists the alkanes having one through twelve carbon atoms in
a continuous string; more complex alkanes contain branches, as we shall
see shortly. The alkane with four carbon atoms, called butane, is a gas;
longer alkanes are liquids or solids under ordinary conditions. When five
or more carbons are present in the alkane, the Latin-based abbreviation
for that number (pent for 5, hex for 6, hept for 7, oct for 8, etc.) is employed
as the prefix to the ending -ane in its name. For example, the molecule
CH3 ¬ CH2 ¬ CH2 ¬ CH2 ¬ CH3, which can be written more simply as
CH3(CH2)3CH3, is called pentane since it has 5 carbon atoms; its formula
is C5H12. When all the carbons lie in one continuous chain (without
branches), the molecule is said to be straight-chained or unbranched, and often
the prefix n- is added to the name; thus the pentane molecule described is
called n-pentane.
The constituent atoms of many organic compounds may be “reshuffled”
in chemical reactions to yield new structures—the ingredient atoms remain
exactly the same, but the way in which they are linked together (their “order
of linkage”) can be altered. So we get distinctly different sets of compounds
with the same molecular formula but different structures, which are called
structural isomers; there are other types of isomerism, too, which we need
Alkanes AP-3
not consider here. Sometimes the difference between isomers is slight—a

matter of small variations in physical properties; sometimes it is enormous—
the biological activity of two isomers may differ profoundly. Alkanes with four
or more carbon atoms have isomers in which the chain of carbon atoms is
branched: Not all the carbons are part of an unbroken path of bonded atoms.
An example is the isomer of n-pentane illustrated below:
H9C9H
H H H
H 9 C1 9 C2 9 C3 9 C4 9 H
H H H H
2-methylbutane
In naming such alkanes and other organic molecules, the short chains
of carbon atoms that comprise the branches are assigned group names ending
in -yl, which are derived by deleting the -ane ending from the name of the
alkane hydrocarbon that has the same length (in terms of linked carbon
atoms). Thus the CH3 ¬ group is called the methyl group, CH3CH2 ¬ is
called ethyl, etc. The names of these groups are listed as prefixes to the name
for the longest continuous chain of carbon atoms, and each is preceded by a
number that indicates the carbon atom of the chain to which the group is
attached. For example, the molecule shown above is called 2-methylbutane,
since butane is the alkane consisting of four carbons in an unbranched chain;
the ¬ CH3 group is bonded at the second carbon atom.
There are compounds in which one or more of the hydrogen atoms in
hydrocarbons such as the alkanes have been replaced by another atom such
as fluorine, chlorine, or bromine. Things that can be substituted for hydro-
gen atoms are called substituents. Some simple substituted hydrocarbons
are encountered in Chapter 2. Examples include the substituted methanes
CF2Cl2 (dichlorodifluoromethane), CHF2Cl (chlorodifluoromethane), and
CF3Br (bromotrifluoromethane) as well as the substituted ethane
CHF2 ¬ CH2F, which is called 1,1,2-trifluoroethane, where the numbers refer
to the carbon numbers to which the fluorines are bonded. Its structure is:
H H
F9C9C9H
F F
1,1,2-trifluoroethane
PROBLEM 1
Write out the structural formula and the condensed formula for each of the
following alkanes: (a) n-pentane; (b) 3-ethylhexane; (c) 2,3-dimethylbutane.
Alkenes and Their Chlorinated Derivatives

In some organic molecules, one or more pairs of the carbon atoms are joined
by double bonds; since each carbon atom forms a total of four bonds, there are
only two additional bonds formed by such carbon atoms. The simplest hydro-
carbon of this type is a colorless gas called ethene, usually known by its older
name ethylene:
H H
C"C
H H
ethene (ethylene)
Notice that the actual planar geometry of this molecule, with bond angles of
about 120° around each carbon, can be shown in the structural formula.
Condensed formulas normally show the double bond: CH2 “ CH2 or
H2C “ CH2.
A C “ C bond can be a part of a longer sequence of carbon atoms that
are joined together by other single, double, or triple C–C bonds. For example,
propene is a three-carbon chain with one adjacent pair of carbons joined by a
double bond:
H H
H C
C"C H or CH2 " CH 9 CH3
H H
propene propene
The name for a hydrocarbon chain containing a C “ C bond is the same as

that used for the alkane of the same length, except that the -ane ending of
the alkane is replaced by -ene. The molecule is numbered such that the
C “ C unit is part of the continuous chain and such that the C “ C unit is
at the lower-numbered end of the chain. Collectively, hydrocarbons contain-
ing C “ C bonds are called alkenes. If there are two C “ C bonds in a
Alkenes and Their Chlorinated Derivatives AP-5
hydrocarbon, the prefix di- is placed before the -ene ending; thus the hydrocar-
bon below is called 1,3-pentadiene:
H H
H C
H C"C H
C"C H
H H
1,3-pentadiene
The numbers preceding the name are those assigned to the first carbon atom
that participates in each of the double bonds. The alternative numbering
scheme, i.e., assigning the CH3 carbon on the right to be #1, is not used since
the first double bond would then start at carbon #2 and the name would be
2,4-pentadiene; thus the first double bond would not have the lowest possible
number.
In some derivatives of ethene, one or more of its hydrogen atoms
have been replaced by chlorine atoms. The chloroethenes, like ethene
itself, are planar molecules. The simplest example is CH2 “ CHCl, called
chloroethene but known in the chemical industry as vinyl chloride; it is pro-
duced in huge quantities since the common plastic material polyvinyl
chloride (PVC) is subsequently prepared from it.
A number is usually placed in front of the name of the substituent to indi-
cate the specific carbon atom to which it is bonded; thus Cl2C “ CH2 is called
1,1-dichloroethene to distinguish it from 1,2-dichloroethene, CHCl “ CHCl.
The molecule 1,1,2-trichloroethene, CCl2 “ CHCl, is a liquid solvent that
has extensive uses. Note that the prefix numbers in the compound name here
are superfluous since it has no isomers and thus there is no need to distinguish
one isomer from another. This compound is usually referred to by its tradi-
tional name trichloroethylene. The structural formulas of a few substitution
products of ethene are:
Cl H Cl Cl
C"C C"C
Cl H Cl Cl
1,1-dichloroethene tetrachloroethene
The liquid compound tetrachloroethene, CCl2 “ CCl2, is used on a large

scale as the dry-cleaning solvent used commercially to remove grease spots
and other stains on clothing. The prefix 1,1,2,2- is not used as part of its name
since it is superfluous (no other arrangements of chlorine being possible).
Note that when all the hydrogens in a molecule have been replaced by a
given atom or group, the prefix per can be used instead of the actual number;
thus tetrachloroethylene is also called perchloroethylene, giving rise to its
nickname “perc.”
PROBLEM 2
Write structural formulas for each of the following: (a) 1,1-dichloropropene,
(b) perchloropropene, (c) 2-butene.
PROBLEM 3
Determine the correct name for each of the following: (a) CHCl2CHCl2,
(b) CH3 ¬ CH2 ¬ CH “ CH2, (c) CH2 “ CH ¬ CH “ CH2.
Symbolic Representations
of Carbon Networks
Organic molecules often contain extensive networks of carbon atoms.
Chemists find it convenient to construct shorthand visual representations of
such molecules using a symbolic system of lines that indicate only the posi-
tion of the bonds (not including bonds to hydrogen atoms), rather than
writing out a structure in which the C and H atoms are shown explicitly.
To indicate the presence of a carbon atom, a “kink” is shown in the chain’s
representation. For example, the molecule n-butane can be represented as
(a) or (b) below:
CH3 9 CH2 9 CH2 9 CH3

(a) (b)
The hydrogen atoms are not shown at all in the “stripped-down” version; the
number of them at any carbon atom can be deduced by subtracting from
4 the number of bonds to that carbon that are displayed explicitly. Thus in
the representation below for 2-chloropropane, carbons #1 and #3 must pos-
sess 3 hydrogens, since they are shown as forming one other bond, whereas
carbon #2 has one hydrogen, since it is shown as forming three other bonds:
Cl
2-chloropropane
Common Functional Groups AP-7
PROBLEM 4
Write out the full structural formulas for each of the following molecules:
(a) (b) (c) Cl
PROBLEM 5
Draw symbolic (“kinky”) bond diagrams for each of the following molecules:
CH2
(a) CH3 9 CH2 9 CH 9 CH3 (b) CH3(CH2)4C
CH2Cl CH3
Cl
Cl
(c) CH2 " CH 9 CH2 9 C
CH2 9 CH3
Common Functional Groups

In addition to being replaced by simple single-atom substituents like Cl and
F, the hydrogen atoms in alkanes and alkenes can be replaced by more com-
plex “attachments” called functional groups—these are typically headed by
oxygen or nitrogen atoms. The common functional groups are listed in Table 2.
The simplest such polyatomic group is ¬ O ¬ H, usually simply shown as
¬ OH; it is called the hydroxyl group. Compounds that correspond to alkanes
or alkenes with the hydrogen of one C ¬ H bond replaced by an ¬ OH group
are called alcohols. Familiar examples are methyl alcohol or methanol (also
called wood alcohol) and ethyl alcohol or ethanol (grain alcohol):
H H H
H9C9O9H H9C9C9O9H
H H H
methanol, CH3OH ethanol, CH3CH2OH
The use of alcohols as fuels is discussed in Chapter 8.

TABLE 2 Some Common Functional Groups
Name of Compound Type Functional Group
Chloride —Cl
Fluoride —F
Alcohol —OH
Ether —O—
O
Aldehyde 9C
H
O
Carboxylic acid 9C
OH
Amine 9N
Compounds called ethers contain an oxygen atom connected on both

sides to a carbon atom or chain:
H H
H 9 C 9 O 9C 9H
H H
dimethyl ether, (CH3)2O
In more formal names for such compounds, the ¬ OCH3 group is known
as methoxy, and the ¬ OCH2 ¬ CH3 group is known as ethoxy, so that
dimethyl ether would be named methoxymethane. The use of ethers as gasoline
fuel additives is discussed in Chapter 8.
There are organic compounds analogous to alcohols and ethers in which
sulfur occurs in the position otherwise occupied by oxygen. The prefix thio- is
used to denote this substitution; thus we have thioalcohols, or just thiols,
such as CH3SH, and thioethers, such as CH3 ¬ S ¬ CH3.
As discussed in Chapter 3, carbon – oxygen double bonds are found in
some organic molecules. Molecules that contain the H ¬ C “ O group
bonded to hydrogen or to a carbon are known as aldehydes; the important
examples encountered in polluted air are formaldehyde, H2C “ O, and
acetaldehyde, CH3C(H) “ O. (Atoms or groups shown inside parentheses are
Common Functional Groups AP-9
bonded to the preceding carbon but do not themselves participate in the

bond displayed next in the formula.)
H H3C
C"O C"O
H H
formaldehyde, H2CO acetaldehyde, CH3CHO
If the C “ O group is connected to an ¬ OH group, the system is called a

carboxylic acid; examples are formic acid and acetic acid:
O O
H9C H3C 9 C
O9H O9H
formic acid, HCOOH acetic acid, CH3COOH
If the hydrogen atom of the !OH group is replaced by an organic group, the
compound is called an ester.
Groups headed by nitrogen atoms are known as amino groups; they are
found attached to carbon chains in some organic molecules. Compounds in
which the amino group is bonded to a hydrocarbon chain are called amines.
Note that nitrogen atoms form a total of three bonds, some (or all) of which
can be directed to carbons. Two examples are:
H H H H H
H9C9N9H H9C9N9C9H
H H H
methylamine, CH3NH2 dimethylamine, (CH3)2NH
Molecules that contain both the carboxylic acid group and an amino group
are called amino acids. They are the most important groups in proteins,
which include the enzymes that accelerate specific biological reactions. The
amino acid called cysteine is illustrated below; notice that it contains a thiol
group as well as an amino and a carboxylic acid group.
H
O
HS 9 CH2 9 C 9 C
OH
NH2
cysteine
Alcohols, acids, and amines that contain short carbon chains are quite
soluble in water. The reason is that molecules of these three types contain
O ¬ H or N ¬ H bonds, which possess a hydrogen atom that is partially
depleted of electron density by the highly electronegative atom (O or N)
to which it is bonded. The partial positive charge ␦ of the hydrogen is
attracted to regions of unbonded electron density—lone pairs—on atoms of
adjacent molecules:
O 9 H O9H
H
hydrogen
bond
Such interactions are called hydrogen bonds; the forces holding the two
atoms together—and therefore also holding together the two molecules to
which the atoms belong—are not nearly as strong as those of a regular bond
within a molecule, but they are much stronger than the forces that operate
between molecules in hydrocarbons. Water molecules illustrate this situa-
tion. They stick together because each hydrogen atom is hydrogen-bonded to
the lone pair of the H2O molecule closest to it. The attraction between H2O
molecules due to these interactions results in a relatively high boiling point
for liquid water, much higher than anticipated for a molecule of its mass. For
a (nonionic) substance to be freely soluble in water, these secondary bonds
between adjacent water molecules must be replaced by similar interactions
between the substance and the water molecules. Consequently, molecules
that contain N–H or O–H bonds and a short chain of carbons are soluble in
water because the hydrogen bonds they form with H2O molecules replace
those that are broken when the substance is incorporated into the liquid.
Hydrogen atoms bonded to carbon cannot form hydrogen bonds with water
molecules, since the carbon is not sufficiently electronegative to produce much
of a positive charge on a hydrogen atom bonded to it. In addition, there are no
lone pairs of electrons on the carbon atoms. Consequently, there is no driving
force that can disrupt the extensive network of hydrogen bonding within liquid
water in order to incorporate a large number of molecules of hydrocarbons or
chlorinated organic molecules. In both hydrocarbon and chlorinated organic
molecules, all the hydrogens are bonded to carbon; for this reason, such mole-
cules are not very soluble in water. Even molecules with one O ¬ H or N ¬ H
group and many carbon atoms are insoluble in water, since their overall charac-
ter is dominated by the large number of carbons. The forces of attraction that do
exist between organic molecules that contain no hydrogen-bonding capacity are
Benzene AP-11
quite nonspecific and nondirectional; consequently, different hydrocarbons are

quite soluble in each other, and organochlorine molecules are soluble in hydro-
carbons. We can restate the familiar generalization that “like dissolves like”:
Compounds tend to dissolve in other substances having the same types of inter-
molecular interactions.
PROBLEM 6
Write the structural formulas and symbolic diagrams for each of the follow-
ing: (a) ethyl alcohol, (b) ethylamine, (c) acetic acid (the carboxylic acid
with a methyl group bonded to the carbon).
Rings of Carbon Atoms

Networks of carbon atoms exist as rings in many organic molecules. The most
common rings are those that contain five, six, or seven carbon atoms. Mole-
cules containing rings are named by placing the prefix cyclo in front of the
usual name for the carbon chain of that length. Thus, a ring of six carbons, all
joined by single C–C bonds, is called cyclohexane. The molecule shown at the
right below is called methylcyclopentane.
CH3
or
cyclohexane methylcyclopentane
PROBLEM 7
Write out both simple and symbolic bond diagrams for the following
molecules: (a) cyclopropane, (b) chlorocyclobutane, (c) any isomer of
dimethylcyclohexane.
Benzene
One of the most common and most stable organic structural units is the
benzene ring, which is a planar hexagon of six carbon atoms. In the parent
hydrocarbon, it also contains six hydrogen atoms, one bonded to each carbon
and lying in the C6 plane:
A B
Each carbon in C6H6 is bonded to two carbons and to one hydrogen, so in

order to form four bonds, it must be doubly bonded to one of its neighboring
carbons. The two ways of achieving this result are shown in the so-called
Kekulé structures (A and B at the bottom of the previous page). In fact, ben-
zene molecules adopt neither of these two forms, each of which would have
alternating short C “ C and long C ¬ C bonds; rather they exist in an aver-
aged “resonance” structure in which all C–C bonds have the same interme-
diate length. (The term resonance here alludes to the mathematics of
the bond description and is commonly interpreted as “blend” or “hybrid.”)
This result is represented by the structure shown below, with the hexagon
containing an enclosed circle to represent the three double bonds; often,
however, just one of the Kekulé structures is shown, it being understood, at
least by chemists, that no actual alternation of bonds is meant.
Since the molecule is planar and has six equal sides, each C ¬ C ¬ C and
C ¬ C ¬ H angle is 120°. When benzene occurs as a substituent group in
another molecule, it is given the name phenyl.
Alkenes readily react by addition of molecules such as H2, HCl, and Cl2
across the double bonds—i.e., with one atom attaching itself to each of the two
carbons on the double bond—and thereby convert the C “ C units to single
bonds. For example, the addition of HCl to ethene produces chloroethane. The
corresponding reactions do not readily occur to the bonds in benzene or its
derivatives. Benzene can be hydrogenated, i.e., hydrogen can be added to its
double bonds, but only under rather extreme conditions. This difference in the
behavior of benzene compared to alkenes is an example of the special stability
of a six-membered ring containing three sets of alternating double and single
bonds. The electrons of the bonds interact with each other in a manner that
makes the molecule energetically much more stable than would be expected
from adding up single- and double-bond energies appropriate to alkanes and
alkenes. The extra stability disappears if even one of the three double bonds
is hydrogenated or otherwise added to by other molecules. Thus the six-
membered benzene ring is a unit of great inherent stability and survives intact
in media that would destroy other C “ C bonds. Benzene and other molecules
that possess this extra stability are said to be aromatic systems.
An exception to the rule that benzene does not add to its double bonds
occurs when the attacking atom or molecule is a free radical such as a chlo-
rine atom; recall that such species possess an unpaired electron. Thus,
whereas molecular chlorine, Cl2, itself does not add to the double bonds in
benzene, a single chlorine atom does. In fact, as early as 1825, Michael
Faraday found that chlorine gas would react with benzene if the reaction
mixture was exposed to strong light, which we now realize splits the Cl2
molecules into free Cl atoms. Once such a reaction starts, it continues
Chlorinated Benzenes AP-13
until all the carbon atoms have added one chlorine atom, and 1,2,3,4,5,6-
hexachlorocyclohexane is produced:
UV light
C6H6 3 Cl2 C6H6Cl6
Chlorinated Benzenes
Although benzene does not readily undergo addition reactions with mole-
cules or ions that are not free radicals, it does participate in substitution
reactions: One of its hydrogen atoms can be replaced by a group such as
methyl, hydroxyl, etc., that forms a single bond. Of particular interest is sub-
stitution by chlorine, since many compounds of environmental concern
contain chlorine-substituted benzene rings. When benzene is reacted with
chlorine gas in the presence of a catalyst such as iron(III) chloride, FeCl3,
one of the hydrogens (explicitly drawn on the ring below for clarity) is
replaced by chlorine, and HCl gas is released:
H Cl
FeCl3
Cl2 HCl
Notice that the aromatic C6 ring survives intact. Notice also that in these
structures the lone pairs on the chlorine atoms are not shown, as they were in
the previous structures for alcohols and amines. Chemists use both types of
structures—those that show the lone pairs and those that do not—for such
compounds.
If the reaction is allowed to continue, i.e., if excess Cl2 is available, one
or more hydrogen atoms of the chlorobenzene molecules will in turn be
replaced by chlorine. There are three isomeric dichlorobenzenes, all of which
could in principle be produced in such a reaction:
Cl Cl Cl
Cl
Cl
Cl
1,2-dichlorobenzene 1,3-dichlorobenzene 1,4-dichlorobenzene
The numbering scheme begins at one of the “substituted” carbons; the direction
of numbering around the ring is chosen to yield the smallest possible number
for the second substituent. In older nomenclature, 1,2-disubstituted benzene is
called the ortho substituted isomer, 1,3-disubstitution calls for the prefix meta, and
the 1,4 isomer is termed para. Thus the compound 1,4-dichlorobenzene, shown
above at the right, is also called para-dichlorobenzene or p-dichlorobenzene.
When using the Kekulé structure for benzene in which double and single
bonds are displayed, it is important to remember that the choice of a structure
(A or B on page AP-11) for the positions of the double bonds is an arbitrary
one. This has the consequence that there are only three, not five, isomeric
dichlorobenzenes. For example, 1,6-dichlorobenzene is not different from the
1,2 isomer; they represent the same molecule viewed from different perspec-
tives. (To avoid any such complications, many chemists use only the circle-
containing hexagon symbol shown on page AP-12.)
In some derivatives of benzene, there are two or more types of substituents,
even other benzene rings. In such cases, the carbon having the most important
substituent is called C-1, and the numbering continues in the direction that
gives the smallest number to the first substituent of the second kind. Many
examples of multiply substituted benzenes are encountered in Chapters 10–12.
PROBLEM 8
Deduce the structures and names for the three chemically different
trichlorobenzenes.
Review Questions
1. What is the name of the hydrocarbon 7. Draw the structural formulas and symbolic repre-
CH3(CH2)4CH3? Is it an alkane? Draw its struc- sentations for cyclopentane and for cyclopentene.
tural formula.
8. Explain what the term hydrogen bonding
2. Draw the structural formula for 3-ethylheptane. means. Explain why a short-chain alcohol such
as methanol is soluble in water whereas
3. What would be the name for the substituent
a long-chain one such as octanol is not.
group CH3CH2CH2CH2 ¬ ?
9. Is the six-membered ring system in benzene
4. Draw structural and condensed formulas for
particularly stable or unstable?
(a) trichloroethene and (b) 1,1-difluoroethene.
10. Do molecules such as H2 readily add to
5. What is the main use for the compound
benzene? Do free radicals such as atomic hydrogen
CCl2 “ CCl2? What two names are used for this
readily add to benzene?
compound?
11. What is another name for perchlorobenzene?
6. Draw structural formulas for each of the follow-
Do you expect it to be more soluble in aqueous or
ing: methyl alcohol, methylamine, formaldehyde,
in hydrocarbon media?
and formic acid.
Further Readings
For more extensive background in organic chem- Organic Chemistry, 4th ed. (New York: W. H.
istry, consult a modern introductory textbook Freeman and Company, 2003).
such as K. P. C. Vollhardt and N. E. Schore,
Answers to Selected
Odd-Numbered Problems
CHAPTER 1 2-5 CF3O O3 9: CF3OO O2
Problems CF3OO O 9: CF3O O2
1-1 (a) 427 kJ/mol; junction of UV-B with UV-C
(b) 299 kJ/mol; junction of UV with visible Green Chemistry Questions
region 1. (a) 2
(c) 160 kJ/mol; junction of visible and (b) 1, 4
infrared regions 3. No, not if the carbon dioxide is a waste
(d) 29.9 kJ/mol; beginning of thermal by-product from another process.
IR region 5. Harpin is applied to the plant, which elicits
1-3 390.7 nm; 127.5 nm the plant’s own natural defenses.
1-5 307 nm
1-7 OH O3 9: HOO O2 Additional Problems
HOO O 9: OH O2 1. (b) 4 1015 g
3. (a) 140
Overall: O3 O 9: 2 O2
(b) 10
Box 1-1, Problem 1 [O*] k1 [O2]/(k2 [M]
(c) 141
k3 [H2O])
7. Worse, since less Br is tied up in inactive
Additional Problems forms.
1. Net is O2 UV photon 9: 2 O
Each O reacts as O O2 9: O3 CHAPTER 3
Overall: 3 O2 UV photon 9: 2 O3
3. ClONO2 photon 9: Cl NO3 Problems
NO3 photon 9: NO O2 3-1 1.4 1014 M; 0.35 ppt
Cl O3 9: ClO O2 3-3 Increases the ozone concentration.
NO O3 9: NO2 O2 3-5 8 NH3 6 NO2 9: 7 N2 12 H2O
ClO NO2 9: ClONO2 0.0092 g
Overall: 2 O3 2 photons 9: 3 O2 3-7 1.2 107 M
5. 491 nm; visible 3-9 0.59 ppm
7. 3 103 molecules cm3 s1; 3-11 156 kg
2.5 1012 g cm3 y1 3-13 I O3 9: IO O2
9. 1.5 106 2 IO 9: I2O2
3-15 3:1 ratio; area is bigger with smaller
CHAPTER 2 particles.
Box 3-1, Problem 1 (a) 0.032 ppm
Problems (b) 7.9 1011 molecules/cm3
2-1 Cl O3 9: ClO O2 (c) 1.3 109 M
Br O3 9: BrO O2 Problem 3 (a) 9.3 1011 molecules/cm3
ClO BrO 9: Cl Br O2 (b) 74.2 ␮g O3/m3 of air
Overall: 2 O3 9: 3 O2
AN-1
AN-2 Answers to Selected Odd-Numbered Problems
Green Chemistry Questions CHAPTER 5

1. (a) Both are volatile and flammable hydrocar-
Problems
bons (VOCs); vapors would contribute to
5-1 CFCs have no H or multiple bonds, so they
pollution of the troposphere; flammability
don’t react with OH or light and thus don’t
would reduce worker safety.
oxidize. No, since CH2Cl2 has H atoms and
(b) It is a VOC and would contribute to
so it will react with OH.
tropospheric pollution, but it is not
5-3 Quite endothermic.
flammable.
5-5 If a C-bonded H is abstracted by OH, the
(c) It is a greenhouse gas, but waste carbon
C-centered radical H2COH will lose the
dioxide is used and recycled.
hydroxyl H by O2 abstraction, producing
3. First pair: The cation has a delocalized charge
formaldehyde. If instead OH abstracts the
and two nonpolar groups. Second pair: The
OH hydrogen initially, the resulting
charge on the anion is dispersed over the
C-centered H3CO radical loses H to O2
four chlorines, and the cation has a bulky
abstraction, producing formaldehyde.
nonpolar group. Third pair: Both the cation
5-7 Overall: H2CO 2 NO 2 O2 sunlight
and anion have nonpolar bulky groups, and
9: CO2 H2O 2 NO2
the charge on the anion is delocalized.
No increase in the number of free radicals.
Fourth pair: The charge on the anion is
5-9 Overall: CH3(H)CO 7 O2 7 NO 9:
delocalized, and the cation has four nonpolar
2 CO2 7 NO2 4 OH
bulky groups.
5-11 Same as for Problem 5-7.
5-13 CH3OOH and O2
Additional Problems
5-15 (a) O3, ClO, BrO, HOO
1. 4 1010 molecules cm3 sec1;
(b) O3, ClO, BrO, HOO, NO2
4 105 molecules cm3 sec1; that with O3
(c) O3, ClO, BrO, HOO, NO2
3. (a) O N2 9: NO N
(d) ClO, NO2, and perhaps BrO
rate k [O] [N2]
(e) When 2 O3 or 2 HOO react.
(b) Factor of 2.2 103
5-17 (a) ClO NO2 9: ClONO2
5. (a) O3 2 KI H2O 9: I2 O2 2 KOH
(b) 2 ClO 9: ClOOCl
(b) 120 ppb
(c) Reaction of ClO with UV or O or NO;
7. 1.0%
photolysis of ClOOCl.
9. 8 days
5-19 Cycle destroys ozone if NO2 reacts with O,
but not if NO2 decomposes in sunlight.
CHAPTER 4
Additional Problems
Problems
1. CO OH 9: HOCO
4-1 NH4 3 H2O 9: NO3 10 H 8 e
HOCO O2 9: HOO CO2
Additional Problems HOO NO 9: OH NO2
1. 4.3 105 M; 0.68; western NO2 UV 9: NO O
3. 3.7 109 g O O2 9: O3
5. 0.18 m2/y
Overall: CO 2 O2 UV 9: CO2 O3
7. 0.024 g
3. CO OH 9: HOCO 7-5 1,2,3-; 1,2,4-; and 1,3,5-trimethylbenzene

HOCO O2 9: CO2 HOO 7-7 2.274 tonnes
HOO O3 9: OH 2 O2 Green Chemistry Questions
Overall: CO O3 9: CO2 O2 1. (a) 2
(b) 1, 5, 7, 9, 10
5. NO2: O 9 N " O 3. Growing crops requires fertilizers and pesti-
cides. Energy is needed to plant, cultivate,
HNO2: H 9 O 9 N " O and harvest; to produce, transport, and apply
fertilizers and pesticides; to make and run
O
tractors; and to transport seeds, biomass,
HNO3: H 9 O " N monomers, and polymers. Use of land to
produce crops for chemicals also removes
O land that could be used to produce food
and feed.
CHAPTER 6
Additional Problems
Problems 3. 1.4%
6-1 52°C 5. 1.83 m
6-3 CO and NO; their stretching frequencies 7. (a) 16%
must lie outside the thermal IR range. (b) 22%
6-5 0.440 tonne; 0.27 g For all kinds, 40%
6-7 1 108 kg
6-9 485 Tg CHAPTER 8
6-11 No; yes; no
Problems
Green Chemistry Questions 8-1 68%
1. (a) 2 8-3 387°C
(b) 1, 3, 4, 5, 6 8-5 Slightly exothermic, small loss.
Additional Problems 8-7 –128.6 kJ mol1; increase
1. (a) Symmetric and antisymmetric stretch and 8-9 O2 2 H2O 4 e 9: 4 OH
bending vibrations for both. 2 OH H2 9: 2 H2O 2 e
(b) Only the SO2 symmetric stretch will O2 2 H2 9: 2 H2O
contribute much. 8-11 23.7 kg; 12.0 kg; Mg
(c) Short atmospheric lifetimes. 8-13 120 kJ g1; H2 is superior by weight, but
3. 0.48 methane is superior by volume.
7. Sharply increased air temperature.
9. 1180 L; 13,500 L; 23,500 L
1. 81%
3. Transesterfication (addition–elimination)
CHAPTER 7
5. The high vapor pressure of methanol may
Problems result in vapor lock, whereas the low vapor
7-1 t 0.69/k; 17.3, 23.1, 46.2, and 69.3 years; pressure of both ethylene glycol and glycerin
115 years; 4.6% may cause difficulty in starting at cold
7-3 0.00112, 0.00152, and 0.00254 mol CO2/kJ temperatures.
Additional Problems (2) It reduces pesticide risks to nontarget

1. 5.6 1024 J; 0.007% organisms.
3. One-third of the CO (3) It reduces the potential for contami-
3 C 4 H2O L 2 CH3OH CO2 nation of valued environmental
7. 0.0011 EJ resources.
(4) It broadens adoption of IPM or makes
CHAPTER 9 it more effective.
(b) 1 and 2
Problems
5. (a) 3
9-1 (a) 218 84Po
218
(b) 1, 4
(b) 84Po 7. 1, 2, and 3
(c) 42He
Additional Problems
(d) 238
92U 1. About 12 g
9-3 49%; 65%; yes, substantially above 3. 7.4 ␮g
9-5 21H + 32He ¡ 42He + 11p (or 11H) 5. Yes, since concentration is 4.7 ppb.
2 32He ¡ 42He + 2 11p (or 2 11H)
Additional Problems CHAPTER 11
1. 01e; 22 22 0 13 13
11Na ¡ 10Ne + 1e; 7N ¡ 6 C + 1e
0
Problems
235 11-1 No, the same
3. The effusion rate of UF6 is 0.43% faster
than that of 238UF6. Since very little enrich- Yes
ment occurs in a single step, it is necessary The unique ones are 1,2; 1,3; 1,4; 1,6; 1,7;
to repeat the process hundreds of times to 1,8; 1,9; 2,3; 2,7; 2,8.
achieve suitable enrichment. 11-3 (a) 2,3,5,6- and 2,3,4,5-tetrachlorophenols
(b) Two 2,3,5,6-tetrachlorophenols produce
CHAPTER 10 the 1,2,4,6,7,9-PCDD.
Two 2,3,4,5-tetrachlorophenols pro-
Problems duce the 1,2,3,6,7,8-PCDD.
10-1 (a) 4.0 105 ppm; 0.040 ppb 11-5 1.87 105 molecules
(b) 3.0 ␮g/L 11-7 2,3; 2,4; 2,5; 2,6; 3,4; 3,5; 2,2
; 2,3
; 2,4
;
(c) 300 ppb 2,5
; 2,6
; 3,3
; 3,4
; 3,5
; 4,4
10-3 5.0 ppm With rotation, 2,2

and 2,6
intercon-
10-5 (a) Yes vert, as do 2,3
and 2,5
, as well as 3,3
(b) No and 3,5

.
10-7 0.00010 mg/kg/day; 0.0055 mg/day 11-9 1,2; 1,3; 1,4; 2,3; 2,4; 3,4; 1,6; 1,7;
Box 10-3, Problem 1 In air: 9.9 1011 mol/m3 1,8; 1,9; 2,6; 2,7; 2,8; 3,6; 3,7; 4,6
In water: 2.3 1011 mol/m3 dichlorodibenzofurans
In sediment: 5.7 107 mol/m3 11-11 28.6 pg
Green Chemistry Questions Box 11-1, Problem 1 2,6-dichlorophenol
1. (a) 3 2,3,4-trichlorophenol, or
(b) 4 2,3-dichlorophenol
3. (a) A pesticide must meet one or more of the 2,3,6-trichlorophenol
following requirements: Box 11-2, Problem 1 1-chlorodibenzofuran,
(1) It reduces pesticide risks to human and 1,4-, 1-6-, and
health. 1-9-dichlorofurans
Green Chemistry Questions 13-19 1.02 103 M

1. (a) 2 13-21 30 mg CaCO3/L
(b) 1, 4, and 6 13-23 8.2 107 g
Additional Problems Green Chemistry Questions
1. (a) One 2,3,4,5- and one 2,3,4,6- 1. It removes the outermost layer of the raw cot-
tetrachlorophenol ton fiber, know as the cuticle, which makes
(b) One 2,3,4,6- and one 2,3,5,6- the fiber wettable for bleaching and dyeing.
tetrachlorophenol 3. (a) 2
(c) One 2,3,4,6- and either 2,3,4,5- or (b) 1, 3, 4, 6
2,3,5,6-tetrachlorophenol
3. Dechlorination; dioxins more toxic than the Additional Problems
originals may be produced. 3. (a) SO42 10 H 8 e 9: H2S 4 H2O
5. 2,3-, 2,2
-, and 2,3
-dichlorobiphenyls; 2,3,2
- (b) pE 5.75 (5/4) pH (1/8) log
trichlorobiphenyl (PH2S/[SO42 - ])
7. 2, 4, 5, 3
7 2, 4, 3
, 4
7 2, 4, 2
, 6
(c) 10136 atm, absolutely negligible
9. 2.0 1012 mol/m3; 1.5 1010 mol/m3; 5. 9.17
4.9 105 mol/m3 7. 6.1 mg/L; polluted
CHAPTER 12 CHAPTER 14
Problems Problems
12-5 Less; larger 14-1 Ca(HCO3)2 Ca(OH)2 9:
12-7 3.7 years; 45,000 2 CaCO3 (s) 2 H2O
1:1 ratio
Additional Problems
14-3 1; OH ; NH3 HOCl
1. (b) 1.52 ppb 14-5 11 ppm nitrogen; slightly less stringent
(c) 0.172 ␮g 14-7 Fe(s) 9: Fe2
2 H2O 2 e 9: H2 2 OH
CHAPTER 13 Fe(s) 2 H2O 9: Fe2 2 OH H2(g)
Problems 14-9 4 Fe C2Cl4 4 H2O 9:
13-3 8.1 mg 4 Fe2 C2H4 4 Cl 4 OH
13-5 16 mg/L 14-11 5.5 105; 0.0055; 0.55; 55
13-7 7.9 103 M; 6.3 1020 M; 8.32; 2.51 14-13 NO, NO2, NO2, NO3
13-9 15.2 14-17 214.3 kJ/mol; 558 nm; 45%
13-11 (a) NO3 2 H 2 e 9: Box 14-3, Problem 1 t [ln (k1/k2)]/(k1 – k2)
NO2 H2O Green Chemistry Questions
(b) 14.9 1. It is biodegradable and its synthesis is performed
(c) 14.9 pH 0.5 log ([NO2]/[NO3]) under mild conditions; it uses only water as a
(d) pE pH 15.9 solvent; and excess ammonia is recycled.
(e) 6 105
13-13 8.3 105 M; solubility increases with Additional Problems
increasing temperature. 1. 0.79; 0.54; 0.27; 0.10
13-15 8.0 104 M 3. 0.441 mL; 11 L
13-17 10.3 5. An O—O bond, as in HOSO2OO ; –1, so it
needs to gain an electron to become –2.
7. (a) CH3CCl3 e 9: CH3CCl2 Cl 16-7 (a) 2 C12H6Cl4 25 O2 9:

(b) CH3CCl3 OH 9: CH2CCl3 H2O 24 CO2 2 H2O 8 HCl
9. CO32 OH 9: CO3 OH (b) C12H6Cl4 23 H2 9:
Strong acid or a soluble calcium or magnesium 12 CH4 4 HCl
salt; about 104 M.
11. 3.73, 0.019%; 4.23, 0.059%
1. It is biodegradable; as a result, it places less of
a load on the environment. The Donlar syn-
CHAPTER 15
thesis of polyaspartate has only two steps and
Problems requires only heat and hydrolysis with sodium
15-1 M2 H2S 9: MS 2 H hydroxide.
M2 2 R!S!H 9: 3. (a) 1
R!S!M!S!R 2 H (b) 1, 5, 6
15-3 0.051 g
Additional Problems
15-5 0.5 mg; 2.0 105 g
1. About 8000 homes
15-7 2 105 g
3. 1.14 kg
15-9 6.0 ␮g/dL; 0.29 ␮mol/L
7. UV-B; need sunlight exposure to decompose;
Green Chemistry Questions 399 kJ/mol
1. (a) 3
(b) 4 APPENDIX
3. Lower air pollution, better corrosion
1. (a) H H H H H
protection, and reduced waste.
Additional Problems H9C9C9C9C9C9H
1. Yes; yes, the answer changes. H H H H H
3. H3AsO4 for pH 6 2.20; H2AsO4 from
2.20 to 6.89; HAsO42 from 6.89 to 11.49; CH3CH2CH2CH2CH3
AsO43 for pH 7 11.49; 17; 0.17
5. H liberates metals from sulfides; liberated
metals enter the food chain and affect human (b) H H H H H H
health. H9C9C9C9C9C9C9H
9. 13 mg m3, must be greater than the thresh-
old limit. H H H H H
CHAPTER 16 H9C9H
Problems H9C9H
16-1 3.9 L H
16-3 C3H3O2
16-5 O (CH3CH2)2CHCH2CH3
C9O
M
C9O
O
(c) H 7. (a) H H
C
H9C9H H
H9C9C
H H H H
H
H9C9C9C9C9H
H H H (b) H H
H9C9H H9C9C9H
H C 9 C 9 Cl
H Cl
(CH3)2CHCH(CH3)2 H H
3. (a) 1, 1, 1, 2-tetrachloroethane (c) H C H

(b) 1-butene H C C CH3
(c) 1, 4-butadiene H CH3
H C C H
5. (a) H H
H C H
Cl
(b)
Cl Cl
(c)
INDEX
Absorption lake acidification from, 151, light absorption by, 246f, 247
by aerosols, 247 153, 154f light reflection by,
particulate, 160, 161f pH of, 147 246–247, 246f
by particulates, 247 regional transport of, 147–148, nitrate, 137, 146f
Absorption spectrum, 30 150–152 sulfate, 136–137, 146f,
for carbon dioxide, soil acidification from, 247–249
217–218, 218f 150, 150f Agent Orange, 471
for DNA, 34f soil neutralization of, Agriculture
for nitrogen dioxide, 100f 149–150, 150f acid rain and, 155
for O2, 31f Acid(s) ground-level ozone and, 155
for ozone, 32f dry deposition of, 148 haze and, 163
Abstraction wet deposition of, 149, 151f irrigation in, groundwater
of hydrogen atom, 81 Acid volatile sulfide, 744 depletion from, 621–622
in stratosphere, 194 Activated carbon, in water Air pollutants
in troposphere, 178f, 179, purification, 602, 603b concentration units for, 92,
181, 182 Acute toxicity, 434 93b–94b
of oxygen atom Addition polymer, 728 dry deposition of, 148
from ozone, 195 Adsorption hazardous, 166
in stratosphere, 194 of volatile organic long-range transport of,
Acceptable daily intake compounds, 649 525–528, 527t, 528f
(ADI), 440 Advanced oxidation methods in Mexico City, 104
Acetaldehyde, 334, AP-8 (AOM), 649–650 in North America, 104
Acetic acid, 458, AP-9 Aeration, of drinking water, PAHs as, 509–512, 510f
Acetochlor, 455 602, 603f particulate, 132–137, 516.
Acetohydroxamic acid, 389 Aeration zone, 618, 618f See also Particulates
Acetol, 348, 349f, 350 Aerobic decomposition, 566–567 point sources of, 125
Acetone, 165 as nitrous oxide source, 242 smoke as, 162–163
Acetylcholine, 441 stage in landfill, 717 standards for, 159, 159t
Acid–base reactions Aerobic metabolism, as methane threshold concentration of, 156
in natural waters, 578–588 source, 237 wet deposition of, 149, 151f
Acid dissociation (ionization) Aerobic treatment of wastes, Air pollution
constant (Ka), 127 753–754, 754f agricultural damage from, 155
Acidity Aerosols, 133, 135. See also in Asia, 131–132, 157–158,
of natural rain, 147 Particulates 162–163
soil, 150, 152, 739–740 atmospheric cooling due to, cancers and, 156
Acid rain, 147–155 208, 247–249, 250b, 252f in China, 148, 157–158, 163
agricultural damage from, 155 climate-modifying effects of, in Europe, 104, 118, 131,
in China, 148 246–251 156–157
critical load and, 152–153 components of, 146, 146f forest decline from, 154–155
decline in, 150–151 fine, 146 haze from, 146. See also Haze
discovery of, 147 global distribution of, 249f, health effects of, 155–171,
ecological effects of, 148–153 250–251 166–167, 170–171
forest decline from, 154–155 global warming and, 248–251 from carbon monoxide,
global patterns of, 149f haze and, 146 167–168
I-1
I-2 Index
Air pollution (continued) classes of, 333 Angina pectoris, 169

from formaldehyde, esters as, 333, 346–347 Anthracene, 509, 510f
164–166 ethers as, 333, 345–346 Anthropogenic chemicals and
from nitrogen dioxide, 167 Alumina, 702 ozone depletion/destruction,
of outdoor, 155–163 Aluminosilicates, 589–590 77–79
from smog, 156–160 Aluminum Antifreeze, 350
indoor, 163–171 in natural waters, 596–597 Antiscalants, 721–723, 722f
from asbestos, 170–171 Aluminum hydroxide Antisymmetric stretch vibration,
from benzene, 166–167 in natural waters, 596 216, 229, 245
from formaldehyde, Aluminum ion Aquifer, 618f, 619
164–166 in lakes, 153–154, 154f Arctic region
from nitrogen dioxide, 167 Aluminum ion, in nature warming of, 253
in Mexico City, 104, 157, water, 596 Aromatic hydrocarbons, 274,
158, 160 Aluminum sulfate, in water 509. See also Polynuclear
transport of, 158 purification, 605 aromatic hydrocarbons
Air pollution, ground-level, 91 Alzheimer’s disease, aluminum (PAHs)
Air Quality Accord, 117, 131 and, 597 Aromatic systems, AP-12
Air quality indices, 137–138 Amalgams Arsenate ion, 695
Air quality standards, 138, 159t mercury, 668–669 Arsenic, 663, 664, 664t, 695
Air sample particle size Ames test, 439 anthropogenic sources of,
distribution in, 139–140 Amines, AP-9 696–698
Air stripping, 648 Amino acids, AP-9 as carcinogen, 698–699,
Air toxic, 156, 166 Ammonia, 100, 169, 612, 717 701–702
Alachlor, 438t, 455 natural sources of, 95t in drinking water,
Albedo, 207, 247, 327 oxidation of, 562, 639b 698–700, 701f
surface, 251, 252f Ammonium bisulfate, 136 in food, 704
Alcohol-gasoline mixtures, Ammonium ion, 136, 152 as insecticide, 418
334, 335f Ammonium nitrate, 136, 621 removal of from water,
Alcohols, 519, AP-7 Ammonium perchlorate, 625 702–703
as alternative fuels, 333–335 Ammonium sulfate, 136 standards for, 700–702
Aldehydes, 99, 102f, 103, 109, Amosite (brown asbestos), 171 toxicity of, 695, 698–700,
169, 187, 188f, 190, AP-8 Anaerobic decomposition, 145, 703–705, 705t
Aldicarb, 438t, 446–447 181, 566–567 Arsenite ion, 695
Aldrin, 420t, 432 acid stage in landfill, Arsine, 704
Alkalinity 717–718 Artificial global warming, 211
of natural waters, 592–595 carbon dioxide from, 315 Artificial marsh, 644–645
of soil, 149–150, 150f greenhouse gas(es) from, 315 Asbestos
Alkanes, 272, 274, 277b, methane from, 315 health effects of, 170–171
AP-1–AP-3, AP-2t methanogenic stage in Ash, incinerator, 720–721
Alkenes, AP-4–AP-6 landfill, 718 Asia, air pollution in, 131–132,
Allethrin, 438t as source of methane, 157–158, 162–163
Alpha (␣) particle, 368–369, 236–237, 240 Asian brown cloud,
369t, 372, 372f, 375, 378 as source of nitrous oxide, 163, 248
Alternating current/direct current 242–243 Asthma, air pollution and,
(AC/DC), 330–331 Anaerobic degradation of 156, 163, 165, 169
Alternative fuels wastes, 754 Atmosphere
advantages of, 333 Anastas, Paul, 4 reactivity in, 28
alcohols as, 333–335 Androgens, 517 regions of, 28
Index I-3
Atmospheric cooling Bicarbonate ions, in natural Borohydride ion, for hydrogen

by aerosols, 208, 247–249, waters, 578, 579f, 580b, 581f, storage, 358–359, 359f
250b, 252f, 253 581t, 590t Bottom ash, 720
by particulates, 208, 247–249, Bioaccumulation, 425–427, 428f, British anti-Lewisite
250b, 252f, 253 429, 430 (BAL), 665
Atmospheric reactions of heavy metals, 666 Broad-spectrum insecticides, 449
in ozone creation/destruction, Biochemical oxygen demand Bromate ions, from water
40–43 (BOD), 563–566 disinfection, 610
steady-state analysis of, Bioconcentration, 425–426, 428f Bromine nitrate, 55
44b–47b Bioconcentration factor (BFC), Brown asbestos (amosite), 171
Atmospheric residence time, 425–426 Brundtland Report, The, 2
231–234 Biodiesel, 346–350, 349f BTEX, 281
for greenhouse gas(es), 234 Bioethanol, 335–340 BTX, 281
Atmospheric window, 230–231 Biofuels, 334–348 in groundwater, 628–629, 630f,
Atom economy, 7 Biogas, 718 632t, 633
Atomic chlorine. See also Chlorine Biomagnification, 427, 428f Builders, in detergents, 640–641
in ozone destruction, 53–55 of heavy metals, 666 1,3-butadiene, 156, 169
Atrazine, 426t, 453–455 Biomass, 342f, 349 Butane, 272, 277b, 277f, AP-2
Autocatalytic reaction, 187 carbon dioxide and, 224 4-butanone, 165
Average lifetime, 233 as energy source, 312, 313f By-products, 6, 8, 10
Azinphos-methyl, 438t, 446 ethanol from, 335–340
hydrogen from, 362
as methane source, 237 Cadmium, 169, 380, 663,
Backscattering, 246 Biorefractory materials, 752 664, 664t
Bacteria, disinfection for, 604, 607f Bioremediation, 749 human exposure to, 693–694
Baghouse filter, 720 for groundwater sources of, 692–693
Barium sulfate, 721 decontamination, 631, Cadmium hydroxide, 692
Batteries 632t–633t Cadmium sulfide, 692
for electric cars, 355–356 of organochlorine Calcareous waters, 580
flow, 321 contamination, Calcium aluminosilicates, 289
lead from, 355 754–755, 755f Calcium arsenate, 696
lead storage, 681, 686–687 plants for, 755–757, 756f Calcium bicarbonate, 288, 586
mercury cell, 671–672 of wastes and soil, 751–753 Calcium carbonate, 579,
nicad (nickel-cadmium), 692 Biosurfactants, 749 581, 582–588, 585f,
Bay region, 514, 515b Biphenyls, 478 587t, 721
Beer–Lambert law, 231 Bisphenol-A, 518f, 520 in acid rain neutralization,
Bending vibration, 215, 215f, 229, Bisulfide ion, 685 149–150
235, 242, 244 Blackbody, 206, 209, 213b in carbon dioxide
Bentonite clay, 719 Blowing agents, 79–80 sequestration, 283, 288
Benz[a]anthracene, 510f, 513 Blue-baby syndrome, nitrates and, in sulfur dioxide reduction, 129
Benzene, 274, 281, 281t, AP-11 622–623 water purification and, 604
in groundwater, 627t, 628 Bonds, AP-6 Calcium hydroxide
health effects of, 166 in Lewis structures, 176b in lake deacidification, 151
Benzene hexachloride (BHC), 431 molecular, 214–216 Calcium hypochlorite, in water
Benzene ring, AP-11 strength of, 177, 179 chlorination, 612
Benzenes, chlorinated, AP-13 Bond-stretching vibration, 215, Calcium ions
Benzo[a]pyrene (BaP), 510f, 513, 215f, 234, 242, 244 in drinking water, removal of,
514t, 515b Boric acid, as insecticide, 418 602, 603f, 604
I-4 Index
Calcium oxide emissions international agreements on,

in carbon dioxide from hydrocarbon 304–306
sequestration, 283 oxidation, 187, 188f photosynthesis and, 220, 224
in sulfur dioxide reduction, 129 from methane oxidation, sources of, 271
Calcium silicate, 288 183, 183f trends in, 264–269, 264f, 265f,
Calcium sulfate, 129, 721 as greenhouse gas, 264 266f, 268f, 293–294, 294f
Calcium sulfite, 129 as green solvent, 225, 229 Carbon dioxide fertilization, 224
Camphene, 430 in hydrogen production, Carbon dioxide sequestration,
Canada, air pollution in, 105f, 284–285 282, 285f, 286f, 287f
106, 117, 131 IR absorption by, 216, ocean, 285–289, 285f, 286f,
Cancer. See also Carcinogens 217–218, 218f, 219f 287f, 290–291
air pollution and, 156, 160, from landfills, 717–718 in plants, 285f, 291
165–166 lifetime of, 221–223, 253 underground, 285f, 286f,
breast, 387 in natural waters, 566, 579, 289–290
lung, 170, 376–377, 391, 516 581f, 585–588 Carbon disulfide, 135
and ozone depletion/ ocean sequestration of, 579 Carbon emissions, 267, 268f
destruction, 34–35 phase diagram for, 228f Carbonic acid, 147, 578–579,
radiation and, 370, 375 removal of from atmosphere, 579f, 580b, 581f, 581t, 585
skin, 34–35 283–285, 290–291 from carbon dioxide
thyroid, 386 sinks for, 222, 223, 223f, sequestration, 286
CANDU reactor, 384 224f, 234 Carbon intensity, 265–267,
Carbamates, 446–447 sources of, 223, 223f, 224f 265f, 266f
Carbamic acid, 446 and stratospheric cooling, 214 Carbon monoxide
Carbaryl, 438t, 446, 455 structure of, 177 health effects of, 159–160,
Carbofuran, 438t, 446 supercritical, in computer chip 167–168
Carbon manufacture, 227, 228b, in methane oxidation,
in carbon dioxide 228f, 229 183, 183f
emissions, 267 waste, use of, 225, 228 oxidation of, 177
fixed, 220 Carbon dioxide, liquid standards for, 159, 159t
old, as methane source, 238b as solvent, 119–120, 120f structure of, 177
Carbonate alkalinity, 593 Carbon dioxide–carbonate system, Carbon networks
Carbonate ion, 740 in natural waters, 578–580, as rings, AP-11
Carbonate ions, 354 579f, 581f, 581t, 585–588 symbolic representation of,
in natural waters, 578–579, Carbon dioxide emissions, 222f, AP-6
580b, 581f, 581t, 244, 252f. See also Carbon rings, AP-11
582–585 Greenhouse gas(es) Carbon taxes, 306
Carbon black, climate effects allocation methods for, Carbon tetrachloride, 514t,
of, 247 305–306 627t, 629
Carbon dating, 238b anthropogenic, 220–221, 223, Carbon tetrachloride, as ozone
Carbon dioxide, 28, 96, 207, 263 223f, 224f destroyer, 78f, 79, 84
absorption spectrum for, carbon content of, 267 Carbonyl sulfide (COS), 75b, 135
217–218, 218f from deforestation, 220–221, Carboxylic acid, 108, 169, AP-9
atmospheric concentrations of, 223, 223f Carboxylic acids, 738
218, 219f, 220 energy sources of, 319f, 331 Carcinogens, 435, 610
and biomass, 224 from ethanol, 336 Ames test for, 439
as blowing agent, 80 fate of, 221–224 arsenic as, 698–699, 701–702
concentration of, 268–269, from fossil fuel combustion, chlorination by-products as,
269f, 293–294, 294f 220, 223, 223f 614–616
Index I-5
dioxins as, 471, 502–503 Chapman mechanism (cycle), 43 Chlorine monoxide, 54, 66, 67f
insecticides as, 419–420 steady-state analysis of, 44b–46b Chlorine nitrate, 65
N-nitrosamines as, 623–624 Chelating agents as chlorine reservoir
polynuclear aromatic biodegradable, 642–643, 643f molecule, 54
hydrocarbons as, 513–517, in detergents, 641 Chlorite ion, 611
514t, 515b Chemheterotrophs, 460 Chloroacetamides, 454–455
radiation as, 370, 375, Chemical absorption, of carbon Chloroacetic acid, 454–455
376–377 dioxide, 283 Chloroethene, AP-5
radon as, 376–377 Chemical feedstocks, 295 Chlorofluorocarbons(CFCs),
tritium as, 385 Chemical oxidation, in soil 84f, 251, 252f
in vehicle emissions, 516 remediation, 750 as blowing agents, 80
Carrying capacity of Earth Chemical oxygen demand ozone depletion/destruction by,
defined, 1 (COD), 563–566 55, 77–78, 78f
Carson, Rachel, 3, 421 Chemiluminescence, 199b–201b phase-out of, 83–85
Casava, ethanol from, 336 Chernobyl nuclear accident, replacements for, 80–82
Catalysts, 48 385–387 residence time for, 234, 253
in catalytic converters, China sinks for, 78, 80
110–111 air pollution in, 131–132 as trace greenhouse gases, 244
Catalytically inactive molecules, atmospheric cooling in, 250b Chloroform, in drinking water,
54–55 Three Gorges Dam in, 314 614, 614b, 627t, 629
Catalytic converters, 109–115, Chip manufacture, supercritical Chloronicotinyl, 451t
111f, 243 carbon dioxide in, 225–229 Chlorophenols, 476. See
three-way, 110 Chloracne, 434, 493 also Dioxin
two-way, 110 Chlor-alkali process, mercury as pesticides, 473
Catalytic oxidation, 648 in, 670 Chlorpyrifos, 438t, 444, 451t, 455
Catalytic processes Chlorate ion, 611 Chromated copper arsenate
of ozone destruction, 47–48 Chlordane, 420t, 514t, 527t (CCA), 697–698, 707
by atomic chlorine, 53–55 Chloride ion, 589, 590t Chromate ion, 705
by bromine, 55 Chlorinated benzenes, AP-13 Chromatogram, 399b
by nitric oxide, 50–51 long-term transport of, 526, 527t Chromium, 663, 664, 664t,
without atomic oxygen, Chlorinated cyclopentadienes, 705–706
51–53 431–432 Chronic exposures, 434
Cataracts, 35, 36f Chlorination Chrysotile, 170
Caterpillars, insecticides for, advantages of, 616–617 Cigarette smoke, 516
449–450 by-products of, 613–616 Cinnabar, 671
Cattle and sheep, as methane history of, 611–612 Clathrate compounds
source, 237 Chlorine, 670 as methane source, 241
Cayahoga River, 3 atomic, 53, 66 Clathrates, 272, 287, 287f
Cellulose, 717 catalytically inactive for hydrogen storage, 359
ethanol from, 339–340 activation of, 64–66, 65f Claus reaction, 124
as replacement polymer, molecular, 65 Clay minerals, 735
120–122, 123–124 in ozone destruction, 53–55 Clean Air Act (1970), 4, 131
Cellulostic ethanol, 339 Chlorine, in pulp-and-paper Clean coal, 129
Cement kiln incinerators, 761 production, 488–489 Clean Water Act (1972), 4
Cesium, 382–383 Chlorine dioxide Climate change
CFCs. See in pulp-and-paper projections for, 298–300, 299t,
Chlorofluorocarbons(CFCs) production, 489 301, 302t, 303
Chain reaction, 380 for water purification, 611 rate of, 298
I-6 Index
Clouds Computer chip manufacture, 2,4-D

global warming and, 207, 210, supercritical carbon dioxide in Agent Orange, 471
211, 230, 254 in, 225–229 compounds, 438t, 458
low-lying vs. high-lying, 254 Concentration Dams and reservoirs, 313–315
Coal steady-state, 231–234, 232f Daughters, radon, 372f, 375–376
arsenic in, 696 Concentration scales, 28–29, 92, DDE, 422–425, 424f, 429,
carbon dioxide emissions 93b–95b 521–522, 524
from, 319f conversion of, 92, 93b–95b DDT, 3, 6, 421–425, 518f
clean, 129 for liquids, 420–421 analogs of, 429
components of, 270 for particulates, 137–138 bioaccumulation of,
energy supply and, 313f Condensation polymers, 731 426–427, 428f
reserves of, 270 Condensed formula, AP-1 bioconcentration of, 426–427,
Coal combustion, 270 Congeners, 472 427f, 428f
emissions from, 124, 129, Containment, 747 biomagnification of, 427, 427f
270–271 Control rods, 380, 381f as carcinogen, 437
reducing emissions from, Coolant, 380 history of, 421, 423
129–130 Cooling in humans, 423,
sulfur dioxide from, 94, 99, atmospheric, 208 424–425, 424f
124, 129 stratospheric, 214 long-range air transport of, 423
Coal gasification, 284 Copper chromite, 349–350 long-range transport of,
Coal tar, 629 Copper sulfate, 542 526, 527t
Coarse particulates, 132, 133, Coral reefs, 256 metabolites of, 422, 424, 521
133f, 137, 139f, 161 Corn, ethanol from, 335, persistence of, 423
sources of, 134 337–338 as POP, 420t, 423
Cocarcinogen, 698 Corrosive wastes, 758 regulation of, 423–424
Cofactors, 698 Cost-benefit analysis, in sediments, 742
Cogeneration, 327, 327f 440–441 structure of, 422
Colburn, Theo, 517 Cracking, 512 in wildlife, 421, 423, 424, 427
Colloidal particles, removal from Creosote, 512, 629 Decision trees for oxidation,
drinking water, 605–606, 607f Critical load, 152–153 178f, 181
Combined chlorine, 617 Critical point, 228b Deforestation. See Forest(s),
Combustion Crocidolite (blue asbestos), 171 decline/destruction of
emissions from, 237 Crude oil, 274 Degradation reactions, 459–461
incomplete Crutzen, Paul, 83 DEHP, 520–521
polynuclear aromatic Cryogenic separation Denitrification, 66, 75b, 242, 243f
hydrocarbons from, of carbon dioxide, 283 Dense nonaqueous-phase liquids
512–513 Cryptosporidium, in drinking (DNAPLs), 629
products of, 761–762 water, 604, 609, 618 Dental fillings, mercury in,
molten salt, 762 Cultural eutrophication, 640 668–669
Combustion cleaning, 130 Curie (Ci), 374 Depleted uranium, 378
“command and control laws,” 4 Cyanazine, 454 Depolymerization of plastics,
Commercial energy, 262 Cyanide, 746 731–732
Comprehensive Environmental Cyanides, in wastewater, Desalination
Response, Compensation 646–647 electrodialysis for, 643, 644f
and Liability Act. See Cycloalkanes, 274 ion exchange for, 643
Superfund Act Cyclodienes, 431–432 reverse osmosis for, 608, 608b
Compressed natural gas Cyclohexane, 274, AP-11 DES (diethylstilbestrol), 523
(CNG), 273 Cyclopentadienes, 431, 433b DeSimone, Joseph, 119–120
Index I-7
Destruction and removal Dinitrogen pentoxide, 75b Dose, 435

efficiency, 760 Dinitropyrene, 516 lethal (LD50), 437
Detergents, water contamination 1,4-dioxin, 470 lethal oral (LOD50),
by, 640–641 Dioxins, 420t, 469–477, 518f, 523 437, 438t
Deuterium, 380, 384, 393–394 bioaccumulation of, 492 threshold, 438, 439
Diacylhydrazine insecticides, as carcinogens, 471, 502–503 Dose–response relationships,
449, 450f chlorine content of, 435–438, 436f, 439
Diatomic nitrogen, 28, 216. 491–492, 491f Drugs, in wastewater, 645–646
See also Nitrogen decrease in, 492 Dry-cleaning solvents,
Diatomic oxygen, 28, 91–92, 207, deducing origins of, 475b replacements for, 120
216. See also Oxygen environmental contamination Dry deposition, 148
light absorption characteristics by, 470–471 Dust, 132. See also Particulates
of, 30 in food and water, 500–501,
in paper production, 91 500f
Diazinon, 438t, 444, 455 detection of, 476–477 Earth
Dibenzofurans (DFs), 484–485. health effects of, 502, 503, 504f energy balance of, 212,
See also Furans long-range transport of, 214, 214f
Dibenzo-p-dioxin, 471, 474 526, 527t energy emissions of, 209–212
Dibromoacetonitrile, 611 numbering system for, 471–473 energy source of, 206–207, 312
Dicamba, 459 in pentachlorophenols, 474 Earth Day, 3
Dichloroacetic acid, 614 production of, 470–471 Ecoestrogens, 519
Dichlorobenzene, 419 sources of, 470–471, 487–489, Ecological footprint, 1, 2–3
1,4-dichlorobenzene, 508 490–492, 721 EDTA
Dichlorodiphenyldichloroethene TEQ factors for, 498–500, 499t (ethylenediaminetetraacetic
(DDE), 422 toxicity of, 496–498 acid)
1,2-dichloroethane, 514t Diphenol ether, 529 as chelator, 665
1,1-dichloroethene, AP-5 Diphenylamine, 446 in water hardness testing, 595
1,2-dichloroethene, AP-5 Direct chemical oxidation, 652 Effective concentration, 571
Dichloromethane, 717 Dirty dozen chemicals, 419, Einstein, Albert, 1, 36
Dichloroperoxide, 68 420t, 423 Electric cars, 355
2,4-dichlorophenoxy acetic acid Disinfection. See also Electricity, from solar energy,
(2,4-D), 458–459 Water purification 326–327, 330
Dichlorprop, 459 of water, 602–618 Electrochemical soil remediation,
Dichlorvos, 438t, 443f, 444 by-products of, 611 749–750, 750f
Dichromate ion, in chemical Disinfection by-products Electrodeposition, 684
oxygen demand, 563–564 (DBPs), 611 Electrodialysis, in wastewater
Dichromomethane, 514t Dispersants, 721–723, 723f treatment, 643, 644f
Dicofol, 423 Disposal Electromagnetic spectrum,
Dieldrin, 420t, 426t, 432, 518f, of hazardous wastes, 759 30, 31f
527t, 628 Dissociation reaction, 37–38 Electron capture detection, of
Di-2-ethylhexyl phthalate for O2, 38–39, 42 pesticides, 537b–539b
(DEHP), 514t, 520–521 Dissolved organic carbon (DOC), Elemental chlorine, in pulp-and-
Digestors, 566 153, 564–565 paper production, 488–489
Dimethoate, 438t, 446 Distillation, 337 Elimination, rate of, 231–232
Dimethyl ether, 345 petroleum, 275, Endocrine system, 519
Dimethylmercury, 672 276b–278b, 277f “end-of-the-pipe solutions,” 4
Dimethyl sulfide (DMS), 135 Disulfide ion, 568t, 569 Endosulfan, 432, 433b–434b, 438t
oxidation of, 251 Dobson units (DU), 59 Endosulfan sulfate, 433b
I-8 Index
Endothermic reactions, 328, Environmental estrogens, 517–525 Ethers, AP-8

49b–50b, 49f, 179 dose–response curve for, as alternative fuels, 333,
Endrin, 420t 525, 525f 345–346
Energy, 5, 6 effects of Ethoxy group, AP-8
commercial, 262 in humans, 522–525 Ethoxylates, 519–520
Earth’s emissions of, 209–212 on wildlife, 521–522 Ethyl alcohol, 334
light, 37–40 sources of, 519, 520–521 Ethylbenzene, 166, 281
maximum emission of, 206 structure of, 518f Ethylene, 185, 728, AP-4
photon, 37–40 types of, 519–521 Ethylenediaminetetraacetic acid
released in nuclear processes, Environmental Protection (EDTA)
394–395 Agency (EPA), 3, 4 as chelator, 665
renewable, 312–333. See also Environmental regulation in water hardness testing, 595
Renewable energy history of, 3–4 Ethylene dibromide, 514t
rotational, 217 Environmental tobacco smoke Ethylene dibromide, in
source of Earth’s, 206–207, 312 (ETS), 168–170 gasoline, 688
sources of, 312–313, 312f Environmental toxicology, Ethylene dichloride, in
vibrational, 217 434–441 gasoline, 688
Energy balance, of Earth, 212, dose–response relationships in, Ethylene glycol, 350
214, 214f 435–438 Ethylmercury, 676
Energy conversion risk assessment and, 439–440 Europe, air pollution in, 104, 118,
limitations on, 328–329 Equilibrium, 43 131, 156–157
Energy-dense fuels, 333 Epidemiology, 434 Eutrophication, 640
Energy efficiency Epilimnion, 566 of reservoirs, 314
carbon dioxide emissions and, Epoxidation, 461 Exajoule (EJ), 262
291–292 Esters, AP-9 Excited state, 38
Energy emission as alternative fuels, 333, Exothermic reactions, 42, 49b–50b,
rate of, 209, 210, 211–212 346–347 49f, 177, 179, 195
Energy payback, 318 Estradiol, 518f, 645. See also Exposure controls, 4
Energy use Environmental estrogens Eye conditions
in developing countries, 313 Estrogens, 517. See also ozone depletion/destruction
trends in, 262–263, 292–293 Environmental estrogens and, 35–36
in United States, 312 Ethane, 272, 277b, 277f,
Energy vector, hydrogen as, 360 422, AP-1
Engines Ethanol, 727, AP-7 Farman, Joe C., 60
catalytic converters for, 98, attractions of, 336 Federal Water Pollution Control
109–115, 111f from biomass, 335–340 Act Amendments of 1972.
homogeneous charge from carbohydrate See Clean Water Act
compression, 115 fermentation, 335–337 Feedback
knocking in, 280 controversy over, 337–338 negative, 230
particle traps for, 115 from corn, 335, 337–338 positive, 230, 240
Enhanced greenhouse effect, 211, disadvantages of, 334–335 Fenitrothion, 438t, 444
241, 255 and emissions, 334, 336, Fermentation, 566, 753
Enhanced oil recovery (EOR), 289 337–338 acid, 717
Enthalpy (heat) changes, 37 production of, 335–340, 339f to produce ethanol, 335–337
Entropy, 328–329 as vehicular fuel, 334–335, Ferrate ion, 652
Environmental chemistry, 337, 338 Ferric arsenate, 703
defined, 1 Ethene, 155, 185, 335, Ferric chloride, 478, 703
Environmental disasters, 3 728, AP-4 Fertilization, carbon dioxide, 224
Index I-9
Fertilizers Fluorinated surfactants, 533 Lewis structures of, 176b, 177

as source of nitrous oxide, Fluorine, in ozone destruction, 56 methyl, 54, 180, 182
242–243 Fluorosilicic acid, 591 nitrate, 191
nitrates from, 621–622 Fluorotelomer alcohols, 534 in oxidation, 95–97
Filtration, for water purification, Fly ash, 720–721 Fuel cells, 353f
605–609, 607f Food alkaline, 353, 353f, 354
Fine aerosol cadmium in, 693 hydrogen–oxygen,
composition of, 146f dioxins in, 476, 500–501, 500f 351–352, 352f
Fine particulates, 132, 133, 133f, furans in, 494, 500–501, 500f methanol in, 356
134–137, 139f, 146, 161 heavy metals in, 666 molten-carbonate (MCFC),
Fipronil, 451t mercury in, 673–674 353f, 354
Fire retardants, 528–529, 532–533 nitrosamines in, 624 other uses for, 356
Fires. See also Combustion PCBs in, 493–494, 500f phosphoric acid-based
air pollution from, 125–127, Food chain, 427, 428f (PAFC), 353f, 354
162–163 Food web, 427, 428f polymeric–electrolyte–
dioxins and furans from, Fool’s gold, oxidation of, 569–570 membrane (PEMFC),
490, 492 Forest fires 352, 352f, 353f
First-order relationship, 231 air pollution from, 162–163 in power plants, 354–355
Fish Forest(s) solid-oxide (SOFC), 353f,
dams and, 314 as nitrous oxide source, 243 354–355
dioxins in, 476, 500f decline/destruction of in vehicles, 352–353
furans in, 500, 500f from acid rain, 154–155 Fuel NO, 99
heavy metals in, 666 gas emissions from, 106, Fuel rods, 381, 381f
mercury in, 314, 670, 673–674, 108–109 reprocessing of, 383f
673f, 674f, 676 Formaldehyde, 169, AP-8 Fuels
PCBs in, 500, 500f health effects of, 164–166 alternative, 333–350
pesticides in, 421, 425–427, 430 Formaldehyde gas energy-dense, 333
water acidification and 104, decomposition of, 178f, 180 organic, 333
105–106, 105f, 154 in methane oxidation, 182, 183f Fugacity, 462b–464b, 463f
Fission products, 382, 385–387 Formic acid, AP-9 Fugitive emissions, 762
Fission reactors, 379–383, Fossil fuel combustion Fulvic acid, 738
379t, 381f emissions from, 271 Fumigants, 418, 419
future of, 385 Fossil fuels. See also Coal, Natural Functional groups, AP-7–AP-9,
Fission, 379. See also Nuclear gas, Petroleum AP-8t
energy/power definition of, 220 Fungicides, 416–417, 416t,
advantages/disadvantages hydrogen from, 362, 363 419, 473
of, 386f as methane source, Furans, 420t, 484–487,
process of, 380–383 237–238, 238b 486b–487b
Fixed carbon, 220 as nitrous oxide source, 243 bioaccumulation of, 492
Flame ionization detector, Four Rs, of waste management, 723 chlorine content of,
398b–401b Fractions, petroleum, 275 491–492, 491f
Flaring, 125, 273, 277b Free-radical reactions in food, 494, 500–501, 500f
Flavonoids, 520 rates of, 49b–50b, 49f health effects of, 503
Flow batteries, 321 Free radicals, 48 long-range transport of, 526, 527t
Flue-gas desulfurization, 129 fate of, 178f, 189–192 sources of, 487–489,
Fluidized bed combustion, 130 hydroperoxy, 176b, 180 490–491, 721
Fluorapatite, 591 hydroxyl. See Hydroxyl TEQ factors for, 489, 499t, 500
Fluoride ion, 589, 590t, 591 free radicals toxicity of, 497–498
I-10 Index
Fusion, 379. See also Nuclear Gasoline engines Grasshopper effect, 528
energy/power catalytic converters for 83–88, Great Lakes, phosphate
Fusion reactors, 393–394 84f, 87f, 98, 109–115, 111f contamination in, 640
particle traps for, 115 Green chemistry, 1, 3
Gas scrubber, 721 arsenic/chromium removal
Galena, 681 Genetically engineered from pressure-treated
Gamma (␥) particle, 369, 369t plants, 457b wood, 707–708
Gas Genistein, 518f, 520 awards for, 7
carbon dioxide emissions Geoengineering, of climate, 248 benign paper bleaching agents,
from, 319f Geothermal energy/power, 489–490
energy supply and, 313f 322–325, 322f, 323f biodegradable antiscalant and
Gas chromatography (GC), drawbacks of, 324 dispersing agent, 721–723,
398b–401b for electricity and heating, 722f, 723f
Gas chromatography/mass 323, 324 biodegradable chelating agent,
spectrometry (GC/MS), energy supply and, 313f 642–643, 643f
540b–543b potential sites for, 323–324, 323f biodegradable polymers,
Gas(es) Giardia lamblia, in drinking water, 295–297
in clean air 67–72, 92, 95–97 609, 618 chemical feedstocks from
concentration scales for, Glass, recycling of, 724 glycerin, 348–349
28–29, 92, 93b–94b Glazes, lead in, 683 definition of, 4
interconversion of, Global circulation models, enzymatic cotton textile
93b–94b 254–255 processing, 565–566
fate of, 178f Global warming, 205, 206 lead replacement in
from natural sources, 92, 95t aerosols in, 248–251 electrodeposition
oxidation of 67, 92 anthropogenic, 209, 251–252, coatings, 684–685
photochemical decomposition 252f, 255 principles of, 5–6
of, 178f, 179–180, 182 artificial, 211 real-world examples of, 7–12
trace, in clean air, 92, 95t clouds and, 207, 210, 211, recyclable carpeting, 732–733
in unpolluted air, 28 230, 254 reduced risk pesticides,
volume of, 29 contributors to, 251–252, 252f 449–450
Gas(es), atmospheric geography of, 252–254, 253f supercritical carbon dioxide in
infrared absorption by, 210 health effects of, 256, 303–304 computer chip
residence time of, 231–234 particulates in, 248–251 manufacture, 225–229
Gasohol, 334 positive feedback in, 220 targeted insecticides, 449–450
Gasoline, 342f projections for, 297–298 termite control, 450–451,
components of, 279–280 for climate change, 451f, 451t
in groundwater, 629 297–300, 299t Greenhouse effect
lead in, 687–689, 688f for sea level, 300–301 definition of, 211
reformulated, 281 for specific regions, 301, energy emissions and,
Gasoline additives, 281t 302t, 303 209–212, 210f
catalytic converters for, 98, signs of, 255–256 enhanced, 211, 241, 255
109–115, 111f temperature trends and, mechanism of, 206–214
ethanol as, 334 207–209, 208f model of, 211–212, 213b
lead as, 280 Glucose, 335, 336 runaway, 241
methanol as, 341 Glycerin, 347, 348–349, 349f Greenhouse gas emissions, 268
MTBE as, 345 Glyphosate, 455–456 international agreements on,
octane boosters as, 280 Gothenburg Protocol, 118 304–306
particle traps for, 113, 402, 115 Graphite, 380, 411 from reservoirs, 314
Index I-11
Greenhouse gas(es), 210f, 251, Halides, 72, 130 High-level waste (HLW), 388
252f, 254 Halogenated acetic acids, in Homogeneous charge
atmospheric residence time drinking water, 613–614 compression ignition, 115
for, 234 Halons, 78f, 82, 84 Homogeneous gas-phase
carbon dioxide as, 211, 264. Hardness index, for natural mechanism, 192–194,
See also Carbon dioxide waters, 595–596 199–200
chlorofluorocarbons (CFCs) Harpin technology, 86–87 Hormesis, 377
as, 244 Hatters, mad, 671 Hormones, 517. See also
HCFCs as, 244 Hazard evaluation, 439 Environmental estrogens
HFCs as, 244 Hazardous air pollutant (HAP), 166 Human activities
IR absorption by, 219f Hazardous wastes, 721, 758 impacts of, 1–2
major, 217–224, 229–230 management of, 758–759 Human exposure, 439–440
methane as, 234–236 Haze Humic acid, 738
nitrous oxide as, 242–243 aerosols and, 146 Humus, 738–739
trace, 231, 242, 244 from air pollution, 112–113, Hydroxyl free radical
water vapor as, 211 146, 162–163 radiation and, 370
Greenhouse warming, 205 Health effects Hybrid vehicles, 355–356
Green/natural pesticides, 417, of global warming, 303–304 Hydrides, oxidation of, 148, 148f
447–448 Heat exchanger, 326 Hydrocarbons, AP-1
Gross domestic product Heat pumps, 325 anthropogenic, 108–109
(GDP), 262 Heavy metals, 663–664 aromatic, 274
Ground state, 38 bioaccumulation of, 666 emission of
Groundwater, 558, 558f, 618–635, biomagnification of, 666 reduction of, 103, 106–115
618f. See also Water densities of, 664, 664t nonmethane, 184
contamination of, 619–622 poisoning by, 665, 675–676, oxidation of, 185–189, 188f, 191
nitrate, 620–624, 621f 680, 681, 690–691, 705 in smog, 97
organic chemical, 626, speciation of, 664–665 sources of, 98
627t, 628–630 toxicity of, 665–666 as volatile organic compounds
perchlorate, 625–626, 625f Heavy water, 380, 384 (VOCs), 97, 98–99
decontamination of, 630–635 Helium, 368 Hydrochloric acid, 147, 288
bioremediation for, 631, Hemicellulose, 339–340 Hydrochlorofluorocarbons
632t–633t Henry’s law constant (KH), (HCFCs)
iron for, 633–635, 634f 126–127, 560 as trace greenhouse
natural attenuation for, Heptachlor epoxide, 432, 514t gases, 244
631, 632t–633t, 633 Herbicides, 416–417, 416t, Hydrocyanic acid, 646
physical and chemical 452–459, 457b, 473. Hydrodesulfurization, 112
processes for, 630–631 See also Pesticides Hydroelectric energy/power, 312,
reductive degradation for, triazines, 452–454 313–315, 313f
634–635 Hexabromocyclododecane carbon dioxide emissions
in situ remediation for, (HBCD), 532 from, 319f
633–635, 634f Hexachlorinated cyclohexane, 430 and dams and reservoirs,
depletion of, 619 Hexachlorobenzene (HCB), 313–315
nature of, 618, 618f 419–420, 420t, 426t, 514t in developing world, 314
plumes in, 630, 630f Hexachlorocyclohexane, environmental and social costs
430–431, 527t of, 314
Hexaflumuron, 451, 451f, 451t as indirect solar energy, 313
Half-life, 372, 372f High-density polyethylene and wetlands creation,
Half-life period, 232–233 (HDPE), 728–730, 729t 314–315
I-12 Index
Hydrofluorocarbons (HFCs) Imidacloprid, 451t Iodine monoxide (IO), 135

as trace greenhouse gases, 244 Immobilization, 747 Ion chromatography, 657b–660b
Hydrogen, 717 Incineration, 749 Ion exchange, in wastewater
Hydrogen atom dioxins and furans from, treatment, 643–644
abstraction of 490–491 Ionic liquids (ILs), 122–123
in stratosphere, 194 of solid waste, 719–721 Ionizing radiation. See Radiation
in troposphere, 179, of toxic wastes, 759–762 IQ, lead exposure and,
181, 182 Incinerators 689–690, 690f
Hydrogen bonds, AP-10 emissions from, 720–721, Iron
Hydrogen bromide, 55, 529 761–762 in groundwater
Hydrogen chloride, 65, 648 output of, 720 decontamination,
as chlorine reservoir types of, 720, 760–761 633–635, 634f
molecule, 54 Indoor air pollution, 163–171. in natural water, 567, 575f
natural sources of, 95t See also Air pollution, indoor Iron fertilization, 290–291
Hydrogen cyanide, 169 Inductively coupled plasma Iron pyrite, oxidation of, 569–570
Hydrogen economy, 342f, 350 spectroscopy (ICP), Iron sulfate, 570
Hydrogen fluoride, 81 770b–773b in water purification, 605
Hydrogen fuel, 284, 350–363 Infrared light (IR), 30, 206, 207f, Isocyanuric acid, in water
advantages of, 350, 351 210f, 213b, 215–216, 230 chlorination, 613
Hydrogen halides, 97 thermal, 209–210, 210f, 211, Isopentane, 323
Hydrogen peroxide, 126 214, 215, 231, 234 Isoprene, 108
production of, 190, 191 Inhalable particulates, 138 Itai-itai disease, 694
Hydrogen sulfide, 111 Insecticides, 416–417, 416t, 473.
in Claus reaction, 124–125 See also Pesticides
natural sources of, 95t broad-spectrum, 449 Kekulé structures, AP-12
sources of, 124–125 carbamate, 446–447 Kepone, 518f, 519
Hydroperoxy radical natural/green, 438t, 447–448 Ketones, 169
Lewis structures for, 176b organic, 418 Kinetic energy, 317
Hydroxyl free radicals organochlorine, 418–419, Krypton, 380, 382
fate of, 178f 420t. See also Kyoto Accord, 304–305
in hydrogen abstraction, 179, Organochlorine
181, 182 compounds
in oxidation, 92, 95–97, 171, organophosphate (OP), Laccase, 123
177, 178, 178f, 182–183, 441–446, 442f, 443f, Lakes. See also Water, natural
183f, 192, 235 455, 460 acidification of, 151, 153, 154f
radiation and, 370 traditional, 417–418 aluminum ion in,
sink for, 189 In situ remediation, for 153–154, 154f
in smog production, groundwater methylmercury in, 672,
185–187, 188f decontamination, 673f, 674
Hydroxyl group, AP-7 633–635, 634f Landfills, 715
Hydroxyl radical, 64 Integrated pest management carbon dioxide from,
Hypochlorous acid, 65 (IPM), 449, 450 717–718
Intergovernmental Panel on components of, 716, 716f
Climate Change (IPCC), decomposition in, 716–718
Ibuprofen, 645 255, 293 for hazardous waste, 759
synthesis of, 7–11 International Energy Agency leachate from, 717
Ideal gas law, 29, 93b, 94b (IEA), 263 methane from, 718
Ignitable wastes, 758 Iodine, in water purification, 617 as methane source, 237
Index I-13
Leachate Light absorption, 30 Maximum contaminant level

composition of, 717 molecular vibrations and, (MCL), 454
control and treatment 214–216 Maximum contamination level
of, 719 Light energy, 36–40 (MCL), 611
Lead, 663–666, 664t Lignin, 270, 339–340, Maximum contamination level
from batteries, 355 488–489, 488f goal (MCLG), 615
in drinking water, 681–682 Lime, 721 Maximum residual disinfectant
in environment, 679f, 680 Liming, 740 level (MRDL), 611
in gasoline, 687–689, 688f Limiting nutrient, 640 MCPA, 459
health effects of, 689–691, Lindane, 431, 438t Mechanism I, of ozone
690f, 691f Linear-no-threshold destruction, 48, 52f
ionic, 680–682 (LNT), 377 Mechanism II, of ozone
in natural waters, 685–686 Liner, landfill, 716f, 719 destruction, 51, 52f
from radon decay, 372f, 373, Liquid injection incinerators, 761 Mecoprop, 459
375–376 Liquified petroleum gas Medical waste, 721
sources of, 681, 683–684 (LPG), 274 Membrane separation
substitute for, 684–685 LOD50, 437, 438t of carbon dioxide, 283–285
uses of, 679–680, Long-range transport of Membrane technology, in water
683–687 atmospheric pollutants purification, 606–607
Lead acetate, 683 (LRTAP), 525–528, 527t, Mercuric oxide, 671
Lead arsenate, 684 528f, 534 Mercury, 663–666, 664t
Lead chromate, 683 Love Canal, 3 amalgams, 668–669, 670
Lead poisoning, 680, 681, Low-density polyethylene bioconcentration of, 673
690–691 (LDPE), 728–729, 729t biomagnification of, 674
Lead sulfide, 681 Lung cancer, 170, 376–377, 516. in fish, 314, 670, 673–674,
Lethal concentration (LC), 439 See also Carcinogens 673f, 674f, 676
Lethal dose (LD50), 437 Lung disease in food, 314
Lethal oral dose (LOD50), air pollution and, 156, 159 international controls
437, 438t Lyase, 565–566 on, 678
Lewis structures, of free radicals, ionic, 671–672
176b, 177 in natural waters, 671–674, 673f
Life cycle assessment (analysis), Mad hatters, 671 in sediments, 742
734–735, 735f Magnesium carbonate, 288 toxicity of, 664, 667, 670–672,
Light Magnesium chloride, 288 675–676, 687
absorption of Magnesium hydroxide uses of, 666–672, 676–677
by aerosols, 246f, 247 in water purification, 604 in vaccines, 676–677
by particulates, 246f, 247 Magnesium ions, 589, 590t vapor, 664, 666–668
infrared, 30, 206, 207f, 209, in drinking water, removal of, sources of, 667–668
210f, 213b, 215–216, 602, 604 Mercury cell batteries,
230–231, 234. See also Malaoxon, 445 671–672
Thermal infrared Malathion, 426t, 438t, 443f, Mercury emissions, 667–670
reflection of 445, 455 Meta, AP-13
by aerosols, 246–247, 246f Marsh gas, 236 Metabolites, 422
by particulates, Mass balance Metal hydride, for hydrogen
246–247, 246f of arsenic, 703 storage, 357–358, 359f
ultraviolet (UV), 27, 30, 32, of PCBs, 481–482, 481f Metallothionein, 694
33, 207, 207f Mass burn incinerator, 720 Metals
visible, 30, 206, 207f Mass number, 368 recycling of, 724
I-14 Index
Methane, 51, 277b, 277f, AP-1 Methyl iodide Molecular oxygen, dissolved, in
atmospheric concentration of, natural sources of, 95t natural waters, 559–562
235, 236f, 239 Methylmercury Molecular vibrations, light
determination, 398b–401b safe limit for, 677–678 absorption and, 214–216.
trends in, 239–240, 239f sources of, 672–674, 673f, 676 See also Vibration, molecular
as greenhouse gas, 234–236 toxicity of, 672–673, Molecules per cubic centimeter
IR absorption by, 216, 219f, 675–676 scale, 28, 93b
234–235 Methyl orange, in alkalinity Molecules-to-moles conversion,
from landfills, 718 measurement, 593 93b–94b
lifetime of, 235, 253 Methyl parathion, 438t, 445 Mole fraction scale, 29
methanol from, 343–344 Methyl radical, 180, 182, 183f Moles-to-molecules conversions,
natural sources of, 95t Methyl tertiary-butyl ether 93b–94b
oxidation of, 96, 181–184, 183f (MTBE), 345–346 Molina, Mario, 83
reduction of, 292 in groundwater, 628–629, Molten-carbonate fuel cell
from reservoirs, 314, 315 632t, 633 (MCFC), 353f, 354
residence time for, 234 Metolachlor, 438t, 455 Molten salt combustion, 762
sinks for, 235 Metribuzin, 454 Monomethylmercury, 672
sources of, 272 Mexico City, air pollution in, 104, Montreal Protocol, 83–85, 244
Methanearsonate ion, 696 157, 158, 160 Mortality, from air pollution,
Methane emissions, 236, 236f, Micelle, 120, 120f 157, 170
251, 252f Microfiltration, 606, 607f MTBE (methyl tertiary-butyl
sources of, 236–238, Micrograms per cubic meter ether), 281, 281t, 345–346
240–241 (mg/m3), 94b, 137 in groundwater, 628–629,
anthropogenic, 237–238 Micrograms per gram (mg/g) 632t, 633
natural, 236–237 scale, 421 Municipal solid waste (MSW), 715
Methane hydrates, 241, 272 Microorganisms, disinfection Mutagens, 435
Methanesulfonic acid, 251 for, 604
Methanogenic decomposition, 718 Micropollutants, 717
Methanol, 281t, 334, 335, AP-7 Minamata disease, 675–676 Naming organic
advantages and disadvantages Mineralization, 459, 649 molecules, AP-3
of, 341 Mining Nanofiltration, 607, 607f
in fuel cells, 356 cadmium in, 693–694 Naphthalene, 508
as gasoline additive, 341 mercury in, 669–670 Natural attenuation
production of, 342–345, 345f tailings from, 602–603, 642 for groundwater
as vehicular fuel, 341, 345 uranium, 376, 383f, 384 decontamination, 631,
in wastewater treatment, 638 Mirex, 420t, 426t, 432, 527t 632t–633t, 633
Methemoglobinemia, nitrates Mist, 132 Natural gas, 272f
and, 622–623 Mixed oxide fuel (MOX), 391 components of, 272
Methoxychlor, 429, 518f, 519 Mixing ratios, 29 as fuel, 273
Methoxy group, AP-8 MMT (methylcyclopentadienyl reserves of, 272
Methylcobalamin, 672 manganese tricarbonyl), 280 Natural/green pesticides, 417,
Methylcyclopentadienyl Moderator, 380 447–448
manganese tricarbonyl Modular incinerator, 720 Nature’s interest, 1
(MMT), 280 Mole, 93b–94b Negative feedback, 230
Methylcyclopentane, 274, AP-11 Molecular chlorine, in water Nicotine, 438t, 447
Methylene chloride, 627t, 629, chlorination, 612 Nitrate ion, 151, 242, 243f
632t, 633 Molecular nitrogen, 576, 576t in drinking water, 620–621
Methylene dichloride, 514t Molecular oxygen, 177 hazards of, 622–624
Index I-15
Nitrates photochemical decomposition Nuclear fuel cycle, 383–384, 383f

in groundwater, 620–622, 621f of, 101–102, 102f Nuclear waste, 389, 390b
hazards of, 622–623 standards for, 159, 159t high-level, 388
as particulate, 137, 146f Nitrogen oxide gases storage of, 391–392
sources of, 621–622 and smog, 99, 101 Numbering systems, AP-5, AP-13
Nitric acid, 64, 388, 576 Nitrogen oxides, 721
in acid rain, 147 concentration of,
production of, 189–190 chemiluminescent Ocean acidic, 285–288,
in smog, 97, 98 determination of, 579, 586
Nitric oxide, 102f 199b–201b Ocean neutral, 288, 586
and acid rain, 147 detection of, 199–200 Oceans
detection of, 199–200 formation of, 178f, 184, carbon dioxide sequestration
emission of, 97, 98 186, 188f in, 285–289, 285f, 286f,
fuel, 99 from hydrogen fuel, 351 287f, 290–291
natural sources of, 95t oxidation of, 100, 101–103, 102f as carbon dioxide sink, 222,
in oxidation, 99 sources of, 99–100, 98 223, 223f
oxidation of, 100, 101–102, Nitrogen trioxide, 75b sea level rise and, 300–301
102f, 178f, 180, 195 Nitropyrene, 516 as source of dimethyl
in ozone destruction, 50–51 Nitrosamines sulfide, 251
production of, 99–100 as carcinogens, 169 as source of nitrous oxide, 242
in smog, 97, 99, 101, Nitrous acid, 167 Octa, 531
189–191 photochemical decomposition Octachlorodibenzo-p-dioxin
sources of, 100 of, 189, 191 (OCDD), 474. See also
thermal, 99 Nitrous oxide, 50, 251, 252f Dioxins
Nitrification, 242, 243f atmospheric concentration Octane numbers, 280, 281t
Nitrilotriacetate (NTA), of, 242 1-Octanol, 425
641, 642f IR absorption of, 242 Octylphenol, 518f, 519
Nitrite residence time for, 234, 253 Oil
in natural waters, 576–577, sinks for, 243 carbon dioxide emissions
576t, 577f sources of, 242–243 from, 319f
Nitrite ion, 622 as trace greenhouse gas, energy supply and, 313f
in natural waters, 242, 243f 242–243 Oil, vegetable
Nitrogen Nonmethane hydrocarbons, 184 as alternative fuel, 346–348
cycling of, 242–243, 243f Nonpoint sources, 642 Oil recovery, enhanced, 289
Nitrogen, in wastewater, removal Nonylphenol, 518f, 519 Oil shales, 279
of, 638–639 No observable effects level Open uses, 480
Nitrogen compounds, in natural (NOEL), 438, 439–440 Organic fuels, 333
waters, 567, 567f, 575–577, North America, air pollution in, Organic molecules, naming, AP-3
576t, 577f 104–105, 105f, 117–118, 131 Organic solvents, replacements
Nitrogen dioxide, 33, 50, 64 NOX (nox), 100, 118f for, 119–123
absorption spectrum of, reduction of, 106–108, 116–118 Organochlorine compounds
100, 100f NOX emissions bioaccumulation of, 425–427,
formation of, 100–102, 102f from alternative fuels, 333, 428f, 429
health effects of, 167 334, 351 as pesticides, 418
nitric acid from, 103 Nuclear energy/power, 378–395 properties of, 419
nitric oxide oxidation to, carbon dioxide emissions solubility of, 419
100–103, 102f from, 319f toxicity of, 419, 430
in oxidation, 100, 100f energy supply and, 313f Organochlorines, 519
I-16 Index
Organophosphates (OPs), Oxidative transformation, 732 Ozone-depleting substance

441–446, 442f, 443f, 451t, Oxide anion, 354 (ODS), 79
455, 460 Oxycombustion, 24 Ozone depletion/destruction,
classes of, 443, 443f Oxygen, 28 27, 30
health effects of, 442, 447 abstraction of, 195 anthropogenic chemicals and,
as nerve poisons, 441–442 atomic, 195 77–79
Organosulfur compounds, 602 diatomic and cancer, 33–35
Organotin compounds, 697b in paper production, 489 and effects on nonhuman
Ortho, AP-13 loosely bound, 194–195, 194t organisms, 36
Ouch-ouch disease, 694 molecular, 177 and eye conditions, 35–36
“Our Common Future” Oxygenated hydrocarbons, 113 in mid-latitudes
(UN report), 2 Ozone, 92, 251, 252f chemistry behind,
Our Stolen Future (Colburn), 517 abstraction of oxygen from, 195 75b–76b
Overall reaction, 47 and asthma, 156 over Antarctic, 63–70
Oxidation, 92 in clean air, 92, 79 over Arctic, 71–74
of ammonia, 639b creation of in stratosphere, reactions that cause, 67–69, 71f
of carbon monoxide, 177 40–41 in temperate regions, 63
catalytic, 648 destruction of in stratosphere, Ozone destruction
decision tree for, 178f, 181 42–43 catalytic processes of, 47–55
direct chemical, 652 geographic variation in, Ozone holes, 27
of ethene, 149 104–106, 105f above Antarctica, 60–61
as exothermic process, 177, 179 ground-level, 97, 101 above Arctic, 61
of hydrocarbons, 185–189, 188f reduction of, 103, discovery of, 60
hydroxyl free radicals in, 106–109 size of, 61f, 62f, 70–71
70–72, 95–97, 171, 177, in smog, 97, 101–102. variation in, 60, 64,
178, 178f, 182–183, 183f See also Smog 69–70, 73
intermediates in, 182–183, health effects of, 158–160 Ozone layer, 43
182f, 184, 184f in North America, defined, 27
of iron pyrite, 569–570 104–106, 105 location of, 29f, 41
of methane, 96, 181–184, 183f overhead amount of, 59, 61f, physics and chemistry of, 30
microbial, 460–461 62f, 67f
of natural gases, 95–97, 95t variation in, 60, 63f,
of nitric oxide, 102, 102f, 69–70, 69f PAHs. See Polynuclear aromatic
178f, 180 in paper production, 489 hydrocarbons
of nitrogen, 575–577, 576t, 577f seasonal variation in, Paper, recycling of, 725–727
of organic matter in water, 104–105, 105f Para, AP-13
566–567 standards for, 103, 159, 159t Para-dichlorobenzene, AP-13
reactions in, 177–181, 178f stratospheric, 207 Para-dichlorodiphenyl-
of sulfur, 177, 568, 568t transport of, 104–106 dichloroethane (DDD;
of sulfur dioxide, 192–194 tropospheric TDE), 429
tropospheric, 177–193 as greenhouse gas, 245 Para-dichlorodiphenyl-
Oxidation number, 271, 334, 336, IR absorption by, 245 trichloroethane (DDT), 421
559–561, 560b, 566–567, residence time for, 245 Para-dioxin (p-dioxin), 470
568t, 576–577, 576t, 617, sources of, 245 Paraquat, 438t, 460
646, 652, 725, 749 urban, 186 Parathion, 426t, 438t, 443f, 444
Oxidation reactions, 91–92, 96 UV filtering by, 32 Paris green, 696
Oxidation/reduction Ozone concentration Partial pressure, 29, 92
of pesticides, 460 altitude and, 28–29, 29f Particle traps, 115, 516
Index I-17
Particulates Passive smoking, 169, 170 Perfluorooctane sulfonate

absorption by, 160, 161f PBDEs (polybrominated diphenyl (PFOS), 533
acidic, 136–137 ethers), 529–531 Perfluorooctanoic acid
adsorption by, 160, 161f PCBs, 420t, 477, 486b–487b, (PFOA), 534
aerosol, 133, 135, 136, 137. 518f, 519, 523–524 Permafrost
See also Aerosols biomagnification of, as methane source, 238b,
atmospheric cooling by, 482–484, 482f 240–241
247–249, 250b, 252f bioremediation of, Permethrin, 438t, 448, 451t
climate-modifying effects of, 754–755, 755f Peroxyacetylnitrate (PAN),
246–251 commercial uses of, 480 190–191, 334
coarse, 132, 133, 133f, 134, cycling of, 480–484 Peroxydisulfate anion, in
137, 139f, 161 declining concentration of, wastewater treatment, 652
concentration scale for, 483–484, 483f Peroxymonosulfate anion, in
137–138 in food, 493–494, 500f wastewater treatment, 652
definition of, 132 furan contamination of, Peroxy radical, 178f, 180–182,
fine, 132, 133, 133f, 134–137, 484–487, 486b 183f, 184, 186
139f, 161 health effects of, 477, 493, 503 Persistence, 6
PAHs and, 510 long-range transport of, Persistent organic pollutants
global distribution of, 249f, 526–527, 527t (POPs), 419, 420t, 423,
250–251 numbering of, 478–479 431–432
global warming and, 248–251 persistence of, 480–482 pE scale, 571–574, 575f
in haze, 146, 146f prenatal exposure to, Pesticides, 415, 461
health effects of, 160–162 494–496, 495f arsenic in, 696
from incineration, 720–721 in sediments, 742 degradation of, 459–461
inhalable, 138 sources of, 480, 487–489 electron capture detection of,
light absorption by, 246f, 247 structure of, 478 537b–539b
light reflection by, TEQ factors for, 498, 499t in food, 417
246–247, 246f toxicity of, 497–498 fungicides as, 416–417, 416t
nitrogen in, 135, 137 PCE (perchloroethene, perc), in and harpin technology,
organic content of, 135 groundwater, 627t, 628, 629, 86–87
PM index for, 137–138 631, 632t, 633 health effects of, 417, 447
respirable, 138, 161, 169 Penta, 530–531 herbicides as, 416–417, 416t,
settling rate of, 133, 140, Pentachlorophenols (PCPs), 452–459. See also
159t, 161 473–474, 514t, 747 Herbicides
sizes of, 132, 133f Pentane, AP-2 insecticides as, 416–417, 416t.
distribution of, pE-pH diagram, 574–575, 575f See also Insecticides
139b–140b, 139f Perchlorate ion, in drinking natural/green, 417, 447–448
sources of, 134–137 water, 625–626, 625f oxidation/reduction of,
sulfur in, 135, 136, 137 Perchlorocyclopentadiene, 460–461
total suspended (TSP), 138 431–432 persistence of, 418, 459
types of, 132–133 Perchloroethene (PCE, perc), in solubility of, 420–421, 426t
ultrafine, 138, 139f groundwater, 627t, 628, 629, toxicity of, 418, 434, 437–438,
Partition coefficient (Kow), 631, 632t, 633 438t, 442, 444–446, 448,
425–426, 426t Perchloroethylene (PERC), 120, 451. See also Toxicology
Parts per million (ppm), 93b AP-6 types of, 416–417, 416t
Parts per scale, 29, 92 Perfluorinated sulfonates, usage of, 416–418
in aqueous solutions, 533–534 PET (polyethylene terephthalate)
420–421 Perfluoroalkyl acids (PFAAs), 534 substitutes for, 295–297
I-18 Index
Petroleum ozone and, 155 primary, 98, 98f

components of, 274 ozone depletion/destruction secondary, 98
production of, 275, and, 36 in solution, 421
278–279, 279f Photovoltaic cells. See also Pollution
refining of, 276b–278b, 277f Solar cells point sources of, 125
pH carbon dioxide emissions from, thermal, in natural waters, 562
pE and, 571, 574–575, 575f 319f, 331 Pollution control
of rain, 128, 148 Photovoltaic effect, 330 effects-based vs.
Phenanthrene, 509, 510f Phthalate, 732 source-based, 153
Phenolphthalein alkalinity, of Phthalate esters, 518f, 520 Pollution prevention, 5, 6
natural waters, 593–594 Physical absorption at source, 4
Phenols, 456, 458, 488, 752 of carbon dioxide, 283 Polonium, 169
in drinking water, 614 Phytoestrogens, 524 from radon decay, 372f, 375
Phenoxide anion, 458 Phytoremediation, 755–757, 756f Polyacrylate (PAC), 722
Phenoxyacetic acid, 458 Pigments Polyaspartate, 721–723, 723f
Phenoxy herbicides, 456, cadmium in, 692–693 Polybrominated biphenyls
458–459 lead in, 683–684 (PBBs), 498, 533
Phenyl, AP-12 Pinene, 108 Polybrominated diphenyl ethers
Phenylmercury, 677 Piperonyl butoxide, 448 (PBDEs), 529–531
Phosalone, 446 Plank’s constant, 37 Polychlorinated biphenyls
Phosphate ions, 641f Plankton (PCBs), 477–487
in natural waters, 640–641 ozone depletion/destruction Polychlorinated dibenzofurans
Phosphonates, 455–456 and, 36 (PCDFs), 485–486, 486b.
Phosphoric acid, 441 Plants See also Furans
Phosphoric acid-based fuel cells, for bioremediation, Polyethylene
353f, 354 755–757, 756f high-density, 728–730, 729t
Photocatalytic processes, in ozone depletion/destruction low-density, 728–729, 729t
wastewater treatment, and, 36 Poly(ethylene terephthalate)
651–652 Plastics, 729t (PET), 121, 728–730, 729t
Photochemical decomposition, recycling of, 731–732 Polyfluorocarboxylic acids, 82
178f, 179–180, 182, types of, 727–730 Polylactic acid (PLA),
186–187, 195 Plumes, in groundwater, 630, 630f 295–297, 296f
of pesticides, 459–460 Plutonium, 382, 383f, 388–391 Polymeric CH2O, 220
Photochemical reaction, 38, 42 as pollutant, 390b Polymeric-electrolytemembrane
Photochemical smog, 97, 102f, reprocessing of, 388–389 fuel cells (PEMFC), 352,
158, 185–192. See also Smog Plutonium dioxide, 391 352f, 353f
conditions for, 101 PM index, 137–138 Polymers
production of, 185–192 Point sources, 642 biodegradable, 295–297
reactants in, 98 of pollution, 125 from crude oil, 121
sunlight and, 98 Polar stratospheric clouds (PSCs) Polynuclear aromatic
Photoconversion, 326, 330 in Antarctic, 65 hydrocarbons (PAHs), 169,
Photolithography, in chip in Arctic, 72, 72f 508–517, 519
manufacture, 226, 226f Pollutants as air pollutants, 509–512, 510f
Photolysis, 38 distribution of, 462–464 as carcinogens, 513–517,
Photons, 36–40 fugacity of, 462b–464b, 463f 514t, 515b
Photoresist polymer, 226–227, 226f MTBE as, 346 long-range transport of, 526, 527t
Photosynthesis persistent organic, 419, 420t in sediments, 742
carbon dioxide in, 220, 224 plutonium as, 390b, 391 sources of, 511–513, 516–517
Index I-19
structure of, 508–509 Pump-and-treat systems Rainfall

as water pollutants, 512 for groundwater global warming and, 256
Polyphosphate ions, in decontamination, 630 Rate constant, 44b
detergents, 640 PUREX (plutonium and uranium Reactants, 5, 6
Polypropylene (PP), 728, 729t recovery by extraction), 388 Reaction mechanism, 43
Polystyrene (PS), 79–80, 121, p-Xylene, 281, 281t Reaction(s)
728, 729t Pyrazole, 451t atmospheric, 40–43
Polyvinyl chloride (PVC), 121, Pyrene, 510f, 513 autocatalytic, 187
728, 729t, 730 Pyrethrins, 438t, 447–448 Claus, 124–125
in carpeting, 732–733 Pyrethroids, 448, 451t dissociation, 37–38
Pore spaces, 618 Pyritic sulfur, 129 endothermic, 49b–50b, 49f,
Pore water, 742 179, 328
Positive feedback, 230 exothermic, 42, 49b–50b, 49f,
in greenhouse effect, 230 Quaternary ammonium salt, 708 177, 179
methane and, 240 free-radical, 49b–50b
Postcombustion cleaning, 130 oxidation, 91
Postconsumer recycling, 724 Rad (radiation absorbed dose), 371 photochemical, 38
Potassium iodide, 387 Radiation Reactive wastes, 758
Potassium ion, 589–590, 590t alpha, 368–370, 369t Reactivity
Power plant emissions beta, 368–370, 369t in troposphere, 177–181
controls on, 668 blackbody, 206, 209, 213b Reactor-grade plutonium, 389
nitric oxide in, 116–117 gamma, 369–370, 369t Rebound effect, 292
reduction of, 129–132 health effects of, 369–371, Recycling
sulfur dioxide in, 129–132 382–383, 385, 386–387 of carpeting, 732–733
Precautionary principle, 461 measurement of, 371 of hazardous wastes, 759
Precipitation measurement of health danger of metals and glass,
global warming and, 256 from, 376–377 724–725
for water purification, 605–606 Radiation exposure, acute, 371 of paper, 725–727
Precipitation trends, global Radiation sickness, 371 of plastics, 727–732
warming and, 299t, 300, 301, Radioactive decay, 372–374, 372f postconsumer, 724
302t, 303 measurement of, 374–375 preconsumer, 724
Precombustion cleaning, 129 steady-state analysis of, 373b of tires, 727
Preconsumer recycling, 724 Radioactive elements, 169 Red lead, 683, 684
Prefixes, AP-5, AP-6, AP-8 Radioactive waste, 383, 383f, 758 Red limit
Primary pollutants, 98, 98f, 134 Radioactivity of visible light, 206
Products of incomplete nature of, 368–369 Redox equation balancing,
combustion (PICs), 761–762 particles (rays) produced by, 560b–561b
Prometon, 455 368–369, 369t Reductive degradation
Propane, 272, 274, 277b, Radiocarbon dating, 238b in groundwater
277f, AP-1 Radon, 367 decontamination,
Propene, AP-4 daughters of, 372f, 375–376 634–635
Propionic acid, 459 as indoor pollutant, 374 Reductive transformation, 732
Propoxur, 438t and lung cancer, 376–377 Reflection of light
Propylene glycol, 348–350, 349f from uranium-238 decay, by aerosols, 246–247, 246f
Protozoans, disinfection for, 604 372–374 by particulates, 246–247, 246f
Pulp-and-paper mills, dioxins and Rain, natural Reformulated gasoline, 291
furans from, 488–489. See acidity of, 147 Rem (roentgen equivalent
also Dioxins, Furans pH of, 128 man), 371
I-20 Index
Renewable energy, 312–333, 313f Scouring, 565–566 Sludge, 636–637, 637f

biomass, 312, 313f Scrubber processes, 129 disposal of, 647–648
hydroelectric, 312, 313f Sea level, global warming and, Smith, Angus, 147
Renewable resources, 5, 6 256, 257f, 300–301 Smog, 91–92
Reprocessing Seawater. See also Oceans anthropogenic hydrocarbons
plastics, 731 ion concentrations in, 592 in, 97–103, 106–107
plutonium, 388–389 Seawater, thermal expansion components of, 97–103
Reserve acidity, 740 of, 300 diurnal variation in, 102, 102f,
Reservoirs Secondary extraction, 278 189–191
as methane source, 236–237 Secondary pollutants, 98 formation of, 97–98, 102f
Residence time, 231–234 Second law of thermodynamics, free-radical reactions and,
for greenhouse gases, 234 323, 326, 328–329 189–192
Resonance, AP-12 Sediments, 741 geographic distribution of,
Respirable particulates, 138 contamination of, 742, 742f 104–106
Respiratory conditions by heavy metals, haze and, 146
from indoor air pollution, 165, 744–745, 745f health effects of, 156–160
167, 169 remediation for, 751 hydrocarbon oxidation and,
from outdoor air pollution, sample analysis for, 750–751 185–187, 188f
158–159, 162 Selective catalytic reduction, nitric oxide in, 97–102, 102f,
Reverse osmosis 116, 125 189–191
in wastewater treatment, 643 Septic tanks, 621–622, 645 ozone in, 101–102, 102f
in water purification, 607f, Sequestration, of carbon dioxide, photochemical, 97–98,
608–609 282, 285f, 286f, 287f 101–103
Rio Environmental Summit, 304 ocean, 285–289, 285f, production of, 185–192
Risk, 4 286f, 287f soot-and-sulfur, 156–157
Risk assessment, 439–440 in plants, 285f, 291 U.S. standards for, 103
Rogers, Robin, 123 underground, 285f, 286f, volatile organic compounds in,
Rotary kiln incinerator, 289–290 97, 98f, 106
760–761, 760f Sex hormones, 516. See also Smoke
Rotational energy, 217, 229 Environmental estrogens environmental tobacco,
Rotenone, 438t, 448 Sick building syndrome, 165 168–170
Roundup (herbicide), 456, 457b Silent Spring (Carson), 3, 421 second-hand, 168, 170
Rowland, Sherwood, 83 Silicate minerals, 735, 736f sidestream, 168–169
Ruminant animals, as methane Silicon, 330 sources of, 162–163
source, 237 Silicon dioxide, 226, 226f, 288 Sodium arsenate, 696
Runaway greenhouse effect, 241 Silt Sodium arsenite, 452
dams and, 314 Sodium bicarbonate, 613
Silvex, 459 Sodium bisulfate, 613
Safrole, 448 Simazine, 454, 455 Sodium carbonate
Saline water, 591 Sink(s) in natural waters, 595
Sanitary landfills, 716 for carbon dioxide, 222, 223, in water purification,
Sanitary sewer system, 636 223f, 224f 604, 613
Saturated zone, 618, 618f for CFCs, 78, 80 Sodium chlorate, 542
Scattering, 246 for chlorine and bromine Sodium chlorite, 611
SCORR (supercritical carbon compounds, 77 Sodium fluoride, 591
dioxide resist remover), for HFCs, 82 as insecticide, 418
227, 229 for hydroxyl radicals, 189 Sodium hydroxide, 116, 670
Scotchgard, 533 Skin cancers, 34–35, 160 in scouring, 565–566
Index I-21
Sodium hypochlorite, in water in developing world, 332 Stratosphere

chlorination, 612 and emissions, 331 chemistry of, 194–196
Sodium iminodisuccinate (IDS), Solar energy/power defined, 28
as chelating agent, 643, 643f active/passive technologies loosely bound oxygen in,
Sodium ion, 589, 590 for, 326 194–195
Sodium monofluorophosphate, 591 advantages of, 332–333 ozone creation in, 40–41
Sodium nitrate, 116 disadvantages of, 333 ozone destruction in, 42–43
Sodium tripolyphosphate (STP), electricity from, 326–327 temperatures in, 28, 29f, 41
water contamination energy supply and, 313f UV filtering in, 32, 33
by, 641 indirect, 313, 315 Stretch vibrations, 216, 229, 245
Soil types of, 325–326 Strontium, 382–383
acidity of, 150, 152 Solar technology Structural isomers, AP-2
alkalinity of, 149–150, 150f active/passive, 326 Substituents, AP-3
Soil remediation, 746 Solar thermal electricity, Substitution reaction, AP-13
electrochemical, 749–750, 750f 327, 327f Sugarcane, ethanol from,
ex situ Solder, 679, 681 335, 338
containment for, 747 Solid-oxide fuel cell (SOFC), Sulfate aerosol
in situ 353f, 354–355 atmospheric cooling by,
chemical oxidation for, 750 Solid waste, 714 247–248
containment for, 747 landfill disposa1 of, 715–718 in fine particulates, 136
immobilization for, 747 decomposition of, 716–718 lifespan of, 248–249, 253
soil washing for, 748t, 749 incineration of, 719–721 trend in, 250–251
thermal desorption for, recycling of, 723–733 Sulfate ion, 193, 672
747, 748t types of, 714–715, 715f in natural waters, 568, 568t,
types of, 747–750 Solubility product (Ksp), 581 589, 590t
vapor extraction for, 747, 748t Solvents, 5, 6 Sulfhydryl groups, heavy metals
vitrification for, 747 organic, replacements for, and, 664
Soils, 735 119–123 Sulfide ions, 125
acidity of, 739–740 Soot, 132, 247, 511 in natural waters, 568, 568t
components of, 735, 737–739 Soot-and-sulfur smog, 156–157 in wastewater treatment, 638
contamination of Source reduction Sulfur
by heavy metals, 742–745 for hazardous wastes, 758 in Claus reaction, 124–125
by mine tailings, 745–746 for solid wastes, 723 elemental, 568, 568t
remediation for, 746–747, Speciation, 665 total reduced, 125
748t, 749–750, 750f Species diagram, 578–579, 579f Sulfur compounds
minerals in, 735, 736f, 737t Spectra insecticides, 418
organic matter in, 738–739 absorption, 30 Sulfur dioxide, 92, 568, 568t
particle sizes in, 735, 737–738, electromagnetic, 30, 31f and acid rain, 147
737f, 738f visible, 30 in Claus reaction, 124
pH of, 740 SPF (Sun Protection Factor), 35 in clear air, 92
salinity of, 741 Stable species, 184, 184f critical load of, 152–153
types of, 735, 737, 737f Stannous fluoride, 591 effects of, 247, 248
Soil vapor extraction, 747, 748t Steady state, 43 emission of, 124–125, 275
Solar-cell energy Steady-state concentration, 44b, trends in, 131–132,
growth of, 316f 231–234, 232f 249–251, 249f
Solar cells, 330–332 Stockholm Treaty, 419 as fumigant, 418
cost of, 331 Stokes’ law, 133 health effects of, 157–158, 160
in developed world, 332 Straight-chained molecule, AP-2 natural sources of, 95t
I-22 Index
Sulfur dioxide (continued) Sustainable development, 3 Tetrachloroethene, AP-5

oxidation of, 126–128 defined, 2 2,3,4,6-tetrachlorophenol, 473
gas-phase mechanism in, Swamp gas, 236, 566 Tetraethyllead, 687
191–194, 199–200 Swimming pools, chlorination for, Tetramethyllead, 280, 687
sources of, 95t, 98t, 124–125 612–613, 617 Thermal conversion, 325–326
standards for, 131, 157, 159t Switchgrass, ethanol from, 340 electricity from, 326–328
structure of, 177 Symmetric stretch vibration, 216, Thermal desorption, 747, 748t
Sulfur hexafluoride, as trace 229, 245 Thermal distillation, 608
greenhouse gas, 245 Synthesis gas, 342–343, 342f, 362 Thermal expansion of
Sulfuric acid, 64 Synthetic chemicals, 415 seawater, 300
in acid rain, 147 Thermal infrared, 209–210, 210f,
oxidation of, gas-phase 211, 214, 215, 231, 234
mechanism in, 193–194, 2,4,5-T, 458–459 carbon dioxide absorption of,
199–200 dioxin and, 470–471 217–218, 218f, 219f
as particulate, 135 Tailings, 746 methane absorption of,
in smog, 193–194 from uranium mining, 384 234–235
Sulfur–iodine cycle, in hydrogen TAML ligands water vapor absorption of, 229
production, 361–362 in paper production, 490, 490f Thermal nitric oxide, 99
Sulfurous acid, 127–128 Tar, 169, 752 Thermal NO, 99, 333
Sulfur trioxide, in smog, 192–193 coal, 629 Thermal polyaspartate (TPA), 722
Sun as particulate, 169 Thermodynamics, second law of,
as Earth’s energy source, Tar sands, 279 323, 326, 328–329
206–207, 312 TBBPA (tetrabromobisphenol- Thimerosal, 676
Sunlight, 27, 32, 206–207, 207f. A), 532 Thiobacillus ferrooxidans, 569
See also Light TCE (trichloroethene, tric), in Thioethers, AP-8
absorption of, 207, 247, 330 groundwater, 627t, 628, 629, Thiols, AP-8
intensity of, 33f, 34f 631, 632t, 633 Three Gorges Dam (China), 314
in photochemical smog, 98 Temperature inversion, 41 Three Mile Island accident,
positive effects of, 36 Temperature trends, global 385, 387
reflection of, 207, warming and, 207–209, 208f, Three-way converters, 110
246–247, 246f 298–300, 299t, 301, 302t, 303 Threshold concentration, of
in smog formation, 98, 101 TEQ scale, 498–500, 499t pollutants, 156
Sunscreen compounds, 34–35 Teratogens, 435 Tidal energy/power, 325
Supercritical carbon dioxide, in Terawatts, 312 Tires, recycling of, 727
computer chip manufacture, Termites, insecticides for, Titanium, 357
227, 228b, 228f, 229 450–451, 451f, 451t Titanium dioxide, 651, 683
Supercritical fluid, 228b, 228f Tertiary-butyl alcohol, 341 Titanium dioxide,in hydrogen
Superfund Act, 4 Tetraamido-macrocyclic ligands production, 361
Superfund program, 748b, 748t in paper production, Tobacco smoke
Suppes, Galen, 348–349 490, 490f components of, 169
Suppes synthesis Tetrabromobisphenol-A health effects of, 169–170
glycerin and, 348–350 (TBBPA), 532 Tokamak reactor, 394
Surface albedo, 251, 252f Tetrachlorobenzene, 470 Toluene, 166–167, 169, 281, 281t,
Surfactants, 749 Tetrachlorodibenzo-p-dioxin 358, 717
Surfactants, for carbon dioxide, (TCDD), 470, 472 in groundwater, 627t, 628
119–120, 120f 2,3,7,8-tetrachlorodibenzo-p- Total alkalinity, 593
Sustainability. See Sustainable dioxin (TCDD), 472, 489. Totally chlorine free (TCF) pulp-
development See also Dioxins and-paper mills, 489
Index I-23
Total organic carbon (TOC), 564 Triple bottom line, 2 UV-A, 31f, 33, 34, 37
Total reduced sulfur, 125 Tripolyphosphate ion, water UV-B, 31f, 32–34, 37, 42–43
Total suspended particulates contamination by, 641 UV-C, 31f, 32, 37, 40–43
(TSP), 138 Tritium, 384–385, 393–394
Toxaphene, 420t, 426t, 430, Troposphere, 28, 92
514t, 527t chemistry of, 177–194 Vapor pressure, 334–335, 335f
Toxicity, 5, 6 oxidation in, 177–193 Vegetable oil
of heavy metals, 665–666 reactivity in, 177–181 as alternative fuel, 346–348
Toxicity equivalency factor Trost, Barry, 7 Vehicle emissions, 115
(TEQ) scale, 498–500, 499t Turbufos, 438t catalytic converters for,
Toxicity reference dose Two-way converters, 110 109–115, 111
(RfD), 440 reduction of, 109–115, 111f
Toxicology, 434–441 Vehicular fuel(s)
definition of, 434 Ultrafiltration, 606, 607f alcohols as, 333
dose–response relationships in, Ultrafine particulates, 138 alternative, 333–350
435–438 Ultraviolet (UV) light, 30, ethanol as, 334–335, 337, 338
environmental, 434 207, 207f methanol as, 341, 345
risk assessment and, 439–440 energy of, 37 oxygenated, 334, 345
Toxic wastes, 758 filtering of, 27, 32, 33 Vibrational energy, 217, 229
incineration of, 759–762 for water purification, Vibrations, molecular, 231
Trace gases 609–610 antisymmetric stretch, 216,
in clean air, 92, 95t in photochemical 229, 245
Transformation of plastics, decomposition, bending, 215, 229, 235,
731, 732 179–180, 182 242, 244
Transgenic plants, 457b in smog formation, 98, 101 bond-stretching, 215, 215f,
Treatment intensity of, 33f 234, 242, 244
of hazardous wastes, 759 Unbranched molecule, AP-2 light absorption and, 214–216
Triazines, 452–454, 460 Unit conversion methods, symmetric stretch, 216,
Tributyltin oxide, 697b 93b–95b 229, 245
1,1,1-trichloroethane, 752 Units, concentration, 92, 93b–95b Vinyl chloride, 514t, 627t, 631,
1,1,2-trichloroethene, AP-5 Unsaturated zone, 618, 618f 632t, 752
Trichloroethene (TCE, tric), in Uranium, 383f Viruses, disinfection for,
groundwater, 627t, 628, 629, depleted, 378 604, 607f
631, 632t, 633 enrichment of, 383f, 384 Visible light
Trichloroethylene, AP-5 mining of, 376, 383f, 384 red limit of, 207
Trichlorophenol, 470–471 weapons-grade, 384 Visible spectrum, 30
2,3,6-trichlorophenol, 476 Uranium hexafluoride, 383f, 384 Vitamin D, 36
2,4,5-trichlorophenol, 470 Uranium oxide, 378, 383f, 391 Vitrification, 391, 747
2,4,5-trichlorophenoxy acetic Uranium-234, 378 Volatile organic compounds
acid (2,4,5-T), 458–459 Uranium-235, 378, 380–382, 384 (VOCs), 420
Trichlorophenoxy anions, 470 Uranium-238, 381 as solvents, 119–120
Trifluoroacetic acid (TFA), decay of, radon from, 372–374 emission of, 97, 98f
81–82 Urban ozone, 186 reduction of, 107f, 106–109
Triglycerides, 347 Urea, 136, 721 removal of from wastewater,
Trihalomethanes (THMs), in UREX (uranium recovery by 648–649
drinking water, 614–616 extraction), 389 Volcanic activity
Trimethylarsine, 704 UV at ground level, increases in, atmospheric cooling due to,
Tri-n-butyl phosphate, 388 74–75 208, 248
I-24 Index
Volcanic eruptions Cryptosporidium in, 604, pH of, 588, 595

and ozone depletion/ 609, 618 phosphate ions in, 640–641
destruction, 75b–76b drugs in, 645–646 sulfur compounds in, 567,
Vortex and ozone destruction Giardia lamblia in, 609, 618 567f, 568, 568t
Antarctic, 64–66 heavy metals in, use of, 557–558
Arctic, 73 666, 682t Water pollutants, PAHs as, 512
lead in, 681–682 Water pollution
MTBE in, 346 from pesticides, 421, 455
Wallpaper, death by, 704–705 nitrate ion in, 620–624 thermal, 562
Warner, John, 4 perchlorate ion in, 625f, Water purification, 602–618, 603f
Wastewater treatment, 636, 637f 625–626 disinfection in, 603f, 604–618
adsorption in, 649 fresh, 557–558 chemical methods for,
advanced, 637–638, 637f global supply of, 557–558, 610–611
advanced oxidation methods 558f, 559f chlorination for, 611–618
in, 649–652 in hydrogen production chlorine dioxide for, 611
air stripping in, 648 electrolysis of, 360–361 filtration for, 605–609, 607f
biological, 636–637, 637f, thermal decomposition of, iodine for, 617
644–645 360–361 membrane technology for,
catalytic oxidation in, 648 natural, 420b–421b, 425–459. 606–607
chemical, 637–638, 637f See also Lakes microorganisms and, 604
cyanide removal in, 646–647 acid–base reaction in, ozone for, 610
electrodialysis in, 643, 644f 578–588 precipitation for, 605–606
inorganic ion removal in, 638, aerobic decomposition in, ultraviolet light for,
643–644 566–567 609–610
ion exchange in, 643–644 alkalinity of, 592–595 nondisinfection in
mechanical, 636 aluminum in, 596–597 aeration for, 602, 603f
modern techniques for, anaerobic decomposition ion removal for, 602,
648–652 in, 566–567 603f, 604
nitrogen removal in, 638–639 arsenic in, 703–704, 704f Water table, 618, 618f, 630f
phosphate removal in, 638, carbon compounds in, 566, Water vapor
640–642 567, 567f absorption spectrum for, 229
photocatalytic processes in, dissolved oxygen in, as greenhouse gas, 229, 230
651–652 559–562 atmospheric concentration of,
primary, 636, 637f drugs in, 645–646 229–230
reverse osmosis in, 643 hardness index for, 595–596 IR absorption by, 219f, 229
secondary, 636–637, 637f ion concentrations in, stratospheric, as greenhouse
tertiary, 637–638, 637f 589–590, 590t gas, 235
volatile organic compounds lead in, 685–686 Water-gas shift reaction, 343
(VOCs) removal in, mercury in, 671–674, 673f Wave energy/power, 325
648–649 nitrogen compounds in, Weapons-grade uranium, 384
Water 567, 567f, 575–577 Weather patterns,
drinking organic matter in global warming and, 255–257
arsenic in, 698–700, 701f decomposition of, West Nile virus, 417, 445
bottled, 591–592 566–567 Wet deposition, 149, 151f
carcinogens, 614–616 oxidation–reduction Wetlands
chlorination by-products in, reactions in, 559–577 as methane source, 236
613–616 oxygen demand in, 562 White arsenic, 694
chromium in, 706 pesticides in, 422–421, 430 White lead, 683
Index I-25
White-rot fungi, 753–754 Wind speed, 317 World Health Organization

Wind energy/power, 313f, Wind turbines, 317–318 (WHO), 103, 437
315–321 Windmills, 317–318
as indirect solar energy, 315 Wood preservatives
carbon dioxide emissions alkaline quarternary Xylenes, 166
from, 319f (ACQ), 708 in groundwater, 628
economics of, 318–319, 321 arsenic in, 697–698
generation of, 315 chromium as, 707
growth of, 315–316, 316f pentachlorophenols in, Yttrium oxide, as lead substitute,
offshore locations for, 319–320 474–475 684–685
potential sites for, 318 Wood, pressure-treated
pros and cons of, 320t arsenic in, 697–698
in United States, 315, 316, 317f arsenic/chromium removal Zeolites, 641–642
Wind farms, 315 from, 707–708 Zinc oxide, dissociation of, 328
Wind power, 315 chromium in, 707

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What is the book about based on the preface and table of contents?

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Periodic Table

89 90 91 92 93 94 95 96 97 98 99 100 101 102 103

W. H. FREEMAN AND COMPANY

Library of Congress Preassigned Control Number: 2007939344

© 2008 by W. H. Freeman and Company.

Printed in the United States of America

W. H. Freeman and Company

PART I ATMOSPHERIC CHEMISTRY

PART II ENERGY AND CLIMATE

PART III TOXIC ORGANIC

PART IV WATER CHEMISTRY AND

PART V METALS, SOILS,

Appendix: Background Organic Chemistry AP-1

PART I ATMOSPHERIC CHEMISTRY

CHAPTER 2 The Ozone Holes 59

The Chemicals That Cause Ozone Destruction 77

CHAPTER 3 The Chemistry of Ground-Level

CHAPTER 4 The Environmental and Health

CHAPTER 5 The Detailed Chemistry of the Atmosphere 175

PART II ENERGY AND CLIMATE

Energy and Carbon Dioxide Emissions in the Future 292

PART III TOXIC ORGANIC

CHAPTER 11 Dioxins, Furans, and PCBs 469

CHAPTER 12 Other Toxic Organic Compounds

PART IV WATER CHEMISTRY AND

CHAPTER 14 The Pollution and Puriﬁcation of Water 601

Groundwater: Its Supply, Chemical Contamination, and Remediation 618

PART V METALS, SOILS,

CHAPTER 16 Wastes, Soils, and Sediments 713

The Recycling of Household and Commercial Waste 723

Appendix: Background Organic Chemistry AP-1

New to This Edition

• Much of the detail concerning CFCs (Chapter 2) has been cut, as it is

• Chapter 7 now begins with a more extensive discussion of energy usage

• The section concerning PBDEs (Chapter 12) now incorporates a descrip-

Scientiﬁc American Feature Articles

To All Readers of the Text

Colin Baird wishes to express his thanks . . .

Mike Cann wishes to express his thanks . . .

To Paul Anastas (Center for Green Chemistry and Green Engineering

Ann Marie Anderssohn, University of Portland

A Brief History of Environmental Regulation

setting aside land from development. The focus of environmental laws

The 12 Principles of Green Chemistry

In many of the chapters that follow, real-world examples of green chem-

Presidential Green Chemistry Challenge Awards

Real-World Examples of Green Chemistry

H3C ¬ CH2 ¬ CH2 ¬ CH2 ¬ OH + Na ¬ Br + H2SO4 ¬:

H3C ¬ CH2 ¬ CH2 ¬ CH2 ¬ Br + NaHSO4 + H2O

% atom economy (molar mass of atoms utilized/molar mass of

This is one method of accessing the efﬁciency of a reaction. Armed

Ibuprofen is a common analgesic and anti-inﬂammatory drug found in

% atom economy (molar mass of atoms utilized/molar mass of

% atom economy (molar mass of atoms utilized/molar mass of

A by-product from the acetic anhydride (reactant 2) used in step 1 is acetic

CH3 FIGURE In-2 The BHC

Here h is Planck’s constant (6.626218 1034 J s) and c is the speed of light

where E is in kJ mol1 if ␭ is in nm.

O2 9: 2 O H° 498.4 kJ mol1

H° 兺Hf° (products) 兺Hf° (reactants)

H° 2 Hf° (O, g) Hf° (O2, g)

H° 2 249.2 0 498.4

To a good approximation, for a dissociation reaction, H° is equal to the

␭ 119,627 kJ mol1 nm/498.4 kJ mol1 240 nm

O2 UV photon (␭ 240 nm) 9: 2 O

2 rate1 2 rate4 0 [O3]2 [O2]2 [M] k1k2兾k3k4