Energy, Plants & Man

Energy, Plants & Man
David Alan Walker
Digital Edition, 2006

Text copyright 2002 David Alan Walker
Illustrations copyright 2002 Richard Walker
First published in 2002 by Oxygraphics

[email protected]
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All rights reserved. No part of this publication may be reproduced, stored in a retrieval
system or transmitted by any means, electronic, mechanical, recording or otherwise except
for the exclusive use of the purchaser or by written permission of the copyright holders other
than in accord with “fair use”. In this context “fair use” of a copyrighted work is defined as
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figures) for classroom use, scholarship, or research. In determining whether the use made of
this work in any particular case is a “fair use” the factors to be considered shall include the
amount and substantiality of the portion used in relation to the copyrighted work as a whole;
and the effect of the use upon the potential market for or value of the copyrighted work. In
line with academic custom and practice, appropriate acknowledgement of source should
always be made.
ISBN 1 870232 05 4
David Alan Walker, Ph.D., D.Sc., FRS was formerly director of The Robert Hill Institute and is
now Emeritus Professor of Photosynthesis in the University of Sheffield and a member of
‘The Cross Keys’ Literary and Philosophical Society.
His filial collaborator, Richard Walker, M.A., one-time tenor saxophonist with ‘The Potato
Five’ now lectures in Higher Education and otherwise continues to endure a precarious
existence pitched between art, music and contemplation of the universe.
Friday, January 26, 2001
ISBN 1 870 232 05 4
Text copyright 2000 David Alan Walker

Illustrations copyright 2000 Richard Walker
This edition first published in 2004 by Oxygraphics

[email protected]
http://www.oxygraphics.co.uk/
David Walker, Ph.D., D.Sc., FRS was

formerly director of The Robert Hill
Institute and is now Emeritus Professor
of Photosynthesis in the University of
Sheffield.UK
His filial collaborator, Richard Walker, M.A.,

one-time tenor saxophonist with ‘The Potato
Five’ now lectures in higher education and
otherwise continues to endure a precarious
existence pitched between art, music and
contemplation of the universe.
All rights reserved. No part of this publication may be reproduced, stored in a retrieval system or
transmitted by any means, electronic, mechanical, recording or otherwise except for the exclusive use
of the purchaser or by written permission of the copyright holders other than in accord with "fair use".
In this context "fair use" of a copyrighted work is defined as reproduction for purposes of teaching
(including multiple copies of parts of the text or figures) for classroom use, scholarship, or research. In
determining whether the use made of this work in any particular case is a "fair use" the factors to be
considered shall include the amount and substantiality of the portion used in relation to the copyrighted
work as a whole;and the effect of the use upon the potential market for or value of the copyrighted
work. In line with academic custom and practice, appropriate acknowledgement of source should
always be made.
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CONTENTS
“What is the use of a book”, thought Alice, “without pictures or conversations”.
iii
CONTENTS
CONTENTS
INTRODUCTION 1
Chapter 1 A FEW FUNDAMENTALS 9
MATTER AND ENERGY

1.1 Atoms, Molecules and Bonds 10
1.2 Oxidation and Reduction 13
1.3 Electron Transport in Photosynthesis and Respiration 16
THE SOURCE OF ORGANIC CARBON

1.4 The Products of Photosynthesis 17
1.5 Chemical Composition of Leaves 19
1.6 Ashes to Ashes 20
ENERGY TRANSDUCTION IN PHOTOSYNTHESIS

1.7 An Analogy 20
THE PHILOSOPHER’S STONE

1.8 How to be one up 23
1.9 The Laws of Thermodynamics 23
Chapter 2 WHERE IT ALL STARTS 25
SOLAR ENERGY
2.1 The Sun 26
2.2 The Nature of Light 26
2.3 The Energy Content of Light 29
2.4 A Word About Units 31
2.5 Light Intensity 32
2.6 The Availability of Solar Energy 34
2.7 Light as an Energy Carrier 35
2.8 Getting Excited 36
FLUORESCENCE
2.9 A Rich and Ambiguous Signal 38
2.10 Quenching Analysis 40
Chapter 3 HARVESTING THE SUN 43
3.1 The Photoreceptors 44

3.2 Photosynthetic Units 45
3.3 Light-harvesting Antennae 48
3.4 Downhill All the Way? 48
3.5 The Heart of the Matter 49
3.6 Chlorophyll Protein Complexes 50
3.7 PSII Reaction Centre 51
3.8 PSI Reaction Centre 51
3.9 Electron Carriers 51
v
CONTENTS
3.10 Beyond PSI 52

3.11 Where it All Happens 53
3.12 Starch Pictures 55
3.13 Structure of the Chloroplast 59
3.14 Summary 64
Chapter 4 ASSIMILATORY POWER 65
4.1 Equations Old and New 66

4.2 The Reduction of NADP 68
4.3 The Z-scheme 69
4.4 Non-cyclic or Linear Electron Transport 71
4.5 Cyclic Electron Transport 72
4.6 Hydrolysis of Adenosine Triphosphate (ATP) 73
4.7 The Generation of ATP 74
4.8 Assimilatory Power 76
4.9 Utilisation of Assimilatory Power 77
4.10 Where it all Ends 78
4.11 The Phosphate Translocator 79
4.12 The Red Drop 82
4.13 Summary 84
Chapter 5 THE DARK BIOCHEMISTRY 85
C3 PHOTOSYNTHESIS
5.1 Photosynthetic carbon assimilation 86
5.2 The Calvin Cycle 88
5.3 End Product and Autocatalysis 92
5.4 The Reduction of PGA 93
5.5 Energy Inputs 95
5.6 Stoichiometries 95
PHOTORESPIRATION
5.7 Oxygenation 98
5.8 Virtue or Necessity? 98
5.9 A Necessary Evil 99
5.10 All is not lost 101
C4 PHOTOSYNTHESIS
5.11 C4 Plants 103
5.12 Greenhouses within Plants 104
CRASSULACEAN ACID METABOLISM

5.13 Came you not from Newcastle? 107
5.14 Dark Acidification 112
5.15 Light Deacidification 115
5.16 Energy Costs 116
5.17 Should I Compare Thee to a summers Day? 117
5.18 Summary 119
Chapter 6 OF PLANTS AND MEN 121
6.1 All Flesh is Grass 122
vi
CONTENTS
6.2 Eating Potatoes 124

6.3 Defying Thermodynamics 127
6.4 Rods, Poles and Perches 130
6.5 Sunbeams into Cucumbers 131
6.6 Oil into Potatoes 134
6.7 Photosynthetic Efficiency 135
6.8 Efficiency of the Standing Crop 141
6.9 Roofs and Ceilings 143
SAFELY DISSIPATED
6.10 The Need for Dissipation 146
6.11 Acid Bath Technology 148
6.12 The Governor 149
6.13 Summary 150
Chapter 7 DOOM AND GLOOM 151
PREDICTION, SCEPTICISM, OPTIMISM AND PESSIMISM

7.1 Noah and the Ark 152
THE GREENHOUSE EFFECT

7.2 What is it? 153
7.3 How Does it Work? 155
7.4 Generating Hot Air 156
THE GREENHOUSE GASES

7.5 Carbon Dioxide 159
7.6 Methane 166
7.7 Chlorofluoromethanes 171
7.8 New CFCs for Old 173
7.9 Ozone 175
7.10 Oxides of Nitrogen 177
7.11 Summary
Chapter 8 CONSEQUENCES AND UNCERTAINTIES 179
8.1 What Might Happen 180

8.2 Through a Glass Darkly 183
8.3 Back in the Dark Days 185
8.4 The Yo-Yo Concept 192
8.5 Will it Happen? 196
8.6 Down to the Sea 197
8.7 The Missing Sink 199
8.8 What Rubbish! 201
8.9 Will Temperatures Rise and Catastrophe Follow? 203
8.10 Can Population be Maintained? 203
8.11 Malthus Revisited 205
8.12 What Will Happen If We Get It Wrong? 206
8.13 How Will Rising Carbon Dioxide Affect Plants? 208
8.14 Carbon Dioxide as a Fertiliser 209
8.15 Increased Water Use Efficiency 213
8.16 Summary 215
vii
CONTENTS
Chapter 9 IS THERE ANOTHER WAY? 217
9.1 An Excursion into Dangerous Ground 218

9.2 Procreation and Population 219
9.3 An Inversion of Ends and Means 224
9.4 Going Critical 227
9.5 The Virtues of Thrift 232
9.6 Would Energy Conservation Help? 234
RENEWABLE RESOURCES
9.7 Looking at Alternatives 235
9.8 Ocean Energy 236
9.9 Gone with theWind 238
9.10 Let the Sun Shine In 239
9.11 Photovoltaics 239
9.12 Hot Rocks 241
9.13 The Rain Forests 242
9.14 Biofuels 244
9.15 Hydrogen Power 247
9.16 Epilogue 249
FIGURES
Chapter 1
Fig. 1.1 Relationship between photosynthesis and respiration 16

1.2 Electrical analogy of photosynthetic oxygen evolution 21
Chapter 2
Fig. 2.1 Electromagnetic radiation 27

2.2 What Man sees and what the green plant uses 27
2.3 Light as a waveform 28
2.4 Light as a force field 35
2.5 Electronic states of helium 36
2.6 Excitation of chlorophyll by red and blue light 37
2.7 The Kautsky effect 39
2.8 Complex fluorescence kinetics 39
2.9 Organisation of electron carriers in the thylakoid membrane 41
2.10 Q-analysis 42
Chapter 3
Fig. 3.1 Absorption spectra of chlorophylls in acetone 45

3.2 A photosynthetic unit 46
3.3 Organisation of components in thylakoid membranes 47
3.4 Photosystem II 49
3.5 The thylakoid membrane 50
3.6 Three dimensional view of the interior of a leaf 54
3.7 Cross section of a C3 leaf 55
3.8 Starch Picture “Innocence” 57
3.9 Starch Picture of chloroplast structure 57
viii
CONTENTS
FIGURES CONTINUED
Fig. 3.10 Starch Pictures 58

3.11 Metabolic sites in the chloroplast 60
3.12 Electron miocrograph showing chloroplasts 61
3.13 Enlargement of Fig.3.12 62
3.14 Further enlargement of thylakoid membrane 63
Chapter 4
Fig. 4.1 The Z-scheme by analogy 69

4.2 The Z-scheme 70
4.3 Possible routes of electron transport 71
4.4 Pseudocyclic electron transport 72
4.5 ATP hydrolysis by analogy 73
4.6 Hydrolysis of ATP to ADP and Pi 73
4.7 Generation of ATP 75
4.8 Arnon, Allen and Whatley’s Experiment 77
4.9 The Calvin cycle in outline 78
4.10 Starch and sucrose synthesis 79
4.11 The Pi translocator 80
4.12 Absoption and action spectra compared 83
4.13 Action spectrum of O2 evolution by Chlorella 83
Chapter 5
Fig. 5.1 Light and dark events in photosynthesis 89

5.2 The Calvin Cycle in outline 90
5.3 Calvin Cycle in more detail 91
5.4 Reduction of PGA to triose phosphate 94
5.5 Photorespiration 98
5.6 Distribution of newly fixed carbon 100
5.7 Production and utilisation of glycollate 101
5.8 Maximal oxygentation of RuBP in the Calvin Cycle 102
5.9 C4 Photosynthesis 103
5.10 Kranz Anatomy 107
5.11 Crassulacean Acid Metabolism 111
Chapter 6
Fig. 6.1 Cycling of metabolites 125
6.2 Photosynthetically active radiation 132
6.3 Land areas needed to feed one person 133
6.4 Rate of photosynthesis 139
6.5 A degree of photoinhibition 140
6.6 The Z-Scheme 144
6.7 Roofs and ceilings 145
6.8 Rate v PFD in sun and shade leaves 147
Chapter 7
Fig. 7.1 Radiation and atmosphere 153
ix
CONTENTS
FIGURES CONTINUED
Fig. 7.2 The atmospheric heat balance 154

7.3 The greenhouse effect 155
7.4 Atmospheric carbon dioxide concentration 158
7.5 Carbon dioxide in glacier bubbles 159
7.6 World carbon emissions from fossil fuels 160
7.7 Historical carbon dioxide emissions rate, by region 160
7.8 World primary energy consumption 1860-1965 161
7.9 Sources of electrical energy 161
7.10 CO2 emissions from the U.K. 163
7.11 CO2 emissions from India 164
7.12 Concentrations of atmospheric CH4 166
7.13 Monthly concentrations of atmospheric CH4 167
7.14 Divisions of the atmosphere 168
7.15 Present contributions to greenhouse warming 175
7.16 Laughing gas from leaky pipes 178
Chapter 8
Fig. 8.1 Global warming 182
8.2 Increases in sea level 182
8.3 Tentative time scale 186
8.4 Photosynthesis and atmosphere 187
8.5 Effects of ultra violet 191
8.6 The Yo-Yo in action 193
8.7 Greenhouse gases 194
8.8 Effect of carbon dioxide on photosynthesis 209
8.9 Effect of carbon dioxide 210
8.10 Rate as a function of PFD 211
8.11 Temperature and carbon dioxide 212
Chapter 9
Fig. 9.1 A photovoltaic cell 240
TABLES
Chapter 1
Table 1.1 Chemical composition of leaves 19
Chapter 2
Table 2.1 Energy content of monochromatic, visible light 30
2.2 Global irradiance expressed in several ways 34
Chapter 5
Table 5.1 Energy costs of C3, C4 and CAM 116
x
CONTENTS
TABLES CONTINUED
Chapter 6
Table 6.1 A loaf of bread, a jug of wine.. 124
6.2 Potatoes made of oil 134
6.3 Conversion of light energy to chemical energy 142
Chapter 7
Table 7.1 Per capita carbon dioxide emissions 162
7.2 Heating caused by greenhouse gases 165
7.3 Past and projected greenhouse gas concentrations 169
7.4 Carbon dioxide emission from fossil fuels 170
7.5 Atmospheric lifetimes of CFCs 174
Chapter 8
Table 8.1 Geological time scale 184
8.2 Chemical composition of the atmosphere 186
8.3 Carbon dioxide in atmosphere, biosphere and ocean 198
Chapter 9
Table 9.1 Renewable Resources 235
9.2 Wind energy produced in 1985, by location 238
9.3 Hydrothermal electric power plants 241
xi
CONTENTS
PREFACE
The first edition of “Energy, Plants and Man” was published in 1979. At that
time, the title seemed unexceptionable but, lest some might find it offensive now,
may I emphasise that “Man” is used simply as the name of the species (Homo
sapiens) and, like “ape”, “sheep”, “holly” or “ivy” carries no connotations of sex.
The 1979 edition was a mere 36 pages long and was then intended simply as
an introduction to some aspects of environmental biology. In compiling a second
edition it became impossible to ignore contemporary interest in the environment,
pollution, the Greenhouse Effect, the possibility of global warming and the
consequences of ever-increasing populations; hence the greatly increased length. I
also found it impossible to be dispassionate or purely objective about these matters
which have as much to do with economics and politics as with plants, biochemistry,
or physics. I wish to make it clear therefore that, while the underlying “facts” are
as sound and as objective as I could make them, the responsibility for the
accompanying opinions are mine alone and would not necessarily be shared by
others in the Robert Hill Institute, the University of Sheffield, or by any of the grant
awarding agencies that have supported my work in the past.
David Walker, June 1992
xiii
CONTENTS
ACKNOWLEDGEMENTS
Helping, in various ways, to transcribe thoughts and illustrations into printed

text has involved much hard and tedious labour by Jane Evans, Karen Bailey, Joyce
Harnden and, most of all, by Anne Dawson whose calming influence has been as
important as her immense professional contribution. At the eleventh hour, switching
from out-moded to more modern technology would have spelt disaster without the
technical skills and generously given help of Martin Aberdeen, Mike Cheshire, Paul
Leman and George Seaton, the unfailing backing of Terry Croft and long and
unstinting sessions by Andrew Askew at the computer. There was much burning of
midnight oil by Richard Walker who has been entirely responsible for the cartoons,
the technical illustrations, the cover and the lay-out. Nothing would have been
possible without Shirley Walker.
I am most grateful to the University of Sheffield, to Arthur Willis, David

Lewis and Terry Thomas for seemingly endless forbearance and understanding (and
for allowing me continued access to university facilities during a period of partial
retirement); to the Agricultural and Food Research Council which was most
responsible for providing me with a scientific base; to Peter Horton for taking over
the chairmanship of what is now the Robert Hill Institute; to the Royal Society which
gave me, with my late and greatly missed colleague Tom Delieu, the werewithal, to
design and construct the apparatus which has had such a major influence on my
scientific thinking; to Hansatech Instruments for many years of fruitful co-operation.
Most recently, I have been tremendously encouraged by a Humboldt Prize Award
and a Leverhulme Emeritus Fellowship both of which, in different ways, have done
much to further completion of this book.
All scientific books or papers are distillations of ideas which spring from
experiment and experience, from colleagues past and present, and from the relevant
scientific literature (see page 254 et seq). Long, long ago Charles Constable
encouraged me to believe that one day, I might be capable of writing if I kept on
trying. Meirion Thomas warned me about dispossessed gerunds and he and Robert
Hill were my principal scientific guides and mentors. A year with Harry Beevers at
‘Old Purdue’ was an immensely valuable part of my scientific apprenticeship.
Charles Whittingham gave me my first job. To mention everyone else by name that
I am indebted to would be a bit like compiling a list of wedding guests - so easy
to dismay or neglect by omission. I feel sure, therefore that all of those who have
worked in my laboratory and all of those in whose laboratories I have worked,
particularly in Australia, Germany and the United States, will understand if I simply
thank them collectively; their work and mine is inextricably entwined but the
responsibility for all errors, omissions and misconceptions remains mine.
David Walker, June 1992
Illustrations for the front cover and title pages include materials from a variety
of sources including Leonardo da Vinci and a number of ‘copyright free’ woodcuts
from Victorian magazines. The images of skeletons on page 1 are based on original
work by W. E. Le Gros Clarke.
Richard Walker
xv
CONTENTS
David Walker, Ph.D., D.Sc. FRS was formerly Director of the Robert Hill Institute
and Professor of Photosynthesis in the University of Sheffield. He is perhaps best
known for his work on isolated chloroplasts, the role of inorganic phosphate in
photosynthetic carbon assimilation and the development of apparatus for measuring
photosynthetic oxygen evolution.
xvi
INTRODUCTION
ENERGY AND THE FUTURE OF MAN
“Any man’s death diminishes me, because I am involved in Mankind;

And therefore never send to find for whom the bell tolls; it tolls for thee”
.... John Donne
Human predictions about the human condition have a way of turning out
wrong. Only a short time ago, or so it seems, the pundits predicted standing room
only in the western world by the year 2001. Now, although populations in many
countries continue to increase at alarming rates, relative stability has been achieved
in others in which contraception and social and economic pressures have combined
to limit the size of families. In the United States, during the early days of the space
age, it was predicted that, if Higher Education continued to expand at the going rate,
the day would not be far removed when every man, woman, child and dog would
become a Doctor of Philosophy. The fallacy of such dire prediction is self-evident
and the underlying tendencies often self-correcting. In the United Kingdom, for
example, the current destruction of the university system has progressed so far and
so fast that PhD’s may soon become an endangered species. Even so, those who may
have some knowledge of the environment, or feeling for the environment, should not
shrink from prediction or at least from providing a basis of fundamental knowledge
which might help those who would like to curb the worst excesses of environmental
exploitation. What follows is an excursion into that unsafe ground.
Green plants undertake photosynthesis. As we shall see, this is a process

from which energy in light drives the conversion of atmospheric carbon dioxide into
organic materials. As such, it provides us with most of our energy and most of our
raw materials. It has also provided us with the air that we breathe because it produces
oxygen as a by-product. Primeval atmospheres contained little oxygen and possibly
rather more carbon dioxide than now. Photosynthesis has changed all this and now
we have a great deal of oxygen (about 21%) and very little carbon dioxide (about
0.035%). Precisely how much carbon dioxide there is in the atmosphere has, until
relatively recently, been the concern of only a few scientists bent on one of those
esoteric pursuits which invite denigration by politicians and impatience by some
taxpayers who labour under the misapprehension that they support science rather
than science supporting taxpayers. Such scientists have measured the carbon dioxide
content of the unadulterated air of Mauna Loa in Hawaii, with such precision that
they have been able to see it fluctuating (but always moving upward) in accord with
world oil prices. Until recently their labours have gone largely unremarked. Now,
of course, the world at large has suddenly come to realise that the carbon dioxide
content of the atmosphere is not only important but crucial to life on earth as we
know it. The carbon dioxide which was extracted from the atmosphere by millennia
of photosynthesis in the carboniferous age and locked into oil and coal reserves, is
being returned, in a dramatically short time, by Man’s profligate use of fossil fuels.
Unless this process can be checked, it will change our planet out of all recognition.
There are also many other areas for concern which, although they may be less
dramatic, will also require fundamental solutions. In the long term, the return of
carbon dioxide to the atmosphere will be eased because there will be no oil or gas
or coal to burn. The energy crisis of the seventies has receded, for the time being,
largely because the Organisation of Petroleum Exporting Countries (OPEC) has
failed to limit production, because other countries, like the U.K., have disdained such
regulation entirely and because the United States (which returns more carbon dioxide
to the atmosphere than any other nation) has found it politically expedient to sell oil
and gasoline to its citizens at prices which do nothing to deter use. Nevertheless,
limitation of production will inevitably return as it becomes overtaken by
2
diminishing supply. At present, energy usage and carbon dioxide emissions are
closely related. No doubt there are still large reserves to be discovered but oil and
coal are finite. Accurate estimates are virtually impossible because there are so many
imponderables but, if we were to continue as we are at present, oil might be good
for another 50-100 years and coal for another 300-500. Long before that the nature
of current usage will be vastly changed by rising prices. Even in the U.K. (a country
notorious for the way in which it has squandered its coal and its oil) insulated lofts
and double glazing are now more of a norm than an oddity. Energy-efficient light
bulbs are not yet given away by public utilities, as they are in the United States, but
at least they have started to appear in British shops. In the next century the burning
of oil and coal for heating may come to be regarded in much the same way as burning
paper money.
There are, of course, any number of possible alternative energy sources -

some plausible, some not. For instance, many otherwise rational and intelligent
people quite sincerely believe that nuclear fission is the only practical alternative to
fossil fuels and naturally they have been encouraged, in this view, by the nuclear
industry. Perhaps the most remarkable sophistry of all is the latest suggestion (by
unlikely converts to “green” policies) that fission is preferable to fossil fuels because
it liberates no carbon dioxide and would, therefore, spare the “greenhouse” effect.
Quite apart from the dubious arithmetic involved (only about a third of fossil fuel
is consumed in the generation of electricity), this is about as sensible as sharing your
bedroom with a man-eating tiger as a protection against burglary - certainly unsafe,
impossibly expensive and unlikely to be well received by your neighbours.
“Certainly unsafe......”
The main trouble with nuclear fission is that it produces radioactive products,
terribly dangerous to life, which do not decay and cannot be destroyed. All that is
possible is to attempt to contain them and, unless we are indifferent to the problems
of our descendants, this means containing them for “ever”. At the time of writing,
the city of New York is reported to have started to create a pyramid of rubbish which,
3
INTRODUCTION
if ever completed, would be higher than existing skyscrapers. This is a strategy born
of desperation while measures are sought to recycle 50% of new rubbish and to find
more acceptable means of disposal. No one of sound mind (apart from the nuclear
electrical generating industry and politicians more concerned with nuclear status than
human life on earth) could even contemplate creating, quite unnecessarily, nuclear
rubbish dumps infinitely less attractive than mere mountains of garbage. In the
United Kingdom plutonium has already been detected in houses in the vicinity of the
nuclear reprocessing plant at Sellafield. This single installation has also made the
Irish Sea the most polluted in the world. Sheep farmers in Wales and reindeer herders
in Lapland, are still unable to sell their animals for human consumption as a
consequence of the radioactive fallout from Chernobyl. (There is also evidence that
the scale and extent of Chernobyl fall-out was not recognised quickly enough in the
U.K. to prevent children from drinking dangerously contaminated milk.) In what was
the Soviet Union itself, where this single disaster is said to have cost $3.5 billion,
it is no longer believed that nuclear generation of electricity can be regarded as a
safe process and some such installations are being decommissioned both there and
in the United States. Conversely, Electricity Generators in the U.K. have sought, by
sustained advertisement, to persuade public opinion that there is no viable
alternative, prompting the conclusion that if they really had such a good product to
sell they might not need to protest so much. Those who believe in nuclear fission
quite properly point to the appalling past record of human death and misery in coal-
mining and comparable industries but there is no longer any doubt that nuclear
disaster can occur. When it does occur, radioactive fall-out can reach out and damage
human life and welfare well beyond national boundaries and on a scale which
boggles imagination. It is also patently facile to suggest, as some have done, that
Chernobyl was a product of inadequate technology or that it could never happen
again. Nothing devised by man, or operated by man, has ever proved entirely safe
in the long term. Today the problems are also compounded by international
terrorism. Recent wars in the Middle East and the gratuitous murder of innocent
travellers have underlined the fact that no nation will shrink from unleashing
horrendous techniques if desperate and convinced that it has right on its side. There
are also many more mundane considerations. Uranium reserves, like fossil fuels, are
finite and fast breeder reactions bring new problems in their wake. Real costs are
rarely taken into account. Quite apart from the need to secure nuclear plant from
terrorist attack and the insoluble problem of safe disposal of radioactive waste, there
is the price of insurance against accident and of decommissioning once reactors have
become obsolete or unreliable. As it continued to be de-commissioned, the
installation at Three-Mile-Island, in the United States, still consumed dollars much
more efficiently than it ever generated electricity. It has been claimed that safe long-
term storage of nuclear waste in the United Kingdom could cost as much as the
Channel Tunnel. The British Government, intent on the “privatisation” of electricity
generation finally had to concede, in the face of simple arithmetic produced by
would-be investors, what the scientific community and the independent press had
recognised or suspected all along, that the cost of decommissioning nuclear plants
would be so immense that no one would want to buy it.
Recent demonstrations of cold fusion have created considerable interest but

seem unlikely, at least at present, to be of vast significance. In principle, nuclear
fusion could give us limitless energy but, although it occurs ceaselessly in the sun
and is the ultimate driving force behind photosynthesis (a principal subject of this
book) there seems to be no immediate prospect of it being a practical reality on earth.
Even if it were to become practicable, 90 million miles from human habitation might
seem the most desirable safe site for its operation. Fusion generates neutrons which
must be contained. Containment gives rise to radioactive materials which, like
products of fission, would need to be safely disposed.
4
Solar energy and the forces of wind, wave and tide seem much better bets.
Although frequently derided and undervalued by the pro-nuclear energy lobby, there
is no real doubt that these will come to make increasingly important contributions
over the next two or three decades. Equally, there is little doubt that they would
already be playing a much more significant role had not politicians the world over
been seduced into diverting vast resources into nuclear fission (£17 billion on nuclear
research alone in the U.K.) or determined to represent factories producing plutonium
for bombs as electricity generating stations. It would be optimistic to suppose that
the world will not experience considerable problems in meeting its energy
requirements during the rest of this century but equally pessimistic to dismiss the
possibility of new solutions. For example, solar photovoltaic (amorphous silica)
generation of electricity, is already practicable, fast becoming cheaper and, at about
30% efficiency, would not call for inconceivably large areas of global surface
(according to George Porter about 50 million hectares, or roughly twice the area of
the United Kingdom, in order to provide existing world populations of 3-4 billion
with 5 kW per head). Electrolysis of water would, in turn, produce a fuel (hydrogen)
which, if ways can be found to safely contain its formidable reactivity with oxygen,
could power surface vehicles, aircraft and the like. In the U.K., one hydro-electric
facility, utilising the tidal energy of the Severn Bore could generate more electricity,
ad infinitum, than the combined nuclear stations in Britain (about 10-15% of total
requirement).
What is now manifestly clear is that the world should make much better use
of the energy that it already has at its disposal. At least one authority in the field
of energy conservation believes that present use of fossil fuels and electricity could
be cut by 75% if rapidly developing techniques in energy saving were fully and
properly utilised and that this could be achieved not only without detriment to world
economies but with actual benefit. Mankind lived in equilibrium with the
environment when populations were a fraction of what they are now and expansion
only became possible as fossil fuels were used on an increasingly large scale.
Advocating a downward adjustment of population size may seem unethical or simply
unlikely to succeed but there is no doubt that such a decrease would ease the current
problems and there is every likelihood that a decrease will occur by famine,
pestilence or major global disaster if it can not be achieved by consent.
Even if the energy problem is solved, there will still be an increasing shortage
of cheap organic carbon during a period in which oil and coal reserves decline and
prices increase correspondingly. At present we use oil and coal not only as fuels but
also for almost every conceivable material purpose. We live in a world of metal and
plastic which is fashioned out of, or with the help of, the organic carbon of which
these fossils are comprised. Now they are plentiful but, once they become scarce,
we shall be obliged to fall back on contemporary photosynthesis to provide us with
our needs. Past photosynthesis locked atmospheric carbon dioxide in oil and coal
and, as shortages make these increasingly expensive, we shall come to rely more and
more on products of contemporary photosynthesis such as wood. (Already the more
far-seeing are turning to the fermentation of plant materials as a source of alcoholic
fuels although it should be noted that while alcohol is a feasible alternative to
gasoline in some places (as in Brazil) it is unlikely to provide a global solution
because of the implications for land use and the high energy costs of distillation.)
At first glance, the possibility of a real shortage of organic carbon seems ludicrous
in the extreme. Annual photosynthetic carbon assimilation (the conversion of carbon
dioxide into organic carbon by plants in the light) is of the order of 100,000 million
tons of carbon dioxide fixed - much greater than all the oil, coal and minerals used
every year. On the other hand a large proportion of this carbon enters products which
are presently inaccessible or unused by man. Even the desirable commodities, such
5
INTRODUCTION
as food, are in short supply in many places (although starvation is frequently a

consequence of economics rather than real famine). The under-privileged go hungry,
not because the world cannot grow enough food, but because they cannot afford it
or because of political considerations. The European Community grows much more
food than it knows what to do with. This is a reason, in some minds, for
discontinuing research into means of increasing plant productivity while
simultaneously turning a blind eye to the co-existence of food mountains in Europe
and starvation in the Third World.
Famine in Ethiopia and elsewhere should remind us all that total food reserves
are only about 40% of annual world consumption and that even this slender margin
only exists because of the achievement of agricultural science. More people probably
owe their lives to the introduction of new varieties of crop species and to the effect
of selective herbicides on grain production than to the availability of antibiotics.
However, even where famine on a major scale has become a thing of the past (as
on the Indian sub-continent), it has only been prevented by major energy inputs in
the form of chemical fertilisers and is still only too readily brought back by sustained
drought.
The utilisation of energy, and of organic carbon is inextricably linked to

economics and the pattern of human society. Food is expensive because energy is
expensive. The most “advanced” forms of Western agriculture are often little more
than inefficient ways of turning fossil fuels into edible products, of turning oil into
potatoes, depending as they do on the manufacture of synthetic fertilisers, herbicides
etc., and on the construction and operation of farm machinery. Conversely, primitive
agriculture, which uses little energy other than that of the sun, the farmer, his family
and his animals, is often equally sparing in yields and frequently fails to maintain
large populations at acceptable levels of nutrition.
6
Linked to all of these considerations is the “Greenhouse Effect”. Carbon

dioxide and gases like methane (generated by mining, by cattle and by decomposition
of vegetation and garbage) intercept infra-red radiation and therefore diminish heat
losses to space. Deserts, very hot by day, are frequently very cold by night because
water vapour also intercepts infra-red and nights are mostly colder when there is no
cloud cover to act as a heat- retaining blanket. (Hence the “greenhouse effect”, by
analogy, because light entering a greenhouse, or glasshouse, warms the contents and
its glass walls diminish the rate at which heat is lost to the exterior.) If there were
no greenhouse gases, like water and carbon dioxide, the earth would be a frozen
planet with an average surface temperature of about -15°C (rather than about +18°C
as it is now). Until relatively recently, the natural greenhouse gases (such as carbon
dioxide, water vapour, methane, nitrous oxide) trapped about 40% of the infra red
radiation from the earth’s surface and, from about 1850 to 1960, increasing carbon
dioxide was the major contributor to Greenhouse warming. Since 1960, rising
methane, nitrous oxide, and “refrigerator gases” (chlorinated fluorocarbons or CFCs)
have become as great a problem as carbon dioxide because, like Heineken beer, they
reach the parts that carbon dioxide doesn't reach (i.e. they absorb in parts of the
spectrum in which carbon dioxide has not already exhausted any further capacity for
infra-red absorption). For this reason, methane is 25 times more damaging than
carbon dioxide and CFCs 10,000 times more damaging on a molecule for molecule
basis.
A greenhouse would become even hotter if made of glass which transmitted

ultra-violet radiation. This is why the destruction of the ozone layer by aerosol and
refrigerator gases (CFCs) aggravates the greenhouse effect by allowing more ultra-
violet radiation from the sun to reach the earth. (Ozone screens out ultra-violet like
compounds used to prevent sun-burn). This is why, in letters to the editors of British
newspapers, sighting the first sun-burnt skin has become more newsworthy than
hearing the first cuckoo of spring.
Carbon dioxide in the atmosphere was diminished to something below its

present concentration of about 350 parts per million by past photosynthesis and much
of what was locked into coal and oil during the Carboniferous Era is now being
restored to the air by human activity. In 1868, judging from bubbles trapped in polar
ice and other evidence, atmospheric carbon dioxide was as low as 0.027%. Since
1957, carbon dioxide has increased from 0.0315% to about 0.0350% and is
continuing to accumulate in an ever increasing fashion, threatening to double in
concentration in the next 80 to 130 years. Contemporary photosynthesis cannot keep
pace with this rate of increase even though, as we shall see, it is favoured by high
carbon dioxide. The United Kingdom, for example, is currently producing about 10
tonnes of carbon dioxide per head of its population per annum and with a total area
of about 24 million hectares consumes less than one third of this amount in
photosynthesis. Moreover, much of this carbon dioxide does not remain “fixed”.
Carbon dioxide incorporated into materials like wood remain locked away for a long
time but only mature forests constitute large repositories for fixed carbon dioxide and
these are in balance with the atmosphere returning about as much carbon dioxide and
methane via respiration and organic degradation as they fix in photosynthesis.
Destruction of tropical rain forests, together with their untold genetic treasures, is a
world tragedy which has contributed significantly to atmospheric carbon dioxide but,
while they exist, these forests do not offset the unrelenting increases which result
from burning fossil fuels.
Extrapolation of current increases in carbon dioxide suggests that many of

those alive today will live to see a world in which the atmosphere contains twice as
much carbon dioxide as it does now. Evaluation of the consequences of such
7
INTRODUCTION
doubling is much less certain. There is every prospect that world temperatures will
increase by 2 or 3 degrees. It is much more difficult to predict what will follow
because of the uncertainties relating to ocean currents and such notoriously fragile
aspects of world ecology as the Arctic tundra. At worst, such temperature rises could
change the world out of all recognition, as melting ice caps raise the level of the
oceans and inundate the great cities built at sea level. At best it could unite world
opinion behind measures to protect the environment. At its most facile, it could
become yet another excuse to promote nuclear fission as a source of power.
What follows is an attempt to introduce some of the physical and biological

realities which are involved in man’s utilisation of energy. It discusses the source
of biological energy, the manner in which solar energy is converted into chemical
energy in photosynthesis and the implication of these relationships for plant
productivity and for man. These matters are considered in the context of global
warming, the greenhouse effect and what, if anything might be done to postpone or
limit the consequences of increasing carbon dioxide. This book presumes only the
most modest knowledge of biology, chemistry and physics and craves the indulgence
of those who are much better versed in these subjects than the author. It does not
seek to avoid all political bias and it trusts that the reader has some sympathy for
Alice’s sentiments about books.
8
CHAPTER 1 - A FEW FUNDAMENTALS
MATTER AND ENERGY
1.1 Atoms, Molecules and Bonds
“The theory of the chemical bond, as represented in this book,

is far from perfect” ....Linus Pauling
If we are to understand the energy requirements of Man, and of the plants on

which he depends, we need to delve a little way into the nature of matter itself.
Before Queen Victoria came to the British Throne in the last century, the
people of London used to bathe naked in Hyde Park because it seemed obviously
sensible to undress before going into water. More recently, this has been regarded
as improper, and (for bathing in public) people have worn correspondingly more or
less clothing, according to the perceived morality of the day and the place. At one
time there was thought to be an irreducible minimum called the “bikini”. This was
derived from the atom “test” in which a nuclear bomb was exploded on the Bikini
Atoll in the Pacific. The connexion between the event and the garment is that the
atom was also once regarded as the irreducible minimum. Dalton’s atomic theory of
1803 proposed that all matter is composed of small indestructible particles, or atoms,
which cannot be further divided by ordinary chemical means.
[Elements, the ninety odd chemical “entities” from which all other substances
are formed, contain atoms which are characteristic of that particular element
and are alike in all respects. Compounds, formed from the combination of two
or more elements, are composed of molecules. These, in turn, are comprised
of atoms joined together by various sorts of chemical bonds.]
As the world now knows to its cost, the atom is not indivisible but is itself
composed of elementary, or fundamental, particles such as electrons, protons and
neutrons. Hydrogen is the smallest, lightest and simplest atom. It can be regarded,
for our present purpose, as a nucleus carrying a positive electrical charge (a proton
or hydrogen ion, H+) with a negatively charged particle, or electron, circling around
it. In general, the atomic nucleus is much larger than the electrons associated with
it and comprises more than 99.95% of the mass of an element. In the case of
10
ATOMS, MOLECULES AND BONDS
hydrogen, the proton and electron, taken together, are a bit like the earth with a
single, orbiting, satellite or an Olympic athlete swinging “the hammer” at the end
of a chain. Energy in the form of rocket fuel, is needed to lift a satellite into orbit
and, the more distant the orbit, the more energy is required. Similarly, the electron
may be considered to circle the nucleus at a specific energy level. More energy would
be required to lift it further from the nucleus and energy would be released if it
dropped to a lower level. In certain circumstances, electrons can also move between
atoms and between molecules.
[In physical terms, such movement of electrons is described as an electrical

current; in biologically analogous situations it is described as electron
transport. It may also be noted that, by convention, an electric current is said
to flow from positive to negative, whereas electrons actually flow in the
opposite direction, from negative to positive. This is not as anomalous as it
might at first seem because, as a negative charge moves in one direction, a
positive charge must move in the opposite direction.]
The space satellite circling the earth is prevented from leaving its orbit by
gravitational force, the athlete’s hammer by its chain.
The electrons circling the atomic nucleus are similarly maintained in orbit by
the electrical attraction between positive and negative charges. In a metal conductor,
electrons can separate from their parent atoms and move freely through the metal,
while the atoms which have temporarily lost their electrons, now positively charged,
remain in a fixed position. If such a conductor, (e.g. a copper wire) is used to connect
a “source” of electrons to a “sink” for electrons (as in joining the positive and
negative terminals of a battery) electrons will flow from (negative) source to
(positive) sink. The conductor will offer resistance to this flow of electrons as they
collide with stationary atoms in the metal. In such a collision, the electron will
transfer the kinetic energy (which it had acquired from the electrical field established
by the potential difference between source and sink) to the vibrational energy of the
atom. For this reason, conductors tend to become hot as electrons flow through them
as in “electric fires” or heating elements. The thinner the conductor or wire, the
greater the frequency of collision and the greater the internal generation of heat. All
11
such objects can lose heat by radiation of electromagnetic energy (which moves
through space at the speed of light). If the radiation is at wavelengths (see Section
2.2) which can be perceived by the human eye it is referred to as “visible light”. We
can “create” light in this way if we pass electrons from a source (the negative
terminal of a battery), through the very thin wire (filament) in an electric light and
back to a sink (the positive terminal of the battery). Chemical reactions in the battery
maintain the electron flow. This is an example of energy transduction, the conversion
of chemical energy into light and heat. Plants, as we shall see, can do the converse
and convert light-energy into both electrical energy and chemical energy. In
molecules, the orbiting electrons are shared by two or more atomic nuclei. As a result
of this sharing process, the molecular orbitals are smaller than the combined atomic
orbitals. Accordingly, molecular orbitals are at a lower energy level than
corresponding atomic orbitals, just as it would require a smaller expenditure of
energy to put a satellite into a close orbit, about the earth, rather than a more distant
one. For this reason, the formation of chemical bonds between atoms is always
accompanied by an energy loss. Similarly, an energy input is always required if a
chemical bond is to be broken.
“energy input is always required if a chemical bond is to be broken”
Most human energy requirements are met by forming bonds between

hydrogen and oxygen (see page 129). This occurs when fuels are burned. The fuels
may be foods which are burned (or respired) in the body, or materials like oil and
coal which are consumed in engines or furnaces. Conversely, photosynthesis is the
process which produces, or has produced, such fuels. It involves splitting hydrogen-
oxygen (H-O) bonds in water. To do this it utilises energy which is produced by
nuclear fusion of hydrogen in the sun.
[Four protons (i.e. four H+ or hydrogen ions) fuse to produce one molecule
of helium. The fusion of one gram of hydrogen ions produces about as much
energy as burning 16 million grams of oil.]
The energy produced by nuclear fusion fuels the furnaces of the sun and a
fraction is transmitted to the earth as light (Chapter 2). It is intercepted by leaves and
converted, by them, first into electrical energy and then into chemical energy. Apart
from nuclear fission and ocean tides this is the source of virtually all energy on earth.
12
OXIDATION AND REDUCTION
1.2 Oxidation and Reduction
Burning a fuel is an oxidative process. The formation of a fuel is a reductive

process. Since this is central to the whole of biological energetics it is important that
the concepts of oxidation and reduction (and the associated transport of electrons)
are fully understood. It is better, so it is said, to give than to receive. This is true,
in a sense, of oxidation and reduction which are also linked processes. There is
always a donor and an acceptor. As one becomes oxidised the other becomes reduced
and vice versa. The common feature is electron transport, or transfer. Electrons are
donated in oxidation and accepted in reduction. Reduction implies diminution or
becoming less and, if we remember that electrons are negatively charged, the
terminology starts to make some sort of sense. Obviously accepting something
negative can be regarded as a decrease or reduction.
Electron Transfer
If we look at a few examples, things should become clearer. Perversely, the

most familiar example is perhaps the most difficult to understand in terms of electron
transfer. If we take carbon (in a form such as charcoal) and burn it in a barbecue
it becomes oxidised. Carbon dioxide is formed and energy is given off as heat and
light
C + O2 → CO 2 + energy Eqn. 1.1
Man has been rejoicing in the energy released as heat and light in this and similar
reactions since the beginning of time. It is not difficult to believe that those of us
who live in cold climates prefer “open” fires to “central” heating because the warmth
and flames and sound and smell of burning wood evokes some distant race memory.
But, you might well ask, where in this particular process (i.e. burning carbon, as in
Equation 1.1), can we see evidence of electron transport? Before we attempt to
answer this question, let us first examine some other examples of oxidation and
reduction.
Respiration, whether carried out by people or plants, is essentially the same

process of “burning”, or oxidising, organic compounds. The carbon containing
compounds which are burned in respiration are most likely to be sugars. The
combustion is more controlled but energy is produced and carbon dioxide liberated
just as it would be if sugar were burned on a fire. Conversely, in photosynthesis,
plants use the sun’s energy to “fix” carbon dioxide into organic compounds. One of
13
the major end-products of photosynthesis is, in fact, “ordinary” sugar (or sucrose,
which contains 12 atoms of carbon) but the first formed products include more
simple sugars containing 3, 4, 5, 6 and 7 carbon compounds. (Section 5.2)
Some biological oxidations also involve direct addition of oxygen but, more
often, oxidation of a metabolite (a compound undergoing metabolism, such as a
sugar) occurs mainly by removal of hydrogens. If we represent such a metabolite by
MH2 we can write an equation
MH 2 + A → AH 2 + M Eqn. 1.2
In this equation MH2 donates hydrogens to an acceptor (A). The donor, MH2,
becomes oxidised to give M. The acceptor, A, becomes reduced to AH2. Because
hydrogen is composed of a proton (i.e. a hydrogen ion, H+) and an electron, e-
transfer of hydrogens also always involves transfer of electrons.
H ⇔ H+ + e- Eqn. 1.3
(atom) (proton) (electron)
Accordingly, electrons are transferred, or transported from the substance

which is being oxidised to the substance which is being reduced.
Hydrogen Transfer
In metabolism, there are often long sequences, or chains, of hydrogen (or

electron) acceptors. It is partly for this reason that “burning” a sugar in respiration,
although it eventually involves the addition of oxygen, does not liberate energy quite
so dramatically as it does if sugar is burned on a fire. Instead, energy is released in
a trickle rather than a flood. In addition, much of the energy is not released at all,
immediately, but is conserved, as chemical energy, in “high-energy” substances, such
as ATP, which will be discussed later (Sections 4.6 & 4.7).
As we have now seen, hydrogen transfer always involves electron transfer
14
OXIDATION AND REDUCTION
(because a hydrogen atom contains an electron) but electrons can also be transferred
by themselves i.e. without an accompanying hydrogen ion, or proton (H+). Both in
respiration and in photosynthesis, cytochromes of different sorts are important
electron carriers (constituents of the electron transport chain. Cytochromes are a type
of protein which contain iron (Fe) in the heart of their molecular structure. This iron
can be represented as Fe++ (in its reduced or ferrous state) and by Fe+++ (in its
oxidised or ferric state). The increase in the number of positive signs (in this case
from two to three) indicates the loss of one electron just as it does in H+ (a hydrogen
atom which has lost an electron and therefore a negative charge). When a reduced
cytochrome (Cyt Fe++) is oxidised to Cyt Fe+++, only electrons are transferred and
the reduced electron acceptor can be written A- to indicate that it is now the proud
possessor of an electron carrying a negative charge.
Cyt Fe ++ + A → Cyt Fe +++ + A - Eqn. 1.4
As it happens, electron acceptors are particular about what they will, or will
not, accept. Some, like cytochromes, will only accept and donate electrons. Others,
like quinones (which are also important electron carriers) like to have both an
Hydrogens Offered, Electrons Accepted
Electrons Offered, Hydrogens Accepted
15
electron and a proton; i.e. they are electron carriers only in the sense that they are
hydrogen carriers and because accepting a hydrogen necessarily involves the
acceptance of an electron. All of this may seem somewhat complicated but we need
to understand it if we are to understand the basis of conserving energy in a chemical
form. If a cytochrome is offered a hydrogen (H ⇔ H+ + e-) by a quinone (or a
“quinol” as a “quinone” is more properly called when it is in the reduced state) it
can only accept the electron (e-) which is a constituent of that hydrogen atom. The
proton (H+) is left behind in solution and the solution, therefore, becomes more acid
because of the consequent increase in its hydrogen ion concentration (see Section
1.7). Conversely, if the cytochrome seeks, in turn, to offer its newly acquired electron
to yet another acceptor which is only prepared to accept hydrogens, a proton must
be taken up from solution along with each electron accepted. When such acceptors
are contained within a membrane this can result in protons being “moved” from one
side of the membrane to the other during electron transport. As we shall see later
(Section 4.7), this is the essence of Mitchell’s Chemiosmotic Hypothesis which
offers an explanation for the way in which proton gradients are established across
membranes and how these gradients are then used in the synthesis of ATP (a so-
called “high energy” compound).
What should always be remembered is that oxidation always involves electron

transport. Electrons are transported from the atoms or molecules which are being
oxidised to corresponding acceptors which therefore become reduced (and, in the
sense that they have acquired electrons, more negative). If we return, for a moment,
to the burning of coal or charcoal it is, perhaps, less obvious why the addition of
oxygen to carbon also involves electron transport. In fact, in this and similar cases,
the electrons move within the molecule. In this particular example, they move away
from carbon towards oxygen. This is because oxygen is intrinsically more attractive
to electrons (more oxidising) than carbon. The extent to which substances attract or
repel electrons (their oxidation/reduction potential) is also very important in
biological energetics and helps to determine the manner in which electron carriers
are organised within membranes (see e.g. Fig. 3.5).
1.3 Electron Transport in Photosynthesis and Respiration
Photosynthesis
2H 2 O 2A [CH 2O ] 2A 2H 2 O
_
+ H O +
2
+ +
O2 2AH 2 CO2 2AH 2 O2
_
Respiration
Fig 1.1 Relationship between photosynthesis and respiration. In photosynthesis

H-O bonds are broken, O2 is evolved, and CO2 is reduced to CH2O. In respiration
CH2O is oxidised. CO2 is released and H-O bonds are re-established.
16
ELECTRON TRANSPORT IN PHOTOSYNTHESIS
In photosynthesis, light energy is used to break hydrogen-oxygen (H-O)

bonds. The oxygen is liberated and the hydrogens (at times as hydrogen but at other
times split into their constituent electrons and protons) pass through a series of
carriers or acceptors (designated “A” in Fig. 1.1) to carbon dioxide. When carbon
dioxide becomes reduced in this way we call it CH2O because this is the simplest
way to represent a carbohydrate (a compound containing the elements of carbon and
water, i.e. “hydrated” carbon or carbohydrate)
[Some texts prefer to use C6H 12O 6 rather than CH2O to represent a
carbohydrate but, while compounds with this formula actually exist, and
CH2O is just a symbol, there is little point in thinking about the fate of six
carbons when one will suffice. Moreover, using C6H12O6 could imply that
glucose (which is one of several compounds with this empirical formula) was
the immediate end-product of photosynthesis whereas, in reality, it is not
(Section 5.2)].
In respiration CH2O is oxidised. The hydrogens (or electrons) are passed,

through a series of acceptors or carriers, to O2 which becomes reduced to water
(H2O). Carbon is released as carbon dioxide (CO2) and the energy which is derived
from the re-formation of H-O bonds is made available for metabolic and other life
processes. Incidentally, oxygen does not normally exist as a free atom (O) but as an
oxygen molecule (O2) so that, in order to derive the simplest possible equation,
oxygen is sometimes represented as half a molecule ( 12 O2) rather than a single atom.
2H + + 2e - + 1
2 O2 ⇔ H2O Eqn. 1.5
Man also sometimes burns CH2O in his fires, furnaces and engines to meet
his other energy requirements but, more usually, burns fossilised products of
photosynthesis such as coal or hydrocarbons (C-H compounds) which are more
reduced than carbohydrates.
All living organisms respire but only green plants can utilise light energy to
split water and reduce carbon dioxide. Green plants make their own CH2O; animals
obtain it by eating plants or other animals. Compounds other than CH2O are made
in photosynthesis and consumed in respiration but the underlying principle is the
same i.e. light energy is used to split H-O bonds and the restitution of these bonds
releases energy for other processes.
THE SOURCE OF ORGANIC CARBON
1.4 The Products of Photosynthesis
When we look about us, much of what we see, other than stone and water,
is either a photosynthetic product or something derived from photosynthetic
products. This is obviously true of all living organisms, such as wood and natural
fibres. In addition, coal, oil and natural gas (fossil fuels) were formed by
photosynthesis in the past and metal, brick, glass and ceramics all require the
expenditure of large quantities of fossil fuels to produce them. In processes such as
smelting, fossil fuels may also serve as reducing agents (i.e. compounds which are
ready to donate electrons or, in this instance, to accept oxygens).
17
metal oxide + C → metal + CO 2 Eqn. 1.6
Even soil owes its present form and structure to the action of living organisms and
one-fifth of the atmosphere is composed of oxygen released from water during
photosynthesis (Section 8.3). The atmosphere is also the immediate source of organic
carbon which is all derived from carbon dioxide. Although these facts are
commonplace, many believe that the green plant obtains its nutriment from the soil.
This belief seems entirely reasonable at first glance, and, in everyday life, we accept
it without too much thought because we are used to gardeners who talk about
“feeding” plants and to the extensive use of fertilisers. However, the fallacy of this
supposition was demonstrated as long ago as the seventeenth century by Van
Helmont who grew a willow in a tub of weighed soil. After watering for five years,
the willow weighed 164 lbs more and the soil only 2 ounces less. Being an honest
man, Van Helmont attributed the loss of 2 oounces to experimental error and very
sensibly concluded that the tree had grown solely at the expense of the rain-water
used for watering.
“Van Helmont Waters the Tree”
“But that Experiment of his which I was mentioning to You, he fayes, was this. He
took 200 pound of Earth dry’d in an Oven, and having put it into an Earthen Veffel
and moiften’d it with Raine water he planted in it the Trunk of a VVillow tree of five
pound VVeight; this he VVatered, as need required, with Rain or with Difftill’d
VVater; and to keep the Neighbouring Earth from getting into the Veffel, he
employed a plate of Iron tinn’d over and perforated with many holes. Five years
being efflux’d, he took out the Tree and weighed’ it, and (with computing the leaves
that fell during four Autumnes) he found it to weigh 169 pounds and about three
Ounces. And Having again Dry’d the Earth it grew in, he found it want of its Former
VVeight of 200 Pound, about a couple of Ounces; fo that of 164 pound of the Roots,
VVood, and Bark, which Confituted the Tree, feem to have Sprung from the VVater”.
- a contemporary account of Van Helmont’s experiment (from Robert Boyle, “The Sceptical Chemist”)
Despite what he said, Van Helmont was probably a better experimentalist than he
imagined, and today’s interpretation would be that the willow derived most of its
18
THE PRODUCTS OF PHOTOSYNTHESIS
nutriment from the air, as carbon dioxide, and some essential minerals from the soil
The actual mineral requirement varies with the plant or crop but it is often less than
5% of the dry weight (Table 1.1). This is not to say that fertilisers are unimportant
On the contrary, they are essential but they are not “nutriment”, in the fullest sense
of the word, any more than salt would be regarded as food in human diet. They
become parts of a plant but are not a source of energy. Indeed large amounts of
energy (in the form of fossil fuels) are used in modern agriculture to produce
fertilisers (Table 6.2).
A large number of elements (including so-called trace elements which are

needed in only small amounts) are required for sustained growth. The most
important, in regard to the amount which is required, is nitrogen (N).
1.5 Chemical Composition of Leaves

All plants and animals contain protein. All proteins are made of amino acids and all
amino acids contain some nitrogen, together with carbon and other elements (such
as oxygen and hydrogen and, sometimes, sulphur).
Table 1.1
CHEMICAL COMPOSITION OF LEAVES
Fresh Weight
H2O Usually greater than 90%
Dry Weight
C About 45%
O About 45%
H About 5%
N Often 1-3%
P,S,K,Na,Ca,Mg
and Trace Elements
(Together with N) Usually 1-5%
Green plants are normally unable to utilise atmospheric nitrogen unaided

although some (including beans and other legumes, and a few trees such as alder)
can utilise nitrogen with the aid of certain micro-organisms. Most crops therefore
depend on nitrate and ammonium compounds in the soil and, in principle, continued
removal of grain and other products containing appreciable quantities of nitrogen
should lead to progressively poor yields. In practice this does not always happen. For
example, a plot at Rothamsted Experimental Station, in the UK, has produced more
or less unchanging yields since 1848, perhaps because N2 fixation by algae and other
organisms has maintained the status quo, and presumably because the loss of other
essential elements has been too slow to seriously deplete the soil’s reserves.
Nevertheless, although plants, like people, require only very small quantities of
essential elements, these substances are essential and yields are improved by regular
application of nitrogen (N), potassium (K), phosphorus (P) and other elements.
Moreover, some modern crops have been bred to give maximum yields only in soils
which have been copiously supplied with fertiliser. Much freely soluble fertiliser
may be lost in drainage waters and create environmental problems such as massive
algal growth in lakes in which the natural level of recycling minerals would
19
otherwise be too low to support extensive growth. Fixed nitrogen is also lost to the
atmosphere by bacterial action. Genetic engineering may conceivably extend
nitrogen-fixing ability to species which lack it at present. This in the absence of
unforeseen hazards, could constitute a major agricultural advance but it would
involve expenditure of metabolic energy by the plant.
1.6 Ashes to Ashes
Carbon dioxide comprises only a little more than 0.03% (300 parts per
million) of the normal atmosphere. Said quickly, this sounds small but, on sober
reflection, it is remarkably small. There are more people with red hair per head of
the average population than molecules of carbon dioxide in the normal atmosphere.
This has many implications, including the fact that much of the available carbon
dioxide is constantly recycled and much of it must have completed many cycles
already. Plants fix carbon dioxide in photosynthesis. Plants, animals, microbes and
people return it to the atmosphere through respiration or (in the fullness of time) by
more permanent means.
- with compliments to Spike Milligan.
In medieval times uptake and release of carbon dioxide was in some sort of
balance just as large areas of untouched forest are now. In the last 200 years the huge
explosion in the size of human population has only been made possible by a
corresponding acceleration in the utilisation of fossil fuels (Chapter 8).
ENERGY TRANSDUCTION IN PHOTOSYNTHESIS
In one regard, photosynthesis is the source of organic carbon and material

derived from organic carbon. In another, it is the major mechanisim of converting
light-energy into the energy which Man uses every day for metabolic and other
purposes.
1.7 An Analogy
Many of us learned, at mother’s knee, that if two platinum electrodes are

immersed in acidified water and joined by wires to an electric torch battery, hydrogen
20
AN ANALOGY
s evolved at one electrode and oxygen at the other. This “electrolysis” (electrical-
splitting) of water is complicated in detail but relatively simple in principle. Water
dissociates spontaneously to give very small quantities of hydrogen ions (H+) and
hydroxyl ions (OH-)
H - O - H ⇔ H + + OH - Eqn. 1.7
The H-O bonds in water are ordinary “covalent” bonds in which H and O each share
a pair of electrons. On dissociation, both electrons stay with the hydroxyl ion
(OH-). In consequence this gains a negative charge (becoming OH- rather than OH)
whereas the hydrogen atom (H) loses its electron and is left as a proton or hydrogen
ion (H+). Although this process occurs spontaneously it proceeds only to a very small
extent before reaching equilibrium (when only one out of 10 million molecules has
dissociated).
[This incidentally, is related to the fact that pure water has a pH of 7.0. The
symbol “p” means “negative logarithm of” so that, if the hydrogen ion
concentration is 1 in 10 million, i.e. if the logarithm of the hydrogen ion
concentration is -7, then the negative logarithm will be +7. In theory the pH
of water should therefore be 7. In practice it is frequently more acid because
of dissolved carbon dioxide and other factors.. It should also be noted that
both the nature of the ions which are formed and the mechanism of
electrolysis are both more complicated than the simplified version given here
but the basic principles are essentially the same.]
In a chemical reaction an unfavourable equilibrium can be displaced if it is

possible to provide “sinks” for the products (i.e. if the products can be removed from
the site of the reaction). In electrolysis, the electrodes are sinks.
Fig. 1.2 Electrical analogy of Photosynthetic Oxygen Evolution. Electrolysis of

water driven by an illuminated photoelectric cell rather than a chemical battery (See
text).
The passage of the electric current (a stream of electrons) through the external
circuit (Fig. 1.2) leads to an accumulation of electrons at one electrode (the cathode
or “source” of electrons) and a dearth of electrons (visualised as positively charged

holes from which electrons have been vacated) at the other (the anode or “sink” for
electrons). Accordingly, protons accept electrons at the cathodes and are then
evolved as hydrogen. At the anode, hydroxyl ions donate electrons in reacting
together to give oxygen and water.
In the system illustrated in Fig. 1.2 the conventional battery has been replaced
by a photoelectric cell. On illumination, the current for electrolysis is generated by
the solar cell in an excitation process which is basically similar to the light excitation
of chlorophyll (Section 3.1). Thus light energy is converted into electrical energy and
this in turn is used to break H-O bonds. If the gases which are evolved from the
electrodes are collected in a single vessel and a spark is passed, the H-O bonds are
re-established with explosive violence, as the energy which has been trickled in from
the photoelectric cell is instantly released.
“H-O bonds are re-established”
The electrolytic process is analogous to photosynthesis in the sense that light

energy is used to break H-O bonds in a reaction, involving chlorophyll (Section 3.1)
which is fundamentally similar to that which occurs in a photoelectric cell. As in Fig.
1.2, the photosynthetic process in green plants also involves the liberation of oxygen
and the generation of an electric current but, of course, photosynthetic electron
transport involves the transfer of electrons from carrier to carrier in a membrane
rather than movement of electrons through a wire. As we have already seen,
biological electron transport is an oxidation/reduction process. At one end of the
chain of electron carriers, water (H2O) is oxidised to oxygen (O2) by virtue of
hydrogen removal. In electrolysis this hydrogen is released as a free gas and (with
the help of a bacterial enzyme) the green plant reaction can be made to do the same.
In the intact green plant, however, most of the hydrogen is eventually transferred to
carbon dioxide (CO2) which is thereby reduced to carbohydrate (CH2O). The process
of transfer itself is basically one of electron transfer (Eqn. 1.3). Electrons are
transferred at every stage but only some carriers can also accept a proton (H+) along
with an electron (i.e. accept a hydrogen, because H+ + e- ⇔ H). At such points along
the chain, protons are released and at other points they are taken up. Finally, at the
end of the chain, electrons (once part of water) and protons are added to carbon
dioxide to give CH2O.
In respiration (Fig. 1.1), H-O bonds are re-established and therefore energy
22
AN ANALOGY
is made available once again. Respiration does not proceed with explosive violence
because hydrogen is not reunited with the oxygen in one step. Instead the energy is
released, piecemeal, as hydrogen is transported to oxygen via a long sequence of
intermediate carriers.
Most human energy requirements are met by forming bonds between

hydrogen and oxygen, whether we are thinking in terms of metabolism, agriculture,
industry, transport, building or domestic needs such as heating, cooking, refrigeration
or whatever.
THE PHILOSOPHER’S STONE
1.8 How to be one up
“A good many times I have been present at gatherings of people who, by the
standards of the traditional culture, are thought highly educated and who have, with
considerable gusto, been expressing their incredulity at the illiteracy of scientists.
Once or twice I have been provoked and have asked the company how many of them
could describe the Second Law of Thermodynamics. The response was cold: it was
also negative. Yet, I was asking something which is about the scientific equivalent
of : - “Have you read a work of Shakespeare’s ?”’....C. P. Snow.
In this chapter it is claimed that photosynthesis winds the biological

mainspring, that energy originates in the sun and that photosynthesis is the means
of making this energy available to living organisms. That, you might think, is quite
enough to be going on with but no self-respecting book which seeks to concern itself
with energy and Man, let alone with plants, can get by without at least a nod in the
direction of the Laws of Thermodynamics.
1.9 The Laws of Thermodynamics.
The Laws of Thermodynamics.
First Law Energy can be neither created nor destroyed.

The energy of the universe is constant.
Second Law The entropy of the universe always increases.

There is a universal tendency to chaos and disorder.
Third Law The entropy of a perfect crystal of any element or

compound is zero at absolute zero temperature.
As stated above these “laws” are more than a little daunting and, to mean
anything at all, would propel us immediately into even less user-friendly concepts
like “entropy”.
[Entropy describes the state or conditions of matter in regard to the random

motion of the atoms and molecules of which it is composed. For example, as
the temperature of water increases, or as it changes state from ice to liquid
or from liquid to gas, this motion becomes more vigorous and less ordered.
Entropy is therefore a measure of disorder and the second law supposes a
universal tendency towards disorder. Herein lies the notion of cosmic futility
23
or entropic doom. Only within a crystal at absolute zero does order reign
supreme in the absence of thermal movement. Fleetingly, living organisms
can reverse the general trend towards the random state by becoming more
organised at the expense of their surroundings.]
If we are determined not to be daunted by the laws of thermodynamics we

need only remind ourselves that they are not so much “laws” as summaries of endless
human experience which tells us that we rarely get anything for nothing and that,
if left to their own devices, everything in the universe tends to run down. In these
terms they have been restated as follows:-
First Law You can’t win.
Second Law You can’t break even.
Third Law You can’t stay out of the game.
As stated above, the laws of thermodynamics are easy to remember. So easy

in fact that we are now immediately one up on C.P. Snow’s literary acquaintances
and possibly on our friends. These laws also have clear implications for our present
theme. Most of our energy comes directly or indirectly (as fossil fuels) from the sun.
In either case it is finite. Fossil fuels once burned are gone for ever. Their energy
is not destroyed but it is dissipated. There is no way that Man can easily recapture
heat that has gone up a chimney; energy that has been used to move a vehicle from
place to place. Only living organisms have the ability to create order (low entropy)
out of chaos (high entropy) and this apparent reversal of the “second law” is only
ephemeral - it is all ashes to ashes and dust to dust in the end. To recognise that the
grave beckons, is not necessarily cause for despair even amongst those who see no
prospect of resurrection. It may not happen for some time and consider what liberties
might be taken with entropy in the meantime. The Laws of Thermodynamics should,
on the other hand, behove us not to dissipate energy unwisely or unnecessarily. As
we shall see, living organisms in general are very good at conserving energy and
society at large would do well to emulate them.
24
CHAPTER 2 - WHERE IT ALL STARTS
SOLAR ENERGY
2.1 The Sun
“Stand a little less between me and the sun” ... Diogenes
It has been claimed that many of the world’s energy problems might be solved
if physicists on earth could copy the nuclear fusion processes which occur in the sun
(although there are those who would agree that a furnace of this type is best operated
at a safe distance and that 90 million miles could be just about right). The incredibly
high temperatures (many millions of degrees Celsius) within the sun, permit
hydrogen ions to fuse. Helium is produced and vast quantities of energy (Section
9.4) are released as electromagnetic radiation. Some of this radiation travels through
space, from sun to Earth. It is the source of most of Man’s energy. That part which
can be detected by the human eye is called “visible light” and it is light within this
range of wavelengths which is utilised by green plants in photosynthesis.
2.2 The Nature of Light
“Nature and Nature’s Laws lay hid in night.

God said, Let Newton be, and all was light” .....Alexander Pope
For some purposes, light can be regarded as an electromagnetic waveform,

for other purposes, as a stream of particles. Newton suggested that light was
composed of corpuscles travelling through space at constant speed and that there
were different corpuscles for different colours. Much later, Thomas Young showed
that light had the characteristics of a wave form and, subsequently, Lenard confirmed
its particulate (or corpuscular) nature. Today, light remains an enigma but it can still
be usefully described in these contradictory terms (i.e. particles and waveforms).
Max Planck’s conclusion that electromagnetic radiation (including x-rays, gamma
rays, radio-waves) are absorbed or emitted only in discrete particles, or quanta, of
energy remains central to modern quantum mechanics. In addition, Einstein, bringing
together and interpreting earlier observations and ideas, formulated the concept of
26
THE NATURE OF LIGHT
photochemical equivalence, i.e. that one quantum (or particle or corpuscle) of light
(i.e., one photon if we are talking about visible light) brings about one photochemical
event in any light-driven reaction.
[As we shall see later, 8 photons are needed to bring about the photosynthetic
transport of hydrogen from water to NADP (Chapters 4 & 6) but this is
because this process requires the movement of 4 electrons in 2 consecutive
steps each requiring 1 photon per electron].
-5 -5
4x10 7x10
P.A.R
)
-12 -10 -7 -6 -3 3
l(cm) 10 10 10 10 10 10
Cosmic Gamma X-rays U.V. Infra- Radio
red
Fig. 2.1 Electromagnetic radiation. Photosynthetically active radiation (PAR)
accounts for only a very narrow waveband. Note that values are expressed in metres
(e.g. 4 × 10-5 m = 400 nm)
Described in the above terms, there is a relationship between colour, or

quality of light and energy content. “Visible light” (i.e. light which can be detected
by the average human retina) has wavelengths between 400 and 700 nanometres
(1 nm = 1 × 10-9 metres = 1/1,000,000,000 metres). Below 400 nm (at the blue end
of the spectrum) there is ultra-violet light, invisible to the human eye and, similarly,
above 700 nm (at the red end of the spectrum), there is infra-red. “Photosynthetically
active radiation” lies within the same wavelength limits as visible light (Fig. 2.1).
White light is a mixture of all wavelengths between 400 and 700 nm and can be split
into its primary colours by a prism or the corresponding action of raindrops which
create a rainbow. Leaves appear green, to the human eye, when illuminated in white
light, because their chlorophyll molecules absorb red and blue light and transmit
and reflect green. The peak of human perception is in the green at about 555 nm
(Fig. 2.2) not far removed from the intensity maximum of sunlight (about 575 nm).
1.0
U.V. BLUE GREEN RED
1.0
555
Transmittance
Relative visibility
Absorbance
300 400 500 600 700

Wavelength (nm)
Fig. 2.2 What Man sees and what the green plant uses. By definition “visible” light
is that perceived by the human eye (wavelengths between about 400 and 700 nm, with a
perception maximum at about 555 nm). The green plant also uses light within this
wavelength range but chlorophyll (shaded area) absorbs best in the blue and the red.
27
If we think of waves breaking along a shore, it is evident that they deliver

energy as they pound a beach or breakwater. The amount of energy delivered
depends on the height of the waves (their amplitude) and their frequency.
Waves of the same height will deliver more energy if they arrive more
frequently. In the same way the energy content of photons is related to the frequency
(and therefore the colour) of light at a given intensity. Blue light at 450 nm packs
more energy per photon than red light at 650 nm. A quantum of ultra-violet radiation
carries more energy than a quantum of infra-red.
The relationship between wavelength (λ) frequency (υ) and speed of light (c)
may be expressed as follows:
λ (nm) × υ (per second) = (nm per second) Eqn. 2.1
Alternatively υ = c / λ Eqn. 2.2

(frequency equals speed divided by wavelength)
l
_ +
Fig. 2.3 Light as a waveform. The wavelength is the distance between peaks, the
height of the waves (the amplitude) is a measure of intensity.
These days (see Section 2.4) the wavelength of light is usually measured in
nanometers (nm) in accordance with the Système Internationale d’Unitès (S.I.). The
28
THE ENERGY CONTENT OF LIGHT
S.I. unit of length is the metre and this is sub-divided into:-
millimetres (1 mm = 1 m / 1000 or 10-3 m),
micrometres (1 µm = 10-6 m)
nanometres (1 nm = 10-9 m)
and so on. Before S.I. was established, a thousandth part of a millimetre was
sometimes referred to as a micron and the terms mµ (millimicron) and nm
(nanometre) are therefore synonymous. Physicists also used “Angstroms” (1/10 of
a millimicron) so that:-
1 mµ = 1 nm = 10 Å Eqn. 2.3
To add to the multiplicity of units, the speed of light (c) was usually expressed in
cm per second. In vacuum, c = 3 × 1010 cm/sec and, since 1 cm = 107 nm, this nice
round number unfortunately becomes 3 × 1017 nm/sec.
2.3 The Energy Content of Light
The energy content (E) of one photon of light may be determined by

multiplying the frequency (υ) by a value (h) called Planck’s Constant. It is for this
reason that light is sometimes depicted as hυ in equations such as 4.1 and 4.2. Note
that the symbol traditionally used for frequency is the Greek letter Nu (υ), not v.
Therefore
E = hυ Eqn. 2.4
or, from equation 2.2,
E = hc / λ Eqn. 2.5
“Plank’s Constant”
The value of Planck’s Constant (h) is 6.6 × 10-27 erg seconds so that, for red light
at 680 nm (which is most effective in photosynthesis),
1017 nm 1
E = 6.6 × 10 -27 erg.sec × 3 × ×
sec 680 nm
= 2. 9 × 10 -12 ergs Eqn. 2.6
29
There are 107 ergs to the joule and 4.184 joules to the calorie so that this becomes
2. 9 × 10 -12
calories Eqn. 2.7
4.184 × 10 7
= 0.69 × 10 -19 calories
or
2. 9 × 10 -12
joules Eqn. 2.8
10 7
= 2. 9 × 10 -19 joules
Clearly the energy content of a single photon is very small and it is usually put on
a more convenient basis by the simple expedient of multiplying by Avogadro’s
number (6.023 × 1023), which is similarly used to convert the weight of single atoms
into grams, e.g. the mass of 6.023 × 1023 hydrogen atoms = 1 g). Thus the energy
content of Avogadro’s number (1 quantum mole) of photons (at 680 nm) is
joules are a girl’s

best friend 0.69 × 10 -19 cal × 6. 023 × 10 23 = 41. 5 Kcal Eqn. 2.9
or 41.5 Kcal × 4.184 = 174 Kjoules Eqn. 2.10
For some purposes it is useful (e.g. Fig. 4.2) to convert ergs to electron volts (by
dividing by a factor of 1.6 × 10-12). Then we then find that 1 photon (at 680 nm)
can accelerate 1 electron through a potential of 1.8 volts i.e.
2. 9 × 10 -12 2. 9
= = 1.8 eV Eqn. 2.11
1.6 × 10 -12 1.6
The energy contents of monochromatic light at five visible wavelengths are

expressed in each of these ways (Kjoules, Kcalories and electron volts) in Table 2.1.
TABLE 2.1
Energy content of monochromatic, visible, light
Kjoules Electron volts

Wavelength Colour /mole Kcal/mole Photon
700 nm Red 171 40.9 1.77

680 nm * Red 174 41.5 1.81
600 nm Yellow 199 47.7 2.07
500 nm Blue 239 57.2 2.48
400 nm Violet 299 71.5 3.10
* This is the wavelength of the red absorption maximum of chlorophyll
30
A WORD ABOUT UNITS
2.4 A Word About Units
In Section 2.3 we have arrived at values for the energy content of light "divers weights and divers measures,
expressed in calories and joules. We now have an immediate problem from which both of them alike are abomination
there is no escape and one which will come back to plague us again and again (see, to the Lord" ...Proverbs 20.10
for example, section 2.5). In the beginning, Man related his measurements to things
that he had around him like hands and feet, the length of his stride (a yard), the
distance between outstretched hands (a fathom), how much he could lift (a
hundredweight) and so on. He also used other objects of fixed dimensions (such as
the seed from the carob tree which almost invariably weighs 200 mg or one “carat”
- as used by goldsmiths). As he became more sophisticated, of course, Man’s units
became correspondingly more sophisticated and, in many respects, a mess.
A contemporary attempt to create some order out of chaos was the

introduction of Système Internationale d’Unitès (S.I.) based on metric units.
However sensible this may seem it does not lend itself readily to all uses in all
circumstances. Grams and millimetres have some obvious advantages over ounces S.I. Prefixes
and inches but the fact that Bavarian carpenters still use inches (generations after the
introduction of the metric system into Germany), that pounds are not unknown in Prefix Symbol Value
France, and that much of domestic building in the United States is still firmly based
on ‘Imperial’ units, speaks for itself. Moreover, there is no getting away from the tera- T 1012
problem of translation or conversion. English is fast becoming a universal language. giga- G 109
It is already the lingua franca of science and, if every future book were published mega- M 106
in English, it would certainly make life easier for the English-speaking world. kilo- k 103
Nevertheless, without translation we would still be denied access to the foreign hecto- h 102
language literature. Similarly, even if we were to move universally into S.I. at this milli- m 10-3
moment we would still be unable to understand older scientific measurements unless micro- µ 10−6
we were familiar with obsolete units. For this reason, in Section 2.3 and elsewhere, nano- n 10-9
both calories and joules are used although the joule is now the preferred unit. Sadly, pico- p 10-12
there is also an additional confusion created by dieticians (see Section 8.5). Thus, femto- f 10-15
if and when we talk about calories in “every-day” usage (as we would if we were atto- a 10-18
talking about the calorific content of food) we must bear in mind that, if properly
31
written with a capital 'C', the Calorie = 1 Kcalorie = 4.18 Kjoules. The calorie with
a small 'c' is the amount of heat needed to raise the temperature of 1 ml of water
1°C (strictly speaking from 14.5°C to 15.5°C). So, for example, if we are told that
the calorific content of 1 mole (180 g) of glucose is 672 Calories (= 672 Kcal) this
means that if we were able to ignite a pile of glucose weighing 180 g under a large
beaker containing 10 litres of water (in such a way that we captured all of the heat
released) we could expect a temperature rise of about 67°C (0.1°C per Kcal per 10
litres). This may seem like an excuse for introducing yet more tedious arithmetic but
the intention is simply to give some feeling for the size and meaning of the units
involved. We would all know that “a drop” of water is about 1millilitre (1ml) in
volume and that if our immediate surroundings increased in temperature by 1°C we
would scarcely notice the difference. This in turn gives us some idea of the size of
a calorie as a measure of energy. The joule is also a familiar thing if we take it as
the energy produced per second by the application of a power equal to 1 watt. For
example, an electric light rated in terms of energy at 100 watts, will produce 100
joules of energy (in this case a mixture of light energy and heat energy) every second
that it is switched on. As we have seen in Section 2.3, 1 joule = 107 ergs and this
is a way of relating energy to mechanical work. The International Joule is the work
expended per second by a current of one International Ampere flowing through a
resistance of one International Ohm. These sorts of considerations allow us to start
to relate the energy that Man needs for his metabolism and all other purposes to the
sources of such energy (Chapter 6).
In the absence of units that we can all easily understand and relate to we find
ourselves in immediate difficulties. You might suppose, for example, that a second
is about the interval between the digits 1, 2 , 3, 4 .... and so on, counted in a measured
way. For many purposes such a definition would be hopelessly inadequate but, if we
came face to face with the most precise definition (below), we might find ourselves
in difficulty.
“The second is the duration of 9,192,631,770 periods of

the radiation corresponding to the transition between the two
hyperfine levels of the fundamental state of the atom of caesium 133”
2.5 Light Intensity
In Section 2.3 we calculated the energy content (one Einstein) of one quantum
U.K. mole (Avogadro’s number of photons) of red light at 680 nm; a wavelength which
is particularly effective in photosynthesis. Shorter wavelengths have a higher energy
content. Sunlight does not contain all the colours in the same proportions and the
1 metre corresponding calorific value for the intensity maximum (sometimes put at 575 nm)
is about 50 Kcal (209 Kjoules). Similarly the energy delivered to the earth’s surface
depends upon the quantity of light (intensity) as well as its quality (wavelength).
≡ 100 W
100W For some purposes, “light intensity” is still measured in foot candles or some
similar unit. As the name implies, this is the light given out by one standard candle
and perceived at a distance of one foot. A standard candle emits 4π lumens (1 candle
power) and if placed at the centre of a sphere of 1 foot radius produces a luminous
flux, at its surface, equal to 1 lumen/sq.ft. If the radius is increased to 1 metre the
The mean annual irradiance for same light is spread more thinly, the flux decreasing according to the square of the
the U.K. is about 100W/m2 distance. Since there are 3.2808 feet to the metre and since 3.2808 squared = 10.8
32
LIGHT INTENSITY
it follows that one foot candle (1 lumen/sq.ft.) = 10.8 lux or metre candles (1 lumen/
sq. metre). The human eye is a very good device for comparing the intensity of weak
light sources, but very poor for determining absolute intensity values. This is because
the iris diaphragm closes in bright light, so protecting the retina. Accordingly we tend
to over-estimate the intensity of light if we enter a well-lit room from a dark night. 23
0.5 x 6 x 10
The light intensity in such a room is unlikely to be more than 200 ft candles, whereas
in full sunlight it may be as much as 10,000 ft candles (100,000 lux). For accurate
measurement the human eye (or instruments such as photographic “light meters”
which were designed to mimic its performance) have been replaced by instruments “Half an Avogadro Pair"
which record the incident radiation in units such as photons per sq. metre per sec.
[It is not strictly correct to describe light energy arriving at a surface in terms
of ‘light intensity’. Intensity is a property of the radiating source e.g. a
standard candle emits a flux of 1 candle power or 4π lumens. The
corresponding measure of flux density or light received is 1 lumen/ft2].
At the present time, relatively new instrumentation is fast displacing the need
to cling to these old units, themselves a product of out-moded measuring procedures.
Many contemporary light meters are, in fact, photon (Section 2.2) counters and give
values of light “intensity” expressed as “photon flux density” (PFD), i.e. the number
of photons which strike a unit area per unit time. For biological purposes, this area
is often taken to be one metre and the time one second. It is also convenient (for
reasons which will become clear in Chapter 6) to express the number of photons as
µmole quanta or µmole photons.
[Avogadro’s number of photons is called a “quantum mole”, or “photon

mole”. One micromole of photons is 1 mole × 10-6. The energy content of
1µmole of photons is called a “microeinstein” but this unit seems to be
coming less favoured.]
Microeinsteins
The relationship between some of the units which are still used, or have been
used, is given in Table 2.2 (overleaf) but it should be appreciated that it is often not
possible to give precise equivalents because “white” light from the sun does not have
33
TABLE 2.2
Full sunlight (Global Irradiance) expressed in several ways.
Illuminance Photosynthetically active component

per square metre per second
lux foot Watts/m2 ergs joules cal photons µmole quanta

candles
100,000 10,000 500 5×109 500 120 1.3×1021 2200
This table shows the approximate equivalence between full sunlight (expressed, at left, as
illuminance) and the energy content of its photosynthetically active component, (right)
assuming a mean wavelength of 575 nm.
precisely the same spectral composition as light from a traditional tungsten source
(bulb, globe), or a fluorescent tube or a quartz-halogen lamp (typical of modern
motor vehicles). Accordingly, these sources do not deliver the same energy at
intensities which would be judged to be equal by some of the procedures which have
been employed in the past. Precise evaluation is only possible for “monochromatic”
light or when instruments are used (e.g. “spectroradiometers”) which, in effect, count
how many photons are delivered over the whole spectrum of wavelengths emitted
by a particular source.
2.6 The Availability of Solar Energy
“Hail Smiling Morn, that tips the Hills with Gold”
More solar energy reaches the earth than might be imagined by those who live
in a cold climate. At noon, on a clear day at the equator, each square metre of the
sea’s surface may be rated (according to the energy it receives) at 1 kW. Clearly this
value will fall as the sun goes down or as the distance from the equator is increased.
However, if averaged over 24 hours/day and 365 days/year it is surprisingly
independent of latitude and cloud cover. Thus the mean annual irradiance in the Red
Sea area is about 300 W/square metre, but the corresponding values for Australia and
the USA are as high as 200 W/m2 and 185 W/m2 respectively and even, in the UK,
the average is about 105.
34
LIGHT AS AN ENERGY CARRIER
2.7 Light as an Energy Carrier
In Section 1.2 we addressed the concept of charged particles. A proton

(hydrogen ion, H+) is an example of a particle (in this case an atom) which has
acquired a positive charge as a consequence of “losing” a negatively charged electron
(e-). A “dipole” is a pair of oppositely charged particles separated by a very small
distance. If the two charges can be made to oscillate along the line which separates
them, such an “oscillating dipole” generates a moving, wave-like, force-field which
moves away from its source with the speed of light (Fig. 2.4). The force field has
an electric and a magnetic component; the two components in phase but
perpendicular to one another. The amplitude of the waves gradually diminish as the
force field moves away from its oscillating dipole source. As we have seen in Section
2.2, visible light (and other forms of electromagnetic radiation) can be partially
described in these terms. Light intensity is determined by the amplitude of the waves
(the bigger the waves the brighter the light).
(
( +
(
(
(
(
(
(
(
(
(
( ( (
( ( ( ( (
+ +
- ( ( ( (
) ( (
(
(
(
(
( (
( (
(
(
(
(
+
Fig. 2.4 Light as a force field. Electromagnetic waves radiated by an oscillating

electric dipole. The electric component is shown by the short arrows. The magnetic
component is not shown; it is perpendicular to, and in phase with, the electric
component. The pattern moves away from the dipole with the speed of light, its
amplitude decreasing with distance.
As we have seen in Section 2.2, this description of light is eminently useful

but something less than the whole story. In the preceding paragraph we have talked
about light intensity in terms of “amplitude” (the height of the waves) but elsewhere
we talk about “photon flux density” and so far, in this section at least, we have had
no mention of photons. We shall come back to this in a moment but let us first make
a comparison.
“Just as an oscillating dipole generates an electromagnetic wave, the wave

(a pattern of electric forces) can, in turn, set other dipoles into oscillation of the same
frequency. The process is roughly like the resonant vibration of one tuning fork in
the presence of another, energy being communicated from one fork to the other
through the medium of compression waves in the intervening matter. The
electromagnetic wave is thus a carrier of energy, as one can appreciate by standing
35
in the sunshine. Work must be done in maintaining the oscillation of a dipole, a

corresponding amount of energy is radiated into the surrounding space, and some
of this energy is absorbed by other dipoles when they are set in motion. These other
dipoles in turn radiate energy as a result of their oscillation. We can thus visualise
the interaction of light with matter as a process in which energy is exchanged
between a collection of oscillating dipoles and a radiation field. The oscillation of
the dipoles corresponds to the movements of electrons relative to positively charged
nuclei in matter.”
This analogy, drawn by Rod Clayton, is both useful and easy to understand
in terms of a not uncommon human experience. To set a tuning fork “humming” we
must strike it. A second tuning fork, set next to it, will then begin to hum. So long
as we continue to strike the first, the second will continue to vibrate. In the sun we
have dipoles induced to oscillate by nuclear fusion of protons. These oscillating
dipoles radiate electromagnetic energy. Such energy (at wavelengths in the red and
the blue which chlorophyll molecules can absorb) set dipoles in oscillation within
the light-harvesting antennae of a plant's photosystems (Section 3.3). Energy transfer
between sun and plant has been accomplished.
2.8 Getting Excited
So where do photons come in? The trouble was that the classical picture,
described above, is inadequate. It simply could not account for all of the known
observations. In an attempt to resolve these difficulties, Planck proposed (Section
E2 2.2) that energy could only be exchanged in discrete parcels (quanta). This made it
h u possible, amongst other things, to equate emission and absorption spectra (the
wavelengths at which substances may emit or absorb light) with definite energy
states of atoms. Absorption of a photon changes an atom, primarily by lifting an
outermost, or valence, electron from a “ground state” orbital to a higher “excited
state” orbital. The energy of the atom is thus increased by the energy (hυ) of the
E1 absorbed photon.
Absorbtion
p of light [In terms of the classic theory the electromagnetic wave induces an oscillatory
u
h = E2 - E1 dipole in the atom, the tuning-fork begins to hum.]
He He He
S=0 S=0 S =1
Singlet Excited Excited
singlet triplet
Fig. 2.5 Electronic states of helium.
If the electron drops directly back from the excited state to the ground state
a photon is emitted (see Section 2.9). The transition from ground state to excited state
(and vice versa) takes about 10-15 s. Electrons are like tiny spheres which spin on
their axes. If a pair of electrons that are normally together, spinning in opposite
36
GETTING EXCITED
directions, become separated by excitation they can continue to spin in an anti-

parallel fashion or the direction of spin can change. The “total spin quantum number,
s” can be 0, 1/2 or 1 depending on whether there are 2 electrons spinning in opposite
directions (s = 0, or “singlet state”) or two electrons spinning one way and a third
in the opposite direction (s = 1/2, or “doublet” state) or two electrons spinning in
the same direction (s = 1 or “triplet” state). An “excited triplet” is long lived and
particularly reactive.
What applies to atoms also applies to molecules but there is the added degree
of complexity brought about by the fact that there are now several nuclei involved
as well as the vibratory and rotating movements of these nuclei in relation to the mass
of the whole system which comprises the molecule. Accordingly, there are, in effect,
a number of “ground states” and a corresponding number of “excited states” . The
single sharp line of the atomic-absorption spectrum is replaced by a number of
closely adjacent lines, each a consequence of a transition from a ground state to an
excited state and each brought about by absorption of a photon with precisely the
right energy content to effect such a transition. The height of the line is governed
by the probability of the transition and the lines are usually too close to be resolved
so that a characteristic absorption band is observed rather than the well-defined line
of the atomic absorption spectrum which depends upon a single transition,
consequent upon the absorption of one photon, rather than multiple transitions
consequent upon absorption of a number of photons at different wavelengths.
} Excited
state (two)
Radiationless
de-excitation
} Excited
state (one)
chemistry
u u hu
blue h red h fluorescence
} Ground state
Fig. 2.6 Excitation of chlorophyll by red and blue light. The parallel lines represent
energy sub-state or electronic orbitals. Thus the energy delivered by the absorption of
a blue photon (left) is sufficient to raise an electron to excited state ‘two’ from where
it rapidly returns by a process of radiationless de-excitation, ‘cascading’ through sub-
states, to excited state ‘one’. A photon of red light (centre) only has enough energy
to raise an electron to excited state ‘one’ but this excited state is sufficiently stable
to permit useful chemical work and is, in effect, the starting point of all other events
in photosynthesis. Particularly in organic solvents, excited state one can also dissipate
energy by re-emitting light as (deep red) fluorescence.
Fluorescence, brought about by the emission of photons as electrons fall back

from excited substates in molecules, occurs with a shift towards longer wavelengths
i.e., “the Stokes Shift”. This is because the excited states have an opportunity to lose
37
energy as heat, in small steps between excited substates prior to the abrupt drop from
an excited state to a ground state. Most molecules have two or more excited states
and therefore two or more peaks in their absorption spectra. The tails of these peaks
overlap, permitting easy thermal cascading (heat loss in dropping from one excited
substate to another). This occurs so rapidly (in about 10-12 secs) that there is no
opportunity for photochemistry or fluorescence.
[The excited states of molecules usually persist for for about 10-8 seconds, the
triplet state may have a lifetime of about 10-4 to 10-1 seconds.]
It is for this reason that chlorophyll looks green yet emits red fluorescence
when excited. Chlorophyll has two absorption maxima; (Figs. 2.2 and 3.1) one in
the blue, at about 420nm, (corresponding to excited state 2) and one in the red, at
about 680nm (corresponding to excited state 1). Because it absorbs red and blue
light, and reflects and transmits green light, chlorophyll (and leaves) look green when
illuminated in white light (which is, of course, a mixture of these dominant colours).
If a solution of chlorophyll (e.g. in alcohol or acetone) is viewed from the side,
however, (so that the retina of the observer is not flooded with green photons
transmitted through the solution) a deep red fluorescence is seen. This only emanates
from the red excited state because excited state 2 decays to excited state 1 by thermal
cascading (dissipation of excitation energy as heat in going from one substate to the
next) too quickly (10-12 sec) to allow fluorescence emission from the blue excited
state. Similarly, the red excited state is the starting point, the driving force, of the
chemistry of photosynthesis. Photosynthesis derives no benefit from the extra energy
of blue photons (Table 2.1) because of this rapid heat loss.
[It should be noted that chlorophyll fluorescence is emitted at a deeper (longer

wavelength) red than the peak absorption in the red. This is because of the
Stokes Shift (above) in which some thermal cascading through excited
substates results in an energy loss and eventual emission of photons at longer
(less energetic) wavelengths as electrons finally fall back to the ground
states.]
FLUORESCENCE
2.9 A Rich and Ambiguous signal
Whole books have been written about chlorophyll fluorescence. Emitted from
an illuminated chlorophyll solution, fluorescence is spectactular but otherwise not
very exciting. Emitted from a leaf, it gives what Lavorel and Etienne once described
as “a rich and ambiguous signal”. Chlorophyll fluorescence from leaves is a much
smaller fraction of the excitation energy than that emitted from solution. So small
a fraction indeed (about 3-5%) that it can only be detected by sensitive photodiodes,
protected in instruments, by optical filters and other devices which protect against
other wavelengths. Chlorophyll a fluoresces at about 685nm but, in leaves, the
emission may be shifted further into the red, to a secondary maximum at about
740nm, by re-absorption of fluorescence by chlorophyll.
It has long been proposed that there must be an inverse relationship between
chlorophyll a fluorescence emission from leaves and photosynthetic carbon
assimilation. Fluorescence it was argued must be an indicator of “gainful
employment”. If photosynthesis is driven by the red excited state of chlorophyll the
38
A RICH AND AMBIGUOUS SIGNAL
more excitation energy that is used for that purpose the less would be available for
dissipation as heat or as light. This concept also gains support from so called
“fluorescence induction” (the Kautsky effect). This effect is seen when leaves are
10
OXYGEN AND FLUORESENCE
9
8
7
6 OXYGEN
5
4
FLUORESCENCE
3
Light
2
1
2 4 6 8 10 12 14 16 18
TIME (MIN)
Fig. 2.7 The Kautsky Effect. Photosynthetic carbon assimilation starts slowly when
a leaf in darkness is abruptly illuminated. During this induction period fluorescence
rises rapidly at first and then falls, sometimes displaying secondary peaks, to a quasi
steady-state level.
first illuminated after a period of darkness. Such leaves do not immediately

commence to photosynthesise at maximal rates but only after a lag or induction
period. Chlorophyll fluorescence on the other hand reaches a maximum within a very
Fv
1 min CO2
Fo
Time
Fig. 2.8 Complex fluorescence kinetics. The broken line is CO2 uptake and illustrates
the broadly inverse relationship between fluorescence and carbon assimilation. “E” is
defined by quenching-analysis (Section 2.10) and is the difference between maximal
and variable fluorescence.
39
short time after illumination and thereafter falls, albeit sometimes in a complex way,
through one or more secondary maxima, to a “steady-state” level much lower than
the initial maximum. This is precisely what would be expected if it were supposed
that the “dark biochemistry” took some time to get under way but that the
photochemical events started immediately. Moreover, it is known that the
10 Secs photochemical events do start immediately (for example the Hill reaction, described
in Section 4.1, in which chloroplasts reduce an artificial electron acceptor, starts at
maximal rates without discernible lag). The problem was that, in the words of
air air Lavorel and Etienne, fluorescence is such a “rich and ambiguous” signal. The
“richness” of the signal lies both in the complexity of the initial rise and the
-CO2 secondary kinetics, often seen, in the subsequent fall. The “ambiguity” resides in the
fact that, at one time, the complexity was such that it seemed to defy explanation
and the fact that some changes were exactly the converse of those which might have
been predicted. Perhaps the most important of these was the response (the “gas-
transient”, left) when carbon dioxide was abruptly removed from the atmosphere
surrounding the leaf. This was bound to result in a similarly abrupt cessation of
carbon assimilation. It would follow that there should be more excitation energy
available for dissipation and reasonable to suppose, therefore, that fluorescence
emission might increase. That, in fact, was observed but the abrupt rise in
fluorescence emission which followed removal of carbon dioxide was soon
overtaken by such a large decrease that, within a matter of seconds, the fluorescence
signal had fallen below the level seen during unimpeded photosynthesis. Similarly,
re-addition of carbon dioxide produced a downward excursion followed by a rise
which took the signal back to the original level.
2.10 Quenching Analysis.
“Q-analysis”
Many of the ambiguities have now been explained in terms of two principal
“quenching mechanisms”. The term “quenching” is associated with work by Duysens
and Sweers who proposed, many years ago, that there was an electron acceptor
40
QUENCHING ANALYSIS
(associated with what is now described as photosystem II - Fig. 3.4) which would
accept electrons when in its oxidised state. They designated this acceptor “Q” for
“quencher” on the basis that, if excitation energy was used to lift electrons from
water to Q this excitation energy would not be available for dissipation as
fluorescence and, accordingly, fluorescence would be quenched. If, on the other
hand, Q was, for whatever reason, in a fully reduced state, all of the excitation at
that moment would be available for dissipation and that fraction dissipated as light
would increase the fluorescence signal. Quenching (qQ) associated with the oxidation
reduction status of Q (which, incidentally, turned out to be a quinone) is now
referred to as “photochemical quenching” (qP). This is seen as the explanation for
the initial rise in the fluorescence signal when CO2 is suddenly removed from a leaf.
Once reduced, Q (or more properly “QA”, as the reaction centre in photosytem II is
now called) normally passes electrons, via other electron carriers, to photosystem I
and finally to carbon dioxide via NADP (Sections 4.1 and 4.2). In the absence of
CO2, NADPH2 cannot be re-oxidised via this route (by CO2), fluorescence quenching
by oxidised QA “relaxes” and fluorescence emission rises. The second major
quenching mechanism (formerly qE for “energy quenching”), is now designated qNP,
for “non-photochemical quenching”). Precisely how this works is still not properly
understood but it is associated with the establishment of a proton gradient (∆pH)
across the thylakoid membrane (Chapters 3 and 4). This proton gradient normally
NADP
+
2H fp
Stroma reduc
tase
QA x
Thykaloid
QB
membrane
PSI
2 Photons PQ shuttle 2 Photons
P700
P680 cytf PC
Mn
Inside
H2 O 1_ + +
2 O2 + 2H 2H
+
Fig. 2.9 Organisation of electron carriers in the thylakoid membrane. Note the H
inward movement of protons from the stroma into the lumen of the thylakoid. The X
proton gradient, discharging through the ATPase (see right margin) drives ATP
formation from ADP and Pi. The nature of the carriers is considered in Section 3.9 Chloroplast
stroma
& 3.10.
discharges through the ATPase (Section 4.7), generating ATP from ADP and Pi. In PS I
the absence of carbon dioxide, ATP is not consumed in photosynthetic carbon PS II +
assimilation and ADP is therefore no longer available to discharge the proton H
gradient through the ATPase in this process. In these circumstances the un- Inside
thylakoid +
discharged proton gradient appears to switch dissipation of excitation energy from H
+ H
fluorescence into thermal channels with the result that fluorescence is quenched. +
This, in part, is the source of the decline in fluorescence which pushes the H
(uncoupler)
fluorescence signal from the initial maximum (seen on the removal of CO2) to a Fo
value even lower than before. When CO2 is returned to the atmosphere surrounding CF1
the leaf the converse sequence of events occurs. QA- can become re-oxidised in the
presence of CO2 so that its fluorescence quenching is re-imposed. ATP is consumed
in carbon assimilation making ADP available to discharge the proton gradient. As ADP + Pi + ATP
H
the proton gradient falls, some dissipation of excitation switches back, from thermal
channels, into fluorescence.
41
Major advances in the resolution of the fluorescence signal into its separate
components and consequent understanding of the underlying trends has followed the
introduction of “light-doubling” and the development of sophisticated apparatus by
Schreiber and his colleagues. “Light-doubling” was introduced by Baker and
}
developed by Horton and others. Saturating flashes of light were used in this
Fm :
{ } }
qE (Fv )m
q (Fv )m
(Fv )m
} qQ (Fv )m
s
Fo :
:
} Fv
(Fv) s
saturating 20 s
beam
0
:
measuring actinic
beam beam
Fig. 2.10 Q-analysis Definition of quenching coefficients etc., according to

Schreiber. Fo is the fluorescence displayed by a dark-adapted leaf in very weak
modulated light. (Fv)m is the maximal variable fluorescence first seen when a pulse
of actinic saturating light is applied. Fv is the variable fluorescence seen, once
continuous actinic light is applied and (Fv)s are the peaks to which this fluorescence
is then driven by pulses of saturating light. The derivation of qQ and qE, now called
photochemical quenching (qP) and non-photochemical quenching (qNP or qN), is
explained in the text.
technique in order to drive QA fully reduced, thereby allowing the evaluation of

maximum fluorescence in the absence of qP quenching. A major contribution by
Schreiber and his colleagues was to produce an instrument which combined optics
with very sophisticated electronics. This allows fluorescence, initiated by a very
weak measuring beam (the so-called Fo value), to remain undisturbed by the
saturating flash, thereby allowing accurate measurement of the differences between
Fo and Fmax. The entire process, i.e. the light-doubling and the subsequent evaluation
of the major quenching components by measurement and arithmetic has sometimes
been referred to as “quenching analysis”.
In recent work, quenching analysis has been used to measure photosynthetic

carbon assimilation. i.e. the rate of CO2 fixation can be accurately determined by
evaluating the light emitted from leaves as chlorophyll fluorescence. At Sheffield,
for example, George Seaton has shown that the rates of CO2 fixation in a number
of disparate species can be determined solely by fluorescence, using parameters
derived from a single reference species such as spinach.
42
CHAPTER 3 - HARVESTING THE SUN
3.1 The Photoreceptors
"The changing of bodies into light and light into bodies is very
comfortable to the source of Nature, which seems delighted
with the transmutation” ..... Isaac Newton.
So far we have thought about a few fundamentals (Chapter 1) and examined

the nature of light (Chapter 2). We have even taken a passing glance at the idea of
light excitation. What we shall attempt to do now is to look at the way in which green
plants harvest light energy. In following this, step by step, in the same sequence that
it actually occurs, we should not lose sight of what we have already learned. What
we are considering is essentially a process of energy transduction; the conversion of
light energy to electrical energy in the excitation of chlorophyll. The transfer of
electrons, from the photoreceptors, through the two photosystems which constitute
the Z-scheme and the associated generation of assimilatory power (Chapter 4).
Finally, this transient supply of energy (in the form of the high energy compounds
ATP and NADPH2) is consumed in the “dark biochemistry” of carbon assimilation
(Chapter 5) in which atmospheric CO2 is reduced (Section 1.3, 4.9) to the level of
CH2O and long-lived forms of chemical energy are therefore produced.
The conversion of light energy to chemical energy starts with

“photoreceptors”. In green plants the principal photoreceptors are the chlorophylls,
a and b. These differ somewhat in chemical structure and physical properties but they
have much in common, both with each other and with that other all important
molecule (heme) which gives blood its colour. These are all substituted tetra
pyrroles. In the chlorophylls, the nitrogen atoms of the four pyrrole units are linked
(“co-ordinated”) to a central magnesium atom and, in the hemes, to a central iron
atom. In other respects the chlorophylls are very different from heme compounds.
Most particularly they have an ester of a long-chain alcohol (phytol) as one of the
side chains attached to the porphyrin ring. Phytol contains four isoprene units
(isoprene is a constituent of rubber) and it is phytol which gives chlorophyll its
distaste for water (makes it hydrophobic) and, conversely, its liking for association
with fats (lipophilic). Accordingly it can fit happily into photosynthetic membranes
or lamellae, which are complex structures based on lipids and proteins
(approximately 50% protein, 40% lipid and 10% chlorophyll). For these reasons
chlorophylls are largely insoluble in water but if a leaf is dipped briefly into boiling
water to denature the proteins and then extracted with hot 80% alcohol (80 parts of
alcohol, 20 parts of water) a bright green solution is readily obtained which shows
a deep red fluorescence when illuminated (and viewed from the side). If we emulate
Tswett, who was the first to do this, and run this solution through an icing sugar
column we can separate chlorophyll a from b, which is slightly less blue (more
yellow/green) in appearance. Using more modern techniques, such as thin-layer
chromatography, we can get very good separation very easily and, following elution,
look at the absorption spectrum of each pigment separately, using a
spectrophotometer. Fig. 3.1 shows the results of such an experiment. There are major
bands of absorption in the red and the blue parts of the spectrum which is why the
chlorophylls look green in white light. It will be seen (Fig.3.1) that the absorption
spectra of the two chlorophylls complement each other in the sense that they extend
the range of light wavelengths which can be absorbed. We should also note that the
absorption spectra are shifted a little, in aqueous ethanol, from the peaks that are
displayed by an intact leaf. This is attributable in part to the fact that, in the leaf,
chlorophylls are bound to proteins (Section 3.3).
44
THE PHOTORECEPTORS
CH 3
C C CH 2
1
CH 2
U.V. BLUE GREEN RED
453
420
2 Isoprene
Chl a
1.0
663 4
Chl b
6
Transmittance
8
Chl a 10
80% acetone
extract
20
645
0.5
Chl b 40
60
80
100
400 450 500 550 600 650
Wavelength (nm)
Fig. 3.1 Absorption spectra of chlorophylls in acetone. The absorption in the blue
(left) and the red (right) leaves the “window” in the green which gives chlorophyll its
characteristic colour when viewed in white light. Note that the peaks are shifted
towards longer wavelengths when the pigments are associated with proteins in a leaf.
Chlorophylls are the first step in energy transduction. Excited by blue or red
wavelengths of light, they initiate electron transport. The conversion of light energy
to electrical energy is analogous to the reaction in man-made photoreceptors such as
amorphous silica cells which generate electric currents when illuminated (c.f. Fig.
1.2). Each photon of red light which is absorbed by a chlorophyll molecule raises
an electron from a ground state to an excited state and all of the available energy
is transferred in this process. This excitation brings about an oxidation. Electron
transport (Section 1.2) is initiated, as the electron is lifted into a higher orbit and a
positively charged “hole” is created. Absorption of blue light causes even greater
excitation (because of the higher energy content of the blue quantum) but the
elevated electron then falls back into the “red orbit” too quickly to permit useful
chemical work. Thus, whatever the quality of the light absorbed, the electron reaches
the same energy level more or less immediately after excitation and all subsequent
events derive from this common starting point (excited state I).
3.2 Photosynthetic Units
In a classic experiment which was to have major subsequent impacts,

Emerson and Arnold subjected the alga Chlorella to brief flashes of high intensity
light with a view to achieving saturation of the photochemical events while avoiding
the limitations which would otherwise have been imposed by the “dark
biochemistry” if it had been asked to contend with this situation on a continuous Absorption Spectre
45
rather than an intermittent basis. They also contrived to vary the chlorophyll content
of the Chlorella by growing it under different light intensities. To their complete
surprise, they found that saturation was effected when the number of photons
supplied in a flash were sufficient to excite only about one out of every 2,500
molecules of chlorophyll in the sample being examined. They confessed that they
were really unable to account for this result (which obviously implied that, at least
in this situation, most of the chlorophyll was superfluous). It fell to Gaffron and
Wohl to propose the concept of the “photosynthetic unit” as a way of explaining both
Emerson and Arnold’s findings and their own work (on varieties of plants, relatively
deficient in chlorophyll, which were still able to achieve good rates of photosynthesis
but only at high light intensities). The idea was that there might be photosynthetic
units (assemblies of chlorophylls) in which most of the molecules were not directly
concerned in the evolution of oxygen but in capturing and transferring energy to
those few which were. Bearing in mind the quantum requirement of 8, there could,
for example, be 8 such units each containing a reaction centre associated with about
300 molecules of “antenna” chlorophyll, concerned solely with light-harvesting.
LHC LHC
P700 P680
(120 chl a) (60 chl a)
(70 chl a)(70 chl b)

(40 chl a)(40 chl b)
PHOTOSYSTEM I PHOTOSYSTEM II
Fig. 3.2 A photosynthetic unit. The “cores” of PSI (left) and PSII (right) are
represented by the inner circles; light-harvesting complex, LHC. The areas correspond
to relative proportions of each chlorophyll-protein complex (after Jan Anderson).
Some feeling for the underlying philosophy can be obtained by returning to

the relationship between light intensity and rate of photosynthesis (Section 6.7). The
first part of this relationship is linear. Above about 75 - 100 µmoles photons.m-2.s-1
it becomes curvilinear. At these low light intensities many plants seem to have a
quantum yield of about 0.11 if they are not stressed. Indeed, the Z-scheme (Section
4.3), would dictate a minimum quantum yield of 0.125 (a quantum requirement, the
reciprocal of quantum yield, of 8). Since we derive this from the rate of arrival of
photons, in the linear part of the relationship, it follows that if, e.g., at a light intensity
of 100,
x 100
= 0.125 (or = 8)
100 x
then x must be 12.5 (µmoles of O2.m-2.s-1). For a 100 sq.cm. leaf this would give
us 0.125 (12.5 × 100/10,000) µmoles of O2 per second. If 8 photons are needed to
co-operate in order to produce 1 µmole of O2, 0.125 µmoles of O2 per second
requires 1 µmole (0.125 × 8) photons per second. This fits our arithmetic. Our
circular argument is sound. The leaf is receiving photons at the rate needed to evolve
46
PHOTOSYNTHETIC UNITS
O2 and, if there are about 5 times as many chlorophyll molecules (approximately 5

µmoles in a 100 sq.cm. leaf) as photons intercepted (5 µmoles of chlorophyll, 1
µmole of photons), then 4 out of 5 chlorophylls would not be involved. If we
diminished the light by a factor of 10, the efficiency (the quantum yield) would be
no less (1.25/10 instead of 12.5/100) but 49 out of 50 molecules of chlorophyll would
not be excited at any one moment. Accordingly, it becomes more and more difficult
to imagine how, in the absence of any organisation, 1 out of every 50 molecules of
chlorophyll, randomly scattered throughout the leaf, could interact with precisely the
same efficiency as if they were adjacent. If, however, these chlorophyll molecules
were part of an “antenna” which “harvested” incoming photons; which funnelled
excitation energy to a “centre” (in which the combined energy of the photons brought
about the evolution of oxygen), the problem would not arise.
CF1 CF0 CF1

(
( (
{
PS II PS I
CF1
CF1
( ( (
LIPID
CF1
{
LHC PS II PS I
GRANA REGION STROMA REGION
Fig. 3.3 Organisation of components in thylakoid membranes. Photosystem I

complex, PSI; photosystem II complex, PSII; light harvesting complex, LHC; coupling
factor, CF1; and coupling factor base complex, CF0 ( after Hiller and Goodchild).
It must be borne in mind that this earlier work pre-dated the Z-scheme
(Section 4.3) and work on chlorophyll-protein complexes (Section 3.3) and that
much still remains to be done in assigning function to structures known to be present
but not yet properly understood. For this reason the “photosynthetic unit” has meant,
and will continue to mean, rather different things to different people. For the present
we will take the simplest view that the reaction centres (Sections 3.7 and 3.8) of
photosystems I and II are located in one such unit (Fig 3.2) comprising about 400
molecules of chlorophyll, most of which are incorporated into the antennae.
47
3.3 Light-harvesting Antennae
The light-harvesting chlorophyll-protein complexes (LHC) occur in all higher

plants and green algae. These contain chlorophyll b (and often carotenoids) as light-
harvesting accessory pigments and it is probable that all of the chlorophyll b is
located, with approximately equal amounts of chlorophyll a, in the antennae. As the
name of these complexes implies, their function is to act as antennae which harvest
incoming photons and funnel them to the respective reaction centres of PSII and PSI
where the photochemistry of oxygen evolution, water splitting, and electron transport
to NADP actually occurs. This is why (Section 3.2) light saturation, with respect to
chlorophyll excitation, occurs when less than 1% of the total chlorophyll is excited.
Within the antennae (and the other components of the photosynthetic unit concerned
with light-harvesting) excitation energy is transferred by “hopping” from one
molecule of chlorophyll to another. This is sometimes described as transfer of an
“exciton”. The transfer of an exciton has much in common with the transfer of an
electron. Both can be regarded as transfer of a particle and the process can be
represented by:-
L * R → LR * Eqn. 3.1
where “L” and “R” stand for “left” and “right”, respectively, in order to avoid
confusion between transfer from primary donors to primary acceptors (Section 1.2)
and the asterisk indicates the particle which is transferred. In LHC, this particle is
an exciton. Once the exciton has reached the reaction centre of PSII (Section 3.7)
“L” represents the primary donor (in its first excited single state), “R” is the primary
acceptor and the particle which is transferred is an electron starting on its journey
through PSII, via PSI, to NADP and carbon dioxide.
3.4 Downhill All the Way?
Within the antenna, excitons (Section 3.3) migrate “downhill” from carotenoids
“Wir sind übern Berg” with acknowledgements to Weber
48
DOWNHILL ALL THE WAY
and chlorophyll b at the periphery, via chlorophyll a, to the reaction centre which
constitutes a trap from which there is no escape. Chlorophyll b absorbs photons of
higher energy (shorter wavelength) than chlorophyll a which, in turn, has absorption
maxima at wavelengths lower than that of the reaction centre itself (Section 3.7).
There are, however, a number of forms of chlorophyll a (which cannot, at present,
be separated from the leaf but the presence of which can be inferred from computer
analyses of absorption spectra) and if these were structurally arranged in such a way
(Fig. 4.2) that the longer wavelength (lower energy) forms were arrayed about the
reaction centre it would decrease the number of hops which an exciton would make
by a factor of ten, compared with a purely “random walk” (or random hop). Whether
or not such structural organisation exists, exciton transfer is very rapid and very
efficient (the overall state of excitation of chlorophyll molecules within a
photosynthetic unit lasts less than 1 nanosecond and the observed quantum efficiency
at this primary level is close to 100%).
3.5 The Heart of the Matter
47 43
QA QB
kD Fe kD
LHC-2 LHC-2
Pheo
PQH 2
32 kD 32 kD
D2 D1
b 559 P680
Mn
++
33kD Ca 23
Cl
- kD
2H2O 16kD
+
O2 + 4H
Fig. 3.4 Photosystem II. Diagrammatic representation of PSII and its associated
components as a light-harvesting complex in the thylakoid membrane (Courtesy of Jim
Barber). The water-splitting side gives rise to powerful oxidising species which are
harboured in the D1 polypeptide which binds QB (Photoinhibition [Section 5.9]
involves damage to this QB binding protein).
The light-harvesting complex or antenna (Section 3.3) funnels excitation

energy into the reaction centres (Sections 3.7 and 3.8). No one knows, for sure, if
there are separate photosynthetic units (Sections 3.7 and 3.8) for PSI or PSII with
separate antennae or if the structure is closer to that postulated by Anderson in Fig.
3.2. This shows one unit with common antennae complexes, although there is more
chlorophyll b close to the reaction centre of PSII than close to the reaction centre
of PSI. In any case, there is general agreement that there are two reaction centres,
49
one for each photosystem; that these have absorption maxima at 680 nm (PSII) and
700 nm (PSI); that they constitute traps for the excitons which migrate through the
light-harvesting antennae (Section 3.3) and that they are the sites at which light-
driven electron transport commences, in PSII, and is boosted (by PSI) as electrons
travel onwards to NADP.
ATP
INTRATHYLAKOID
O
ADP CF SPACE
+Pi I
CF THYLAKOID
LIGHT HARVESTING
PSII REACTION
CHLOROPHYLL a/b
CENTRE
PROTEIN FERREDOXIN
ATP CHLOROPHYLL
NADP
ADP PROTEIN COMPLEX
REDUCTASE
+Pi
Cyt
Q PQ B6
A
Cyt B
Cyt f P700
STROMA B559
P680 Pc
Z
Y O2
+ INTRATHYLAKOID
2H2O 4H
PSI CHLOROPHYLL
SPACE
PROTEIN COMPLEX
THYLAKOID
Figure 3.5. The thylakoid membrane. The light-harvesting chlorophyll protein

complex funnels excitation energy to P680, the reaction centre of PSII. From there,
electrons are “raised”, via P680, to QA and then “downhill” through plastoquinone and
cytochrome ƒ to P700, the reaction centre of PSI. Light excitation of PSI raises
electrons a second time to an iron-sulphur protein, the primary electron acceptor of
PSI and then again “downhill” through ferredoxin to NADP. Electron transport creates
a proton (H+) gradient across the thylakoid membrane which discharges through the
ATPsynthase (CF1, CF0) generating ATP from ADP and inorganic phosphate (Pi).
3.6 Chlorophyll Protein Complexes
Chlorophyll does not exist within chloroplasts as a separate chemical entity

but in association with proteins. Such chlorophyll protein complexes are more varied
than was once thought and differences in function related to differences in structure
(e.g. differences in the ratios of chlorophyll a to chlorophyll b etc., and the amino
acid content of the respective proteins) are still largely unresolved. It is clear,
however, that much of the chlorophyll is involved in “light-harvesting” and that
“Light-Harvesting (Chlorophyll-Protein) Complexes” constitute antennae which
funnel excitation energy to the reaction centres (Figures 3.4 & 3.5). The reaction
centres themselves (see Section 3.7) are embedded in core chlorophyll protein
complexes and contain β-carotene and electron carriers (such as cyt b559 which is
closely associated with the reaction centre of PSII). Most of the thylakoid proteins
are organised into four intrinsic protein complexes (PSII, PSI, cyt b/ƒ and the ATP
synthase) and these together with lipids account for the bulk of the thylakoid
50
CHLOROPHYLL PROTEIN COMPLEXES
membrane. The thylakoid however, is not in any sense a homogeneous structure.

There is both marked asymmetry (e.g. electron donors to PSII and PSI at the inner
surface and acceptor sites at the outer surface) and “lateral heterogeneity” (i.e. the
way in which the complexes are distributed along the length of the membrane. Both
of the aspects of structure have profound implications for function.
3.7 PSII Reaction Centre
The reaction centre in PSII accepts electrons from the water-splitting oxygen-
evolving complex and uses light energy to raise them to a higher energy level from
which they can run downhill though a series of electron acceptors to PSI which, with
the help of longer wavelength photons, kicks them further upwards en route to
ferredoxin and NADP (Section 4.2).
The primary electron donor in the PSII reaction centre is pigment 680 (P680),
a special form of chlorophyll a with an absorption maximum, as the name implies,
at 680 nm. Upon excitation of P680, an electron is passed uphill, via an intermediary
acceptor, phaeophytin, to the primary acceptor QA (see e.g. Fig. 2.9). QA is a
covalently bound form of plastoquinone. Electrons pass from QA to QB, a diffusible
form of plastoquinone, and then out of PSII, down a thermochemical (energy)
gradient to PSI and beyond.
3.8 PSI Reaction Centre
My own lasting and endearing recollection of an irreverent, ertswhile Dutch

scientist, Bessel Kok, was of a head, wearing glasses and a serene expression,
swimming gently into the distance in a New England lake. Back in the laboratory
he had made many a notable observation including, in 1956, the fact that there was
a small light-induced absorption change at about 700 nm which he ascribed to
“pigment 700”. The change in P700 was subsequently shown to result from photo-
oxidation of specialised chlorophyll a by far-red light. This chlorophyll was
designated the primary electron donor in the reaction centre of PSI which nestles
within a chlorophyll protein complex (Section 3.3). When illuminated it transfers an
electron to the primary acceptor in PSI which is believed to be a membrane-bound
form of the iron-sulphur protein, ferredoxin (an electron carrier in the chain of
carriers between PSI and NADP). When P700 is oxidised to P700+ by a photon entering
PSI, the “hole” so created is filled by an electron which has been passed, from PSII
via plastoquinone, plastocyanin and cytochrome ƒ (Section 3.9). P700 is involved in
both linear (non-cyclic) and cyclic electron transport.
3.9 Electron Carriers
In the preceding sections in this chapter, we have looked at light harvesting,

at the capture of photons and the initiation of electron transport. We shall return to
this topic again in Chapter 4 but we need, for the moment, to anticipate that
discussion and remind ourselves, very briefly, that two photosystems are involved
in the transfer of electrons from water to NADP and that associated with these
photosystems there are a number of electron carriers (Section 1.2). Precisely where
structure ends and concept begins need not concern us too much for the moment but
it is convenient to think of the two photosystems joined by a bridge of electron
51
carriers (Fig. 3.12). These include plastoquinone, plastocyanin (a blue copper

protein) and a cytochrome (cyt. ƒ) discovered by Robert Hill which only occurs in
leaves (hence ƒ for frons). As we shall see in section 4.7 the nature of these electron
carriers is crucial. They have to have the right oxidation/reduction potential
(willingness to become oxidised or reduced) but, in addition, some will only accept
electrons whereas others will accept hydrogens (section 1.2). This results in the
formation of a proton (H+) gradient across the thylakoid membrane which brings
about the conservation of energy, in the form of ATP, as these protons discharge
through an ATPsynthase (Fig. 2.9).
3.10 Beyond PSI
“Tom, Tom the piper's son

Stole a pig and away he ran
But the only tune that he could play
Was over the hills and far away”
To some, “Beyond PSI” is not over the hill but almost beyond the pale.
In a sense, they are right. It is possible, as Arnon and Whatley showed in their classic
experiment (Section 4.8) to divide photosynthesis into a light part and a dark part.
It is possible to get isolated chloroplasts to generate assimilatory power (ATP,
NADPH2), in the light and then encourage them to use this to “fix” a little CO2 in
the dark. In actuality, in vivo, the early photochemical events are closely linked to
reactions which can be regarded as part of the “dark biochemistry”. Some of these
do not even occur in the chloroplast. Sucrose synthesis, for example, occurs in the
cytosol but it utilises triose phosphate which is synthesised in the chloroplast and
returns inorganic phosphate (via the phosphate translocator - Section 4.11) to the
chloroplast in order that the synthesis of triose phosphate from CO2 and inorganic
phosphate might continue. If the inorganic phosphate content of the cytosol is
manipulated experimentally, say by feeding phosphate through the cut petiole of a
leaf, early photochemical events, such as fluorescence emission from chlorophyll a
in PSII (Section 3.7) is affected within minutes. Similarly, some of the enzymes
involved in the “dark biochemistry” are only “switched on” in the light. All of this
reminds us that, while we can divide photosynthesis into photochemistry and “dark
biochemistry”, the latter actually occurs in the light and any separation of these two
aspects is simply a matter of convenience which has little basis in reality. Having
said that, if we seek to make such a division at all, PSI is where we would do it.
All of the photosynthetic pigments and their associated proteins, the two
photosystems, the electron carriers and the ATPsynthase (Fig. 2.9 and section 4.7),
are located in the thylakoid membranes. Beyond PSI is the “dark biochemistry” of
carbon assimilation. Of course, there is the problem of where the thylakoid ends and
where the stroma begins but this is perhaps not of vast importance in the present
context and we shall note it, as best we can, as we continue.
The job of the constituents of the thylakoid membranes is to absorb photons

and to use this excitation energy to generate ATP and NADPH2). So far, in this
chapter, we have taken a brief look at the components involved in the transfer of
electrons from PSI to the primary acceptor in PSI. Where do they go from there?
The answer, of course, is to NADP but there are some bits and pieces in between.
The primary acceptor in PSI passes electrons to iron-containing sulphur proteins
which in turn transfer them to ferredoxin, a soluble iron-containing protein but one
which seems to be “associated” with the thylakoids. A flavoprotein, also tightly
associated with the stromal surface of the thylakoids, called “ferredoxin-NADP
52
BEYOND PSI
reductase”, then passes these electrons to NADP. Also in some circumstances,

electrons may be passed, from about this point, to the plastoquinone pool (thereby
giving rise to cyclic electron transport - section 4.5) or to molecular oxygen (the
Mehler reaction or pseudocyclic electron transport). If, for the sake of convenience,
we lump most of these together with PSI it is clear that by the time that NADP has
accepted electrons the photochemistry involving the thylakoid is over and the “dark
biochemistry” (Chapter 5) of the stroma is about to begin.
3.11 Where it All Happens
So far we have considered the structure of “the photochemical apparatus”, as

it is sometimes called, but not where it is located. We know now that all these
processes of energy transduction occur within the thylakoid membranes but where
are they within the leaf? It has been known, since the last century and the work of
Sachs in Würzburg, that starch in leaves is normally formed only in illuminated
chloroplasts and, since starch was then regarded as the end-product of
photosynthesis, chloroplasts were identified as the sites of photosynthesis. Hill’s
classic experiments (Section 4.1) raised doubts about this because his isolated
chloroplasts evolved oxygen but did not “fix” carbon dioxide. Eventually, we learned
how to be nice to isolated chloroplasts. So nice, in fact, that they would fix carbon
dioxide at rates which were almost as good as the intact leaf. But they would not
make sucrose, regarded (since the work of Benson and Calvin) as the major end-
product of photosynthesis. Now all is resolved although there are endless details still
to be added. Photosynthetic carbon assimilation occurs in the stroma of the
chloroplast (Fig. 4.8) where it leads to the formation of triose phosphates which can
be converted in the stroma of many (but not all) plants to starch. Alternatively it can
be transported to the cytosol, where sucrose is synthesised. The photochemical
apparatus (chlorophylls, reaction centres, electron carriers, etc) are located in the
thylakoid membranes within the chloroplast. These are embedded in the stroma, a
protein gel in which the carboxylating enzyme, RUBISCO (section 5.2) is a major
component. The stroma is contained within a double envelope (section 3.13). The
chloroplasts themselves (Fig. 3.8) are located in several layers of cells between the
upper and lower epidermis of the leaf (which is perforated with stomatal apertures
which permit exchange of O2 and CO2 between these tissues and the external
atmosphere). In dicotyledenous leaves (i.e., in species like herbs and deciduous trees
which produce two cotyledons or “seed leaves” when their seeds germinate), there
is often a single or double palisade beneath the upper epidermis. These are cells
which look like a fence (hence the name) when seen in cross-section and they
comprise an effective layer of chloroplasts, maximising light interception. Deeper
within the leaf is the spongy mesophyll which still contains chloroplasts but which
has an open cellular structure to facilitate gaseous exchange. C4 species (Fig. 5.11)
have a different (“Kranz” type) anatomy.
One thing worth remembering about chloroplasts is that there are an awful lot
of them and they are very small. They are about the same size and shape as
cyanobacteria (Section 8.3) and red blood corpuscles (but then it may not help to
know that something is the size of a plover’s egg unless you have one in your hand).
Rabinowitch tells us that chloroplasts are flattened ellipsoides about 5 microns (5µ
= 5 µm = 5000 nm) long but that might not help a lot either. Nor might it help, too
much, to know that 5 µm (5000 nm) is about ten times the wavelength of green light
or about as long as 50,000 molecules of water laid end to end. Perhaps, we can begin
to get an idea of size and number if we remember that, in a leaf as big as your hand
(which tells you immediately that this is a very approximate figure), there are about
53
CHAPTER33- -HARVESTING
CHAPTER HARVESTING THE
THE SUN
Fig. 3.6 Three dimensional view of the interior of the spongy mesophyll of a leaf (after
Troughton & Donaldson). To illustrate the open nature of the structure of this tissue which facilitates gaseous exchange.
Carbon dioxide, entering the leaf via the stomatal apertures diffuses freely through the cavernous inter-cellular spaces and
dissolves readily in the thin film of water which always bathes these surfaces. The outline of the chloroplasts lying immediately
beneath the cell walls (see also Fig. 3.11 and 3.12) gives these surfaces a patterned appearance and the fact that the
chloroplasts are distributed in this way within the cells maximises both light interception and transport of CO2. The thin
film of water is constantly replenished by the transpiration stream which conveys water and mineral ions from the roots,
via the vascular tissues of the leaves. Transpiration itself, in which water evaporates within the leaf and diffuses as a vapour
through the stomata, is regulated by the size of the stomatal aperture but there is an obvious trade-off between limitation
of water loss and restriction of carbon dioxide entry.
54 54
WHERE IT ALL HAPPENS
3 to 5 × 109 chloroplasts - i.e. about as many chloroplasts as there are people on

the earth. This is why “starch pictures” (Figs. 3.8-3.10) are so well defined. These,
if you are not familiar with them, are the things that old-fashioned spy stories were
made of, like invisible ink. They are pictures created in starch (within chloroplasts)
in a leaf rather than in particles of silver in a conventional black and white
photographic negative. If you have access to one or two reagents and a slide projector
you can make one for yourself.
Chloroplasts
} Palisade
} Spongy
Mesophyll
Stoma
Vascular
Bundle
Mid-rib
Figure 3.7. Cross section of a C3 leaf. (After Sachs) Shows location of chloroplasts
(black bodies lining periphery of palisade and mesophyll cells - see also Fig. 3.12).
This section is through a mid-rib in which the main vascular tissue (responsible for
supply of water and mineral salts and removal of sugar etc.) is embedded. Some leaves
have more than one layer of palisade cells; all have a spongy mesophyll layer with
spaces between the cells which permit free circulation of air, so that CO2 (entering via
the stomata) can be fixed in carbon assimilation. In starch forming C3 leaves, all of
the chloroplasts will come to contain starch grains after illumination.
3.12 Starch Pictures
What you do is this. First find a leaf. In principle any leaf will do but some
do not make starch and others are not too easy to handle. Molisch, who started all
this, used Tropaeolum (which gardeners, for some reason, usually call Nasturtium).
Geranium (which gardeners ought to call Pelargonium) is better. The first trick is
to get rid of all its starch. In the leaf, as you recall, starch (a polysaccharide made
up of “glucose” units) is present only in the chloroplasts where it is presumed to
represent photosynthetic product in excess of that which could be used by the rest
of the plant in daylight hours. Certainly in a healthy leaf, in its prime, much of this
starch is “mobilised” (i.e. converted to simpler molecules such as triose phosphates
and glucose) by night and transported out of the chloroplast. So if we put a
“geranium” in the dark for 48 hours (72 hours may do it grievous bodily harm) we
55
can expect to find it free of starch. Accordingly, if we remove the chlorophyll from
the leaf (so that it now looks pale cream in colour) and stain for starch we will not
find any. How to remove the chlorophyll? Chlorophyll, as you recall, can be
dissolved in organic solvents but leaves are full of water and solvents such as petrol
(petrol ether) do not mix with water and are messy and dangerous things to handle.
Acetone is fine but it has an awful smell and, in the normal way of things, is far
too dangerous to use (because of flash ignition of acetone vapour). Ethanol is
charming but you may have problems with the law, customs and excise, or whatever.
If in doubt settle for methanol (methylated spirit) containing 10 to 20% water. Kill
the leaf by dipping briefly in near-boiling water. Transfer to warm methanol in a
beaker and heat carefully (best over a hot plate and in a fume cupboard or hood to
avoid fire risk or, failing this, support the beaker over a container of hot water in
a well ventilated space). Once the chlorophyll has been leached from the leaf (it takes
about 15 minutes and it may help to use more than one lot of methanol) rinse it well
in water and add a few drops of iodine solution (0.2 g. iodine + 5 g. potassium iodide
in 100 ml of water). Nothing will happen, except that, if you add too much iodine
the leaf will lose its pleasant cream colour and become pale brown. But this, of
course, is the equivalent of attempting to take a photograph with the lens cover in
place. Before proceeding to extraction and staining you must first make your picture.
The easiest, and least satisfactory, thing to do is to obscure part of the leaf with a
piece of card and put the geranium, pot and all, into bright sunlight for half an hour
or so. Subsequent killing, extraction and staining will produce a black image against
a cream background - cream where the card has stopped the light getting to the leaf.
“Real” pictures of good quality can be achieved by obscuring part of the leaf with
a photographic negative and illuminating overnight with a 100 W lamp at a distance
of a foot or so above a trough of water to filter out heat. If you want to be really
fancy, project an image on to a de-starched leaf using a slide-projector and a lens
(to keep the image small). In this case it is important to hold the leaf between glass
to prevent it moving and, ideally, to place black cloth soaked in bicarbonate solution
behind the leaf to provide it with plentiful CO2 and diminish the possibility of light
being reflected back into the leaf from the surface of the glass. These devices are
all intended to shorten the illumination time to 15-20 minutes and keep the leaf
perfectly still during this period. (Even the fathers of modern photography could not
get good images if their subjects moved during exposure of the film).
Figures 3.8-3.9 are examples of what is possible. This is how to smuggle the
plans out of the country as an image, created in starch within a leaf, now dried and
slipped innocuously between the pages of a book, waiting to be mounted and stained
with iodine. All very well, you might think, but where is its relevance to the subject
of this book? I have included them for several reasons. The first is that I needed a
schematic diagram of chloroplast structure and what nicer way than to persuade
chloroplasts to make me one? The second to re-create the original observation by
Sachs in the last century that starch was only found in illuminated chloroplasts and
that these must therefore be the organelles responsible for photosynthesis. The third
to give a glimpse of chloroplasts at work because they, after all, are what we depend
on for our energy and our existence and here is visual evidence of transduction of
light energy to chemical energy in the form of CH2O. The fourth to show that even
plant biochemistry can be beautiful.
The successive enlargements of the starch picture in Figs. 3.9 to 3.10 illustrate
the degree of resolution which can be attained in this way given the immense number
of chloroplasts in a leaf. In the highest magnification the outlines of stomatal
apertures (through which CO2 enters the leaf) can be seen because starch in stomata
is not mobilised in darkness like that in the mesophyll and palisade tissues and is
therefore stained by iodine regardless of prior illumination, or the lack of it.
56
STARCH PICTURES
STARCH PICTURES
Fig 3.8 (Top right) The figure of "Innocence" was

originally drawn by Pierre-Paul Prudhon (1758-1823).
Here it is executed in starch within a "geranium" leaf
which has been illuminated through a photographic
negative (see text). Every detail of the image is made up of
many millions of starch grains. This starch is formed only
in the chloroplasts which have been illuminated, hence the
definition is as good as that which would be obtained with
photographic paper and provides a striking visual
demonstration of photosynthetic carbon assimilation.
Fig 3.9 (Below) Starch picture created in a

"geranium" leaf by illuminating the starch-free leaf
through a photographic negative. The picture contains a
facimile of the title of the first work by Molisch on this
subject in 1922 and below it, the outline diagram of a
chloroplast.
57
57
CHAPTER HARVESTING THE
THE SUN
Fig. 3.10 Starch Pictures. Successive enlargements of Fig. 3.9. In the lower of these it is just possible to see the
starch grains in the guard cells of the stomata. These cells do not lose their starch entirely in the dark and therefore appear
as small dots (arrowed), providing a convenient scale by which the definition of the picture can be judged. It will be seen that
the much larger black, circular, machine-made areas used by the draughtsman in the diagram of the chloroplast are reproduced
with remarkable precision. There is no discernible formation of starch in the darkened areas, even in the immediate vicinity
of the illuminated cells.
58
STRUCTURE OF THE CHLOROPLAST
3.13 Structure of the Chloroplast
As the diagram within the leaf (Figs. 3.9 and 3.10) indicates, the basic
structure of the chloroplast is very simple. The detailed structure is, on the other
hand, extremely complex and still far from being fully elucidated or properly
understood. That there is still so much to learn is not for want of effort or interest
but it should be appreciated that, even in regard to the overall structure, we are
talking about an object so small that we can comfortably accommodate as many
chloroplasts as there are people in the world within the confines of a leaf of average
size. When it comes down to detail we are essentially talking about molecular
structure and very complex molecules at that. These, apart from those already
touched upon in other sections of this chapter and elsewhere are largely beyond the
scope of this book. For present purposes, Fig. 3.10 will suffice to define the major
compartments. First of all there are the outer envelopes. The first of these is freely
permeable and, in the words of the song, can be regarded as “the skin, that keeps
the rest in” although there is reason to believe that there are one or two bits and
pieces of importance between the two envelopes. The inner envelope is certainly
59
extremely important in function because it houses “the phosphate translocator”.
(Section 4.11). This works like a door guarded by a demon which only allows certain
molecules to pass through and then only in exchange for other molecules which pass
out. This is the principal channel of export of photosynthetic products from the
chloroplast to the cytosol (the compartment of the cell within which other organelles
such as nucleus, mitochondria, etc., are located). Triose phosphate produced by
operation of the Calvin Cycle (Chapter 5) is exported from the chloroplast via this
route in exchange (Fig. 3.11) for inorganic phosphate (Pi). Much of the triose
phosphate is used in the synthesis of sucrose in the cytosol, prior to movement of
this sucrose to other parts of the plant. Sucrose synthesis from triose phosphate
involves release of inorganic phosphate so there is a constant cycling of Pi between
chloroplast and cell brought about in this way.
Fig. 3.11 Metabolic sites in the chloroplast including the Pi translocator.
Within the inner membrane there is the stroma. This can be thought of as a
protein gel containing the enzymes of the Calvin Cycle; inorganic molecules like Pi
and dissolved carbon dioxide and oxygen; ions like K+, Na+, Mg++ and Cl- etc. The
largest single constituent is RUBISCO, the carboxylating enzyme (section 5.2),
which is present in astonishingly large quantities. Lying in the stroma is the thylakoid
compartment. The name is from the Greek and derived from its perceived similarity
to baggy trousers, traditionally worn in some areas of the Mediterranean. There is
probably only one thylakoid compartment within each chloroplast but it is very
difficult to be sure because this sac is often folded repeatedly upon itself (Fig 3.14)
to form stacks of “grana” (so called because they look like “grains” when viewed
alone in the light microscope). The thylakoid membranes are green, unlike the
chloroplast envelopes which are yellow. They house the chlorophylls, some
carotenoids, and the electron carriers (such as plastoquinone, cytochromes,
plastocyanin and ferredoxin - section 3.9) all embedded in a protein-lipid matrix. The
degree of organisation within the thylakoid membranes is immense including, as it
does, the light-harvesting complexes, reaction centres, etc., and the ATPsynthase
which is concerned in ATP synthesis (Section 4.7). During electron transport,
protons are moved from the stromal space, which therefore becomes more alkaline,
into the thylakoid space which becomes more acid. The discharge of protons through
the ATPsynthase drives ATP formation so that the whole system is roughly
analogous to a hydroelectric system in which electricity is “stored” by night by
pumping water into a reservoir from which it is discharged the next day through an
electricity generating turbine. In photosynthesis, light energy generates the electrical
ELECTRON
CELLS MICROGRAPHS
WITH CHLOROPLASTS
Fig. 3.12 Electron micrograph showing chloroplasts lying in a thin film of cytoplasm against the walls of spongy
mesophyll cells. For the location of these cells see Fig. 3.7. The centre of each cell is occupied by a large central vacuole. The spaces
between cells facilitate gaseous exchange. - Courtesy of A.
61
61
CHAPTER
HARVESTING THE
THE SUN
D. Greenwood
Fig. 3.13 Enlargement of Fig. 3.12. Showing thylakoid membranes within chloroplasts
embedded in cytosol surrounding the large central vacuole and bounded, in turn, by the mesophyll
cell wall. - Courtesy of A.
D. Greenwood
62
62
ELECTRON MICROGRAPHS
Fig. 3.14 Further enlargement of thylakoid membranes. Showing stacking (so called "grana", because of their granular
appearance under the light microscope) of thylakoid membranes (c.f. figs. 3.3 and 3.5). - Courtesy of A. D. Greenwood
63
63
energy which pumps the protons from the stroma to the thylakoid compartment. As
the protons discharge through the ATPsynthase, energy is conserved in a chemical
form as ADP is joined to Pi to give ATP (section 4.7).
3.14 Summary
In this chapter we have examined the physical basis of light-harvesting and
the transfer of electrons from water to NADP. We have seen that chlorophyll and
other photosynthetic pigments are located in thylakoid membranes lying in the
stroma of the chloroplast. Chlorophyll is green because it absorbs red and blue
photons whilst transmitting and reflecting green photons. Absorption of photons
causes chlorophylls to become excited and “excitons” migrate down antennae
(lightharvesting chlorophyll protein complexes) to the reaction centres of photosystems
I and II. Excitation of P680 and P700, in the reaction centres of PSII and PSI
respectively, initiates electron transport. Electrons are raised to a higher energy level
thereby creating the “holes” which accept electrons from water. From QA the primary
electron acceptor in PSII, electrons run “downhill” through a series of electron carri-
ers including plastoquinone (PQ), plastocyanin (PC) and the cyto chrome b/| com-
plex, to P700 in the reaction centre of PSI. Here further excitation by incoming photons
boosts electrons on their way to the primary acceptor (A) of PSI, ferredoxin, NADP
and eventually to carbon dioxide. Back at PSII, electrons released from water fill the
“holes” created by excitation of P680 and oxygen is evolved. Four photons, acting
consecutively in each of the two photosystems, combine to evolve one molecule of
oxygen and reduce two molecules of NADP. The very last components of the electron
transport chain are located in the stroma of the chloroplast, the protein gel of enzymes
in which the thylakoid membranes are embedded. As such, NADP and ferredoxin lie
at the boundary between the photochemical events and the socalled “dark biochemis-
try” of the Calvin Cycle (Chapter 5). The entire process, for which these components
are responsible, is one of energy transduction in which light energy is converted first
into electrical energy (electron transport) and then into chemical energy (energy rich
compounds such as ATP and NADPH2).
64
CHAPTER 4 - ASSIMILATORY POWER
4.1 Equations Old and New
Traditionally, the overall equation for photosynthesis has often been written as :-
hυ
_ 6CO 2 + 6H 2 O → C 6 H12 O 6 + 6O 2 Eqn. 4.1
There is nothing wrong with this equation to the extent that it succeeds in
summarising most of the essential features of photosynthesis - the utilisation of light
energy i.e. hv Section 2.3), the release of oxygen and the formation of a carbohydrate
(C6H12O6) from carbon dioxide. In other regards it is misleading. For example, the
first real “product” of photosynthesis is not a free hexose sugar, as C6H12O6 implies,
but rather a triose phosphate (i.e. a sugar containing three atoms of carbon, rather
than six, joined to a terminal phosphate group - Section 5.2).
Although sugars such as glucose and fructose (both of which have the same
empirical formula, C6H12O6) may eventually appear in plant leaves as a result of
photosynthesis they are not formed directly from carbon dioxide and are not even
particularly important compounds in leaf metabolism. Many, but not all, leaves
accumulate polysaccharides, such as starch, which are multiples of C6H12O6 units.
These are mainly temporary storage materials rather than immediate products. For
the moment, therefore, we can simplify equation 4.1 by substituting CH2O for
C6H12O6 while remembering that CH2O is merely a convenient short-hand way of
describing a carbohydrate (all carbohydrates, i.e. hydrated carbon, contain CHOH
groups). Our simplified equation therefore becomes:-
66
EQUATIONS OLD AND NEW
hv
CO 2 + H 2 O → CH2 O + O 2 Eqn. 4.2
But even this equation, like equation 4.1, disguises some important underlying facts.
One is that, equation 4.2, as written, is energetically unfavourable. In order to
proceed it must consume “assimilatory power” (Section 4.8) in the form of ATP and
NADPH2. Another is that, if H2O is added to C to give CH2O, it looks as though
the oxygen evolved is derived from the carbon dioxide and, in such a case, (no matter
how the equation is juggled) part at least of the evolved oxygen would have to be
derived from that source. However, at Cambridge in the 1930’s, Robert Hill
succeeded in isolating active chloroplasts from green leaves and showed that these
green organelles (Section 3.13) would evolve oxygen when illuminated in the
presence of an artificial electron acceptor (Section 1.2). No carbon dioxide was
involved in the Hill reaction, which can be written, as follows, if the acceptor (the
Hill oxidant) is represented by “A”:-
hv
2H 2 O + 2A → 2AH 2 + O 2 Eqn. 4.3
In short, it was clear that, at least in these circumstances, the oxygen resulted from
the photolysis (light-splitting) of water.
[Hill used potassium ferricyanide to accept electrons but a great many

compounds, such as the dye, 2,6-dichlorphenol indophenol (which loses its
blue colour as it is reduced), can be used for this purpose. Moreover, provided
the acceptor has an oxidation/reduction potential (see legend to Fig. 4.2)
which allows it to interact with carriers in the Z-scheme it can be either an
electron acceptor, as such, or a hydrogen acceptor (c.f. Section 1.2).]
The overall equations for photosynthesis, and for the Hill reaction, can be
made compatible by using “AH2” to represent the hydrogen donor required for the
reduction of carbon dioxide:-
hv
CO 2 + 2AH 2 → CH2 O + 2A + H 2 O Eqn. 4.4
If equations 4.3 and 4.4 are now added together, and the A’s cancelled, we get:-
hv
2H 2 O + CO 2 → CH2 O + O 2 + H 2 O Eqn. 4.5
If we go one step further, and cancel one molecule of water at either side of the
equation, we would be back to equation 4.2. However, if we leave equation 4.5
unchanged, we have an equation which is essentially the same as equation 4.2 but
which does not insist that some of the oxygen evolved must come from the carbon
dioxide. Moreover, if we bear in mind the derivation of equation 4.5, it tells us that
photosynthesis involves the reduction and reoxidation of some substance, A, an
electron carrier. In the plant, the real compound “A” is a coenzyme (a non-protein
molecule) which works in conjunction with an enzyme (i.e. a protein catalyst). The
particular coenzyme concerned is called nicotinamide adenine dinucleotide
phosphate (NADP). It is, in this sense, the natural Hill oxidant or hydrogen acceptor
(c.f. Section 1.2 Eqn. 1.2). Like other compounds which function in oxidation/
reduction reactions it also functions as a hydrogen donor, in this instance passing
hydrogens to carbon dioxide.
67
4.2 The Reduction of NADP
NH 2 It would be nice if we could simply write the “natural” Hill reaction as :-

C N
H N C
HC C
CH NADP + H 2 O → NADPH 2 + 1
2 O2 Eqn. 4.6
C
HC C CONH 2 N N
HC +
CH O O and, indeed, you may sometimes find it written just like that. Striving for too much
N
CH2 O P O P O CH2 simplicity can bedevil understanding, however, and (having read and digested
O O Section 1.2) you should not feel too uncomfortable with the fact that hydrogen
H H OH OH H H
H H H
transfer always involves electron transfer (because H ⇔ H+ + e-), and that some
oxidants (acceptors) can accept hydrogens whereas others can only accept electrons.
OH OH OH OPO OH2
Not to be outdone, NADP can accept both. Accordingly, if we wish to represent the
Nicotinamide adenine dinucleotide phosphate reduction of NADP more accurately we should write :-
+
(NADP or NADP )
NADP + H 2 O → NADPH - + H + + 1
2 O2 Eqn. 4.7
indicating that the NADP molecule has been able to accept one hydrogen and one
electron rather than two hydrogens, as equation 4.6 would imply. When acceptors
leave hydrogen ions (H+) behind in solution, as NADP has done in equation 4.7, there
NH 2
are two additional consequences. One is that these acceptors become negatively
C N
H2 + H
+ N C charged (having acquired an e-) and the other is that the surrounding solution
CH becomes more acid because its hydrogen ion concentration has increased (i.e. its pH
C HC C
C C CONH 2 N N has decreased). As discussed in Section 1.7, water spontaneously dissociates, to a
C CH O O small extent, into hydrogen ions (H+) and hydroxyl ions (OH-).
N
CH2 O P O P O CH2
O O
H H OH OH H H H 2 O ⇔ H + + OH - Eqn. 4.8
H H H
OH OH OH OPO OH2 [There are 10-7 gram ions of H+ and OH- in water which is neutral (i.e. neither
+ acid nor alkaline) but it is more convenient to express the hydrogen ion
NADPH 2 (or NADPH or NADPH+H )
(proton) concentration [H+], as its negative logarithm (p), so that [H+] × 10-7
becomes pH 7. Accordingly, we can arrive at a pH scale, or measure of
acidity, which ranges from zero (most acid) to 14 (most alkaline) and reflects
the extent to which acids give rise to H+ ions. If hydrogen ions (protons) are
formed as the result of a reaction such as that described by Eqn. 3.7, the pH
will fall (say from 7 to 6); i.e. the solution will become more acid.]
All of this is mentioned again here for two reasons. One is to explain why,
if we wish to represent the reduced form of NADP as accurately as possible, in an
abbreviated way, we should write NADPH- + H+ rather than NADPH2 (even though
we shall continue to use NADPH2, or even NADPH, in this text where it is most
appropriate to do so). The other is that, although photosynthetic electron transport
involves a number of electron carriers, only some, like NADP, will also accept
protons. This, as we shall see (Section 4.4), generates a change (∆) in pH. This is
important, because the ∆pH so generated, drives the formation of ATP (adenosine
triphosphate) from ADP (adenosine diphosphate) and Pi (inorganic phosphate).
Together, ATP and NADPH2 constitute “assimilatory power” (Section 4.8) i.e., so-
called high energy compounds which are consumed in the assimilation of carbon
dioxide. They are, in effect, the first stable chemical entities in the transduction of
light energy, via electrical energy to chemical energy in the photosynthetic process.
As such, they occur in chloroplasts in relatively small quantities and are utilised
(Section 4.9) as rapidly as they are generated (Section 4.7). Sucrose, the major end-
product of photosynthesis, is also a “high energy” compound in the sense that it
68
THE REDUCTION OF NADP
yields a lot of heat if burned in a calorimeter and generates many molecules of ATP
etc., if consumed in respiration but it serves a very different function (transport and
storage of carbon and energy) and, as such, is accumulated in large quantities in
leaves.
4.3 The Z-scheme
Following excitation of chlorophyll by light (Chapter 3), the first steps in the
conversion of electrical to chemical energy involve the generation of “assimilatory
power” (Section 4.8). This is accomplished by the operation of the Z scheme of Hill
and Bendall (through which electrons follow a Z-shaped path, through two
photosystems and a connecting bridge). This process may be compared to the
unlikely sequence of events depicted in Fig. 4.1.
e-
e-
e-
e-
e-
e-
uh
e-
h
u
Fig. 4.1 The Z-scheme by analogy.
In this scheme, the man on the extreme left delivers energy in the form of a
hammer-blow. This projects a ball upwards into the hands of the second man who
drops it down a steep incline. As it runs downhill it drives a wheel (in the bridge
between the two platforms). On the right, the process is repeated except that the final
catcher then throws the ball into a net. In the Z-scheme proper (Fig. 4.2), the
hammer-blows are photons delivering energy to chlorophyll molecules in
photosystems II and I respectively (the physical nature of the two photosystems is
discussed in Chapter 3). The ball is an electron. Each electron therefore requires the
expenditure of two photons (two quanta of energy) to lift it, from ground level, into
the net (NADP). The passage of electrons down the thermochemical (energy)
gradient drives the wheel (the ATP-generator). Each NADP accepts two electrons.
Four photons are therefore required to bring about the reduction of one molecule of
NADP.
69
The positively charged “holes”, created by light-excitation of chlorophyll

molecules in PSII, are filled by electrons donated by water so that eight photons are
required for the reduction of two molecules of NADP and the associated evolution
of one molecule of oxygen (Eqn. 4.9). In equation 4.9 the formation of one molecule
of ATP is also indicated (Section 4.7), but the ratio of ATP to NADPH2 could be
1.3 to 1, or even higher. Alternatively, extra ATP could be formed by cyclic electron
transport (Section 4.5) involving only one photosystem, or by the reduction of
molecular oxygen instead of NADP. Either alternative would lead to more ATP and
a lower quantum efficiency (greater quantum requirement - Fig. 4.2 Section 6.6).
-1000 PHOTOSYSTEM II BRIDGE PHOTOSYSTEM I

40
-800
THE Z SCHEME
-600 Fe-s
A
FD 30
-400
Einstein light at 680 nm
Free energy ( F-,Kcal/N eV)

NADP
Redox potential (m V)
-200
QA
b 650
a 663
u
h I 20
Zero Plastoquinone
huI
a 669
D
a 673 (<730 nm)
+200 a 677
a 684
b 650 Cyt b/f 95 10

+400 a6
a 663 Plastocyanin P700
a 669 u
h II
+600 a 673
2H
+ a 677
u
h II
Z (<700 nm)
+800 H2O 80
a6 0
_1 P680
2 O2
+1000
F696
Fig. 4.2 The Z-scheme . This is both an energy diagram and a map of electron flow.
Redox potentials (left) are like football league tables or tennis “seeds”. Under given
conditions, a team at the top of the league is likely to beat a team below it. Similarly,
compounds with negative redox potentials are able to reduce compounds with more
positive potentials. Thus, the transfer of electrons from water to NADP (involving the
co-operation of two photosystems) leads to the creation of a hydrogen donor
(NADPH2) used to reduce CO2 to CH2O. The energy needed to drive this electron
transfer (right) is seen to be about 26 Kcal (109 Kjoules) per electron (on a molar
basis) and enters through the two photosystems. Two light-harvesting antennae
(Section 3.3) of chlorophyll molecules funnel photons into P680 and P700 in PSII and
PSI respectively (Sections 3.7, 3.8 and 6.6). Other letters (e.g. PQ, for plastoquinone)
mark the probable position in the energy diagram of various carriers through which
electrons are passed on their way from water to NADP. Each photon (quantum)
entering each photosystem can lift one electron to a higher (more reducing) level so
that, in order to transfer 2 electrons from H2O to NADP, 4 photons are required. Since
4 electrons are transferred for each molecule of O2 released (2H2O + 2NADP →
2NADPH2 + O2) the whole sequence has to occur twice and the quantum requirement
thus becomes 8 per O2. Some of the energy released as electrons flow “downhill”
across the “bridge” between the two photosystems is conserved as chemical energy
in the form of ATP (Section 4.7).
70
NON-CYCLIC OR LINEAR TRANSPORT
4.4 Non-cyclic or Linear Electron Transport
In vivo the donor is H2O and the acceptor NADP but, in experiments with
isolated chloroplast, both artificial donors and acceptors are sometimes used.
B
_1 O + H O Catalase
2 2 2 H2O2 O2
A A
FD FD NADP
FP
Cyt b 6
C
Q NADPH 2
PQ
ADP + Pi
ATP
P700
PS I
P680
H2O _1 O
2 2
PS II
Fig. 4.3 Possible routes of electron transport. A, cyclic; B, pseudocyclic (Mehler
reaction) and C, non-cyclic or linear. See Fig. 3.5 for details of structure. The
hydrogen peroxide produced in the Mehler reaction can be broken down, by catalase
(in the cytosol) or further reduced.
“Non-cyclic photophosphorylation” is a term sometimes used to describe the

generation of ATP (Section 4.7) driven by linear electron transport. Non-cyclic
electron transport in the Z-scheme (Fig. 4.2) involves the “linear” transfer of
electrons from a donor to an acceptor. If the intermediate carriers are omitted, in
order to arrive at a relatively simple equation, non-cyclic photophosphorylation looks
like this :-
2NADP + 2ADP + 2Pi + 2H 2 O →

Eqn. 4.9
2NADPH + 2H + + 2ATP + H 2 O + O 2
but there is continuing uncertainty about the precise stoichiometry of this reaction,
i.e. whether or not, in all circumstances, there is only one molecule of ATP generated
per molecule of NADP reduced. The Calvin cycle consumes 1.5 molecules of ATP
for every one molecule of NADPH2 and, even though it is possible that additional
ATP is generated by cyclic electron transport (Section 4.5) to make up any shortfall,
it seems likely that linear electron transport may be responsible for most of the ATP
required in carbon assimilation.
71
4.5 Cyclic Electron Transport

As the name suggests, electrons in this process travel in a cycle, rather than
in a straight line from A to B. Cyclic electron transport in the Z-scheme usually
implies a return of electrons from a point at “the top” of PSI (possibly bound
ferredoxin) to the plastoquinone pool. In this way, electrons would cycle endlessly
round PSI without giving rise to oxygen evolution or NADP reduction. On the other
hand, as the electrons passed back down “the bridge” from plastoquinone to PSI a
∆pH would be created, just as it is in linear electron transport, and this would drive
ATP generation (Section 4.7). So called cyclic photophosphorylation, i.e. ATP
generation driven by cyclic electron transport, may make up the short-fall (Section
4.4) in ATP needed for carbon assimilation. If this occurs, it will increase the
quantum requirement above 8 (see legend to Fig. 4.2) because of the photons needed
to “lift” additional electrons through PSI. In practice, quantum requirements,
measured under ideal conditions, are closer to 9 than to 8, possibly indicating the
occurrence of this process. O2
A
+ H2O2
2H
Q -
2e
ADP + Pi H2O + _12 O2
ATP
-
2e
PS I
H2O
PS II
_1 O + 2H+
2 2
Fig. 4.4 Pseudocyclic electron transport (Mehler reaction). Although, in the
presence of catalase, there is no oxygen evolution, this is not a true cycle (c.f. Fig.
4.3). Instead oxygen evolution is masked by equimolar oxygen consumption.
Nevertheless, electrons traverse both photosystems and are finally used to reduce
oxygen rather than NADP. The hydrogen peroxide may also undergo further reduction
to water.
Pseudocyclic electron transport is a term sometimes applied to the Mehler

reaction in which molecular oxygen serves as an electron acceptor in PSI rather than
NADP:-
H2O + O2 → H2O2 + 1
2 O2 Eqn. 4.10
but in fact, this involves linear electron transport. “Psuedo” is a good description
because the electron transport involved is actually linear, just as if NADP rather than
O2 was the acceptor.
The concept of a cycle in the Mehler reaction comes from the fact that if the
hydrogen peroxide (H2O2) so generated is broken down as fast as it is formed by the
enzyme catalase (Eqn. 4.11):-
H2O2 → H2O + 1
2 O2 Eqn. 4.11
72
CYCLIC ELECTRON TRANSPORT
there is no net consumption of water or evolution of oxygen as the reaction runs its
course In such circumstances (Eqn. 4.10 and Eqn. 4.11) the oxygen released by
photolysis of water exactly balances that fraction of the oxygen reduced by electron
transfer (Eqn. 4.10) and subsequently released by “catalatic dismutation” of the
hydrogen peroxide so formed (Eqn. 4.11). Chloroplasts prepared for experiments by
normal procedures are usually contaminated by catalase and the Mehler reaction can
then only be followed, by measurement of O2 uptake, if cyanide or azide is added
in small amounts to inhibit the catalase. The Mehler reaction is readily demonstrated
in experiments with isolated chloroplasts. In vivo, hydrogen peroxide may also be
reduced to water.
4.6 Hydrolysis of Adenosine Triphosphate (ATP)
The hydrolysis of one mole of ATP to ADP plus inorganic phosphate (Pi) is
accompanied by a release of energy (about 7 Kcal or 29 Kjoules) - see Eqn. 4.12.
Thus if ATP is consumed in a metabolic reaction (and ADP and Pi are released) it
can be regarded as having contributed about 7 Kcal of energy to that reaction. For
this reason ATP is frequently spoken of as an “energy donating” molecule.
Fig. 4.5 ATP hydrolysis by analogy
Fig. 4.6 Hydrolysis of ATP to ADP and Pi. (Where “A” is adenosine)
Confusion sometimes stems from the implication that energy is released when a
“high energy bond” (e.g. one joining ADP and Pi) is broken. This offends the
principle that bond dissociation always requires an energy input (Section 1.1). No
comfort can be immediately derived from a careful consideration of all the bonds
which are broken and re-formed during the hydrolytic process because at first glance
these are identical and no net gain or loss could be predicted. On this basis “what
is gained upon the roundabouts is lost upon the swings”. In fact, the bond values
depend not only on the atoms which they join, but also on the molecular environment
in which they exist. ATP is subject to internal stress (because of electrical charges
generated by ionisation and opposing resonance within the molecule) and may be
compared to bar magnets (with opposing poles) joined by pieces of string. Energy
would be needed to cut these bonds but the magnets would then spring apart, because
of the magnetic repulsion, producing a net energy gain. Pi is more stable as a separate
entity than as part of a molecule of ATP so that, even though equal numbers of O-
H and O-P bonds are broken and re-formed during hydrolysis, the new bonds are
stronger than the old and energy is released. Conversely an energy input is required
when ADP and Pi are condensed to give ATP and H2O.
4.7 The Generation of ATP
ATP is, like NADP, another co-enzyme but one which is involved in
phosphate (Pi) transfer rather than hydrogen transfer. It can also be regarded as
energy “currency”, or a source of energy in metabolic reactions. If ATP is
hydrolysed,
ATP + H 2 O ⇔ ADP + Pi Eqn. 4.12
energy is released for the reasons outlined in Section 4.6. Conversely, if ADP is
esterified (i.e. if Pi is joined to ADP in a reaction in which water is released,
ADP + Pi ⇔ ATP + H 2 O Eqn. 4.13
energy is required in order to drive the unfavourable equilibrium position of this

reaction towards ATP (c.f. Section 1.7)
As Fig. 4.7 shows, if chloroplasts are isolated from a leaf and illuminated
in the presence of NADP, electron transport occurs from H2O (which becomes
oxidised) to NADP (which becomes reduced). At the same time oxygen is released
and a proton gradient or ∆pH develops across the thylakoid membrane of the
chloroplast. This is largely a consequence of the fact that, when a molecule of
plastoquinone is offered an electron (e-) by excited chlorophyll it is simultaneously
obliged to take a convenient hydrogen ion (H+) to keep this electron company.
Moreover, it “picks up” (Section 1.2) this proton (H+) from the outside of the
thylakoid membrane in which it (plastoquinone) is located and then discharges a
proton to the inside of the thylakoid space as it passes the electron on to the next
carrier in the sequence. Accordingly, the space inside the membrane (the thylakoid
space) becomes more acid (because it contains more protons or hydrogen ions) and
the outside space (the stroma in Fig. 3.8b) becomes more alkaline (because it
contains fewer protons and, consequently, more hydroxyl ions - see Eqn. 4.8). As
this proton gradient builds up, it discharges through an ATPsynthase, an enzyme
which catalyses the esterification of ADP (Eqn. 4.13). No one quite knows how this
works but it is a bit like a head of water, built up behind a dam, discharging through
a turbine which generates electricity. The ∆pH is created by light-driven electron
transport and part of its energy is conserved as chemical energy, in the form of ATP,
74
THE GENERATION OF ATP
H2O Thylakoid Stromal

membrane compartment
e- + - CO2
PS II Calvin
e- + - cycle
_1 O + 2H+ metabolites
2 2 +
+ + +
2H2H PQ(H2 ) 2H 2H 2O
-
2OH
+ -
PS I NADPH
Thylakoid + - +
compartment H
++
Mg Mg
ADP + Pi
+ ATPase
H
-
Cl ATP Envelopes
Fig. 4.7 Generation of ATP. The pigments and electron transport chain are housed
in the thylakoid membrane which itself (see Chapter 3) lies within a protein gel (the
stroma) enclosed within the envelopes (the external boundary of the chloroplast). On
illumination, electrons from water are donated (top left) to chlorophyll in PSII excited
by the absorption of photons. The transfer of electrons to PSI via plastoquinone (PQ)
requires protons. These are taken up from the stroma and released into the thylakoid
compartment. The stromal pH rises and Mg2+ moves as a counter-ion. ATP is formed
as protons are discharged through the ATPsynthase. Electrons which have run “down”
the thermochemical gradient which bridges the two photosystems are finally boosted
“upwards” to NADP by light excitation of PSI. NADPH2 and ATP are utilised in CO2
fixation by the Calvin cycle in the stroma.
as the ∆pH discharges through the ATPsynthase. This concept is in accord with the
“chemiosmotic hypothesis” for which Peter Mitchell was awarded the Nobel prize.
Linear electron transport of 2 electrons from water to NADP is believed to generate
1.3 ATPs. This is consistent with an H+/2e ratio of 4 and an H+/ATP ratio of 3.
“Photophosphorylation” as it is called (i.e. light-driven ATP formation by
chloroplasts) was first demonstrated by Arnon and Whatley. They proposed several
varieties (see Sections 4.4 and 4.5). That which caused the greatest surprise to the
scientific community at the time was “non-cyclic photophosphorylation” i.e. ATP
formation associated with the linear transport (Section 4.4) of electrons from water
to NADP. At the time this seemed as unlikely then as an English tennis player
winning at Wimbledon or Margaret Thatcher being awarded an honorary degree by
the University of Oxford. A generation of biochemists had become accustomed to
the concept that oxidation (by molecular oxygen) of NADH2 generated in respiration,
led to the formation of ATP from ADP and Pi. Now they were suddenly and
unexpectedly asked to accept the fact that water could seemingly run up-hill as ATP
was generated during the reduction of NADP and the evolution (rather than the
uptake) of oxygen. Genius, it is sometimes said, is the recognition of the obvious
before it becomes obvious to everyone else. It was obvious to Robert Hill, but not
to a host of lesser mortals, that water could not run up-hill of its own accord but that
it could be lifted up-hill twice in succession and allowed to run “down-hill”, in
between, doing work as it did so. Hence the Z-scheme. Of course Hill did not get
75
there unaided and would no doubt have been the first to admit his debt to many other
contributions (of which that of Robert Emerson’s “enhancement” was perhaps the
most important and most relevant). Even so the concept of the Z-scheme (which
remarkably failed to impress the Nobel Prize Committee) pulled together all manner
of things which have, at least in this writer’s eyes, done more to advance our
understanding of the photochemical events of photosynthesis than anything else this
century. Amongst these is the simple notion that the reoxidation of QA by PSI is
equivalent to the “down-hill” passage of electrons which occurs when NADH2 is
oxidised in respiration. Arnon and Whatley’s non-cyclic photophosphorylation did
not, after all, fly in the face of thermodynamics. Once electrons had run “down-hill”
from the top of PSII to the bottom of PSI, generating a proton gradient en route, they
were lifted to the top of PSI, and hence to NADP, by light excitation of chlorophyll
essentially similar to that which had lifted them to the top of PSII in the first place.
Light excitation of chlorophyll is, in the end of course, responsible for all biological
“lifting”. How do you suppose NADH2 became reduced in the first place? Quite right,
by accepting electrons from the break-down products of sugars, or whatever, first
formed in photosynthesis. This is why “excited state one”, the red excited state of
chlorophyll is where it all starts. This winds the biological mainspring. This is the
point of transduction of light energy into electrical energy. The subsequent
conversion of electrical energy into chemical energy is all “down-hill” whether it
occurs in the plant or in the tissues of animals which have eaten plants.
Electron transport through the Z-scheme of the sort that we have so far
discussed is always associated with the generation of a proton gradient and this is
“coupled” to electron transport. The coupling may be “flexible” in the sense that
although a given proton gradient will only be able to drive a certain amount of ATP
formation it may give rise to less than the maximum. Experimentally, electron
transport may be uncoupled from ATP formation in various ways and electron
transport then runs faster, just as a locomotive uncoupled from the wagons of a train
could run faster. On the other hand, electron transport by isolated thylakoids also
runs faster when it is coupled to ATP formation (i.e. in the presence of ADP + Pi).
It is less easy to see, at first glance, why both coupling and uncoupling can accelerate
electron transport. The reason is, that as a proton gradient is established, it exerts a
“back-pressure” on electron transport. It becomes more difficult to release a proton
into a space already containing a large number of protons. Both ATP formation and
uncouplers discharge the proton gradient.
4.8 Assimilatory Power
Together, ATP and the reduced form of NADP, constitute “assimilatory

power”. As Arnon, Allen and Whatley showed in a classic experiment, assimilatory
power, generated in the light, can reduce carbon dioxide to CH2O in the dark. In
other words photosynthesis can be divided experimentally into two parts. The “light”
part (the photochemistry), in which the oxygen is evolved, is like the Hill reaction
(Eqn. 4.3) except that it also includes ATP formation (Eqn. 4.9). The “dark” part (the
so-called “dark biochemistry”) in which ATP and NADPH2 are consumed (c.f.
Section 3.10), is the conversion of carbon dioxide to carbohydrate. Similarly, the
photochemical events, which lead to the generation of assimilatory power, are
primarily associated with the thylakoid membranes (within the chloroplast) which
house the photosynthetic pigments. The “dark” events (so called because they can
be “driven” in the dark by assimilatory power even though they normally occur only
in the light) are located in the stroma (Fig. 3.8b). The stroma is a gel of soluble
protein in which the thylakoids are embedded and contains all of the enzymes
(biological catalysts) needed to convert carbon dioxide to CH2O. At the risk of
76
ASSIMILATORY POWER
LIGHT DARK
hu CO2
ADP ATP 14
NADP NADPH 2 CO2 + ATP + NADPH 2
14
CH 2 O
h u
Fig. 4.8 Arnon, Allen and Whatley’s Experiment. Experimental separation of

photosynthesis into photochemistry (left) and “dark biochemistry” (right). At left,
illuminated thylakoids give rise to ATP and NADPH2. At right, enzymes of the
chloroplast use ATP and NADPH2 to reduce (radioactive) CO2 to CH2O in the dark.
tedious repetition, it is probably worth noting once again that although the “dark
biochemistry” did not require light in this experiment (with isolated plastids in a test
tube) the corresponding process in leaves occurs in the light and indeed some of the
enzymes concerned are only fully operational when illuminated. In short, the “dark
biochemistry” (Chapter 5) actually occurs in the light and, in that respect, is just as
much a part of photosynthesis as the photochemical events which lead to the
generation of assimilatory power.
4.9 Utilisation of Assimilatory Power
All plants consume ATP and NADPH2 in a process usually referred to as the
Calvin cycle. This will be described in more detail in Chapter 5. In outline, the cycle
can be divided into three parts; carboxylation, reduction and regeneration. A
“carboxylation” is the addition of carbon dioxide to a pre-existing acceptor in such
a way that a “carboxylic” acid is formed. This is then reduced (Section 1.2), to the
level of carbohydrate (CH2O) by hydrogens from NADPH2. Some molecules of this
newly formed product are used immediately to regenerate the carbon dioxide-
acceptor.
In all, there are 13 reactions in the Calvin cycle. Most occur three times in
order to produce one molecule of product (a triose, or 3-carbon, sugar) from three
molecules of carbon dioxide. This inevitably demands a somewhat complicated
reaction sequence but, at least in outline, its principal features are readily understood
(Fig. 4.9). In order to produce one molecule of triose phosphate from three molecules
of CO2 and one molecule of inorganic phosphate (Pi) the cycle must turn three times
and is therefore best written in triplicate (Fig. 5.2). To do this it requires nine
molecules of ATP and six molecules of NADPH2. All of the NADPH2 and six out
of the nine ATPs are consumed in the only reduction (Section 1.2) sequence in the
cycle - the conversion (Section 5.4) of PGA to triose phosphate. The remaining three
ATPs drive the last stage (Section 5.14, equation 5.12) in the regeneration of the
carbon dioxide-acceptor.
77
Fig. 4.9 The Calvin cycle in outline. Most of the assimilatory power (ATP +
NADPH2) is used in the reduction of the first formed product (PGA) of CO2 fixation
(Chapter 5), the remainder in the regeneration of the CO2-acceptor. Product not used
in regeneration is used in other metabolic processes such as starch and sucrose
synthesis (Section 4.10).
4.10 Where It All Ends.
I know that I shall try the patience of some of my readers to the point of
exasperation unless I am able to offer them an occasional glimpse of the common
thread which strings this strange hotch-potch of subjects together. I hope, of course,
that each chapter will stand on its own feet just as I could reasonably claim that John
Steinbeck’s “Pastures of Heaven” makes good reading even if it is regarded as a
collection of short stories without a common factor. So I would be content with that
at least, but let me say that what I am attempting to do is to trace the conversion
of solar energy into chemical energy and that I hope finally to progress into ways
that Man uses, or misuses, that energy. So far, we have seen how light drives electron
transport and how electron transport produces the assimilatory power which, in turn,
drives carbon assimilation. (More properly ATP and NADPH2 are consumed by
carbon assimilation but that, you might reasonably complain, is a bit of academic
hair-splitting). In Chapter 5 we shall look into all of this in more detail but we might
begin to wonder where it all ends and certainly this part of the tale ends with triose
phosphate, sucrose and starch. These are the “end-products” of photosynthesis. More
about sucrose and starch later. For the moment let us just note that they are both
synthesised from triose phosphate (a 3-carbon sugar phosphate) and, since sucrose
contains two hexose (6 carbon) units, and since starch contains many hexose units,
they must be formed by a process of condensation which involves, at some stage,
the release of Pi. Starch, when it is made in a leaf, is a short-term (mostly overnight)
storage product and it is made in the chloroplast (hence starch pictures - Section
3.12). Sucrose, on the other hand, is made from triose phosphate in the cytosol (Fig.
4.10) and that brings us to a philosophical consideration of where photosynthesis
ends. We have concluded that the “dark biochemistry” starts at the “top” of PSI
(Section 3.10). We can similarly conclude that it finishes with sucrose, even though
78
the reactions which make sucrose from triose phosphate occur in the cytosol rather than in the chloroplast (Section
4.10). Certainly, if we do things to a leaf which affect this part of the “dark biochemistry” we can see an impact
on early photochemical events, like fluorescence, within seconds. That brings us to the question of how the triose
phosphate finds its way into the cytosol from the stroma.
Fig. 4.10 Starch and sucrose synthesis. Both starch and sucrose are made of 6-carbon units. In turn these
are synthesised from triose phosphate (TP). Starch is made in the stroma of the chloroplast, sucrose from TP
exported through the phosphate translocator in exchange for Pi. Release and recycling of inorganic phosphate
(Pi) during sucrose synthesis allow this process to continue.
4.11 The Phosphate Translocator
Isolated chloroplasts have figured large in my own contributions to photosynthesis. As you already
know, (Section 4.1) Robert Hill’s famous chloroplasts would evolve O2 when supplied with an artificial
electron acceptor but would not fix CO2. Arnon and Whatley’s chloroplasts were good at making
“Assimilatory Power”. They also fixed 14CO2. (Fig. 4.3) but in such small amounts that it was stretching
credibility to assume that they were fully functional. My own involvement came from my association with
Robert Hill (my Ph.D. examiner) and my boss in my first job, Charles Whittingham. He suggested that
improved performance by chloroplasts would be a useful enterprise for a young man to embark upon.
Robin Hill (as ever) pointed me in the right direction and, to someone who had learned to prepare record-
breaking mitochondria in Harry Beevers’ laboratory at Old Purdue, it seemed to be no great problem. Of
course it was more difficult than it seemed. There were so many variables that a logical approach would
have taken too long and changing several factors at a time, although desperately unscientific, was the only
way forward. In the end it worked and although, to some extent, my
Fig. 4.11 The Pi Translocator. This is located in the inner envelope and permits a
strict stoichiometric exchange of external Pi with internal triosephosphate
(dihydroxyacetone phosphate or DHAP). Movements may occur in either direction
according to circumstance (after Heldt).
colleagues and I had some of our thunder stolen at the eleventh hour by Dick Jensen
in the United States (who used our techniques plus a magic component called
inorganic pyrophosphate) the first achievement of rates by isolated chloroplasts
similar to those attained by intact leaves was a matter for some rejoicing. Of course
when you have succeeded in isolating fully functional chloroplasts for the first time
there is then the problem of what to do with them. Happily the chloroplasts
Pi
h u
CO 2
triose
phosphate
sucrose
themselves nudged us in the right direction. Firstly, they would not make sucrose,
which everyone at that time regarded as the end-product of photosynthesis. Secondly,
they responded very readily to PGA and triose phosphates (which were not supposed
to cross membranes) and finally they required Pi to function but were inhibited by
the same compound in fractionally larger amounts - an inhibition that was reversed
by triose phosphate and PGA. The reason for the failure to make sucrose was evident.
THE PHOSPHATE TRANSLOCATOR
It had to be made somewhere else. The trouble was that the enzymes concerned in
sucrose synthesis were found in chloroplasts prepared by non-aqueous techniques
and it was a long time before these enzymes could be accepted as contamination from
the cytosol. The Pi requirement was easier to understand because there was a clear
requirement for one molecule of Pi and three molecules of CO2 in the synthesis of
one triose phosphate. The inhibition by larger concentrations of Pi and its reversal
by triosephosphate or PGA was perplexing but finally, in 1970, my colleagues Carl
Baldry, Chris Bucke, Bill Cockburn and myself were bold enough to come up with
the following
“if sugar phosphates are exported from the chloroplast there must be a
corresponding import of phosphate (in some form) if steady-state photosynthesis is
to be maintained. .... A direct obligatory exchange between orthophosphate (outside)
and sugar phosphate (inside) could account for the inhibition of photosynthesis by
orthophosphate and its reversal by sugar phosphates.”
Meanwhile, in the spring of that year (1970), a German colleague, Hans

Heldt, visited Imperial College (where this work had been done) and discussed with
me his use of “centrifugal filtration” in examining the movement of ATP and ADP
across the chloroplasts envelope. I suggested, on the strength of our results, that he
looked, in the same way, at the transport of PGA and Pi. He did and the phosphate
translocator grew from hypothesis into physical reality. So what does the phosphate
translocator do? It facilitates an exchange across the chloroplast envelope, on a one
to one basis, of internal triosephosphate with external Pi. This is its principal
function. The chloroplast is not an independent entity living in a protected
environment of its own within the leaf. It has to maintain itself, of course, but it is
there to supply the plant with the wherewithal for the plant’s existence. If
photosynthesis is to continue unchecked and, if internal cycling of Pi is insufficient
to maintain rates of synthesis, then 1 molecule of Pi must be imported for every
triosephosphate exported. In other words, photosynthesis is a cellular affair. It is not
Photosynthesis and phosphate “a cellular affair”
81
a process which chloroplasts can achieve unaided for very long. This is why
photosynthesis will virtually cease in isolated chloroplasts as external Pi is consumed
and diminishes and why three molecules of O2 are then evolved for every Pi added.
This is why Pi, in relative excess, also inhibits. Clearly if too much triosephosphate
is pulled out of the chloroplasts because there is too much Pi competing for entry,
depletion of Calvin cycle intermediates will diminish replenishment of the CO2
acceptor. Competition is central to this last statement because if we regard the
translocator as a door controlled by a demon (Section 3.13), intent on regulating one-
to-one exchange, regulation will only be maintained if competitive pressures are
maintained. Thus Pi competes with C3 intermediates and vice versa. When internal
triose phosphate is in relative excess, and Pi is freely available externally, all is well
but this implies a fine balance between too little and too much cytosolic Pi.
All of this has implications for a complex system of regulation which is still
not fully understood. Relatively speaking, there is an immense pool of Pi within the
reservoir of the central vacuole but this is not free to enter the cytosol, otherwise
inhibition by excess Pi would rapidly follow. This leaves sucrose synthesis (from
triose phosphate in the cytosol) as the main mechanism for recycling Pi. Fine
regulation of enzymes concerned in sucrose synthesis, including the involvement of
an “effector” called fructose 2,6-bisphosphate, serves to allow sucrose synthesis to
proceed at a rate which matches the availability of triose phosphate for export.
[According to present understanding, fructose 2,6-bisphosphate (Fru2,6P2)

works by ‘sensing’ the availability of triose phosphate. Triose phosphate
increases the amount of substrate available to the FBPase (the enzyme in Fig.
4.10 which splits FBP into F6P and Pi), but decreases the concentration of
Fru2,6P2 (because it inhibits the activity of F6P,2-kinase, the enzyme which
synthesises Fru2,6P2). This decrease, in turn, releases an inhibition of FBPase.
This has a critical effect on sucrose synthesis, because FBPase catalyses the
first irreversible reaction in the cytosol.]
4.12 The Red Drop
This section might seem to those of my readers already knowledgeable about

photosynthesis, to have been added as an afterthought and out of context. In a way
they would be right but it is difficult, as we have already seen at the beginning of
this chapter, to avoid problems of this nature while striving for simplicity. So here
I have erred by neglecting to afford a proper recognition to a key observation which
influenced the development of the whole concept of the Z-scheme and its
formulation by Robert Hill and Fay Bendall. Now is my opportunity to put this right
but, in order to do that, we must forsake carbon assimilation momentarily (before
returning to it in more detail in Chapter 5) and return to the photochemistry.
Robert Emerson made a number of important contributions to photosynthesis

before his life was tragically ended when an aircraft in which he was travelling
crashed into the Hudson River. One of these was his recognition of the “red drop”
and the associated phenomenon of “enhancement”. Fig. 4.12 shows the absorption
spectrum of chlorophyll. It is also possible to derive an “action spectrum” for
photosynthesis to see how effectively different wavelengths of light drive
photosynthesis. Fig. 4.12 shows such a comparison based upon equal numbers of
incident photons at each wavelength. On this basis, the action spectrum closely
follows the absorption spectrum. This is because red and blue photons are more
readily absorbed by chlorophyll and if a leaf is offered equal numbers of blue, green
82
THE RED DROP
relative photosynthetic activity

Relative light absorption and
400 480 560 640 720

Wavelength (nm)
Fig. 4.12 Absorption and action spectra compared. Solid line, absorption spectra
for Ulva. Broken line, relative photosynthetic rates for equal numbers of incident
quanta at each wavelength (after Haxo and Blinks).
and red photons, fewer green will be absorbed. Thus, photosynthesis in weak green
light will be slower than in red or blue light at equal photon flux densities. Fig. 4.13,
on the other hand, shows an action spectrum based on quantum yield (Section 6.6)
at different wavelengths. In other words, it compares effectiveness of red, blue and
green photons once absorbed. We might expect such an action spectrum to be a
horizontal line if photons were equally effective over the whole of the range of
Quantunm yield
0.08
0.05
440 520 600 680

Wavelength (nm)
Fig. 4.13 Action spectrum of O2 evolution by Chlorella. Maximum quantum yield

as a function of wavelength (after Emerson and Lewis). Note the dramatic fall in yield
(the “red-drop”) at wavelengths above 680 nm.
83
wavelengths absorbed by chlorophyll since blue photons as well as red give rise to
“excited state I” (Section 2.8) and even those few green photons which are absorbed
will do the same. The fact that there is a big dip (Fig. 4.13) at about 450 nm may
be due to absorption of photons by carotenoids and inefficient transfer of excitation
energy to chlorophylls. Emerson was much more intrigued by the abrupt drop in
efficiency in red light at wavelengths above 700 nm. The absorption spectrum
indicates that there is still appreciable absorption of light at these wavelengths. The
red drop suggests that these long wave photons are not used to best effect. This led
Emerson to mix red light with weak blue light. Such mixtures supported more
photosynthesis than the sum of both applied singly and the “extra” photosynthesis
resulting from adding red light between (700 and 730 nm) to blue light is now known
as “enhancement”. We can now explain this in terms of the Z-scheme - a concept
which this observation did much to create. Excitation energy from short wave (higher
energy) red photons or blue photons can be readily transferred “down-hill” to
chlorophyll molecules in both photosystems but “up-hill” transfer of excitation
energy from red photons at 700 nm above is difficult. Accordingly, light at, say, 680
nm is more effective in operating both photosystems than light at 700 nm which
favours PSI. Similarly a mixture of both short and long wave photons is better than
either alone. Hence “enhancement” and the inference, that came to be drawn, that
two photosystems must be involved. All of this, of course, bears on Emerson’s long-
standing controversy with Warburg (Section 6.7) because a quantum efficiency of
8 is implicit in the Z-scheme which requires input of 4 photons in each of its two
photosystems in order to drive linear transport of electrons from water to NADP.
4.13 Summary
In outline, and in principle, photosynthesis can still be described in terms of

a classic experiment (Fig. 4.8). Light energy (hυ), absorbed by chlorophyll initiates
electron transport (i.e. light energy is converted into electrical energy at this stage).
Electron transport, in turn, generates chemical energy as assimilatory power (ATP
and NADPH2). In linear (non-cyclic) electron transport, electrons from water are
lifted uphill, to NADP, by the combined effort of photons absorbed by each of the
two photosystems (PSII and PSI) which constitute a major part of the Z-scheme. In
cyclic electron transport there is no consumption of water or generation of NADPH2.
On the contrary, electrons simply cycle round PSI. However, both cyclic and linear
electron transport generate a proton gradient which discharges through an
ATPsynthase driving the formation of ATP from ADP and inorganic phosphate. In
effect, ATP and NADPH2 are the end products of the photochemistry. They are used
by the “dark biochemistry” to join carbon dioxide to an acceptor and reduce it to
CH2O. Triose phosphate produced in carbon assimilation (which is considered more
fully in Chapter 5) may be used to form starch in the stroma of the chloroplast or
sucrose in the cytosol of the cell. Export of triose phosphate from the chloroplast
occurs via the phosphate translocator. Inorganic phosphate released by sucrose
synthesis in the cytosol is recycled, entering the stroma in exchange for exported
triose phosphate. Once again this inorganic phosphate is combined with ADP to give
ATP in the reactions driven by electron transport. Once again ATP is consumed in
carbon assimilation so that the whole process of energy transduction (light energy
→ electrical energy → chemical energy) can continue indefinitely.
84
CHAPTER 5 - THE DARK BIOCHEMISTRY
5.1 Photosynthetic Carbon Assimilation
Photosynthesis, as we have seen, is a process of energy transduction in which

light-energy is first of all converted into electrical energy and then into chemical-
energy. In the first stage, light energisation of chlorophyll initiates some cyclic
electron transport but principally linear electron transport from water to NADP
which, accordingly, becomes reduced to NADPH2 (see Chap 4). ATP is also formed
during electron transport by addition of Pi to ADP, thereby conserving another
fraction of this electrical energy in a chemical form. Together ATP and NADPH2
constitute “assimilatory power” (Section 4.8). This assimilatory power is then used
in photosynthetic carbon assimilation (Fig. 5.1). There are three main forms of
carbon assimilation which are referred to, for reasons which will become clear, as
C3, C4 and CAM. In a sense they are not photosynthetic processes at all, because
all of the individual reactions can be made to work in the dark and indeed they are
sometimes referred to, often rather dismissively, by photochemists and biophysicists,
as “the dark biochemistry”.
86
PHOTOSYNTHETIC CARBON ASSIMILATION
[There is a sort of hierarchy amongst those who work in photosynthesis,

which is such a vast subject that it embraces all manner of scientific
disciplines and occupations. At one end there are the physicists, the
biophysicists and the photochemists. At the other end there are the farmers,
the foresters and the horticulturists. By the very nature of things, concepts in
physics tend to be more difficult to grasp than concepts in farming. Relativity,
or quantum mechanics, is less easily grasped than the need to plough, fertilise
or spray. In general we all tend to respect skills which we perceive as useful
but do not understand. Sadly, those to whom we afford our respect do not
always respond with due humility. All of us must surely have come across
the medical practitioner who addresses his patients like a school teacher
explaining things in a kindergarten. In this hierarchy, therefore, the
biophysicist is undoubtedly perceived as rather superior to the agronomist
even though agronomy (like ecology) is an immensely complicated subject.
In this context there was also the classically slanderous remark, attributed to
C. P. Darlington (a former Professor of Botany at Oxford) who, paraphrasing
Oscar Wilde, described ecologists as “the incompetent in pursuit of the
incomprehensible”.]
So the “dark biochemistry” may not be really photosynthesis (although it

must always be remembered that, even though it can be made to go in the dark, it
normally occurs in the light and involves many enzymes which are light-activated).
That is not to say that it is in any way less important than the photochemistry or that
its elucidation has been anything other than a triumph for plant biochemists. Central
to all forms of carbon assimilation is the Calvin cycle - named after Melvin Calvin
who was honoured by the Nobel Prize for its elucidation. It is also sometimes
referred to as the Benson-Calvin cycle by those who feel that the Nobel committee
might have been more generous to Andy Benson, the second most senior investigator
in the team that Calvin then led. There are also more neutral names like “the
reductive pentose phosphate pathway” which reminds us that this is a reductive
process (Section 1.2) in which carbon dioxide becomes CH2O, and that 5-carbon
sugar phosphates (pentose phosphates) are key intermediates.
87
C3 PHOTOSYNTHESIS
5.2 The Calvin Cycle
In concept, carbon assimilation, via the Calvin cycle, is simple. It involves the
addition of a molecule of carbon dioxide to an acceptor molecule. The newly formed
addition compound then undergoes a series of changes (Figs. 5.2 and 5.3) including
reduction, which are designed to form (and set aside) a product. At the same time,
the acceptor is regenerated so that the process might continue.
In actuality, the Calvin cycle, is rather more complicated than this but not as
complex as it is sometimes portrayed. The CO2 acceptor is a sugar phosphate,
containing five atoms of carbon (i.e. it is a pentose) In addition it contains two atoms
of phosphorous. It is called ribulose 1,5-bisphosphate.
[To a chemist this name indicates that the sugar is a ketose, like fructose
(containing a C=O group), rather than an aldose, like glucose (containing a
CHO group) - hence ribulose rather than ribose. The term 1,5-bisphosphate
means that there are two phosphate groups, one at either end of the molecule,
attached to carbons 1 and 5 respectively.) Reflection would also tell the
chemist that this is rather an unhappy structure, that it has been wound up by
its very nature into a rather unstable configuration and that (given an
opportunity, a catalyst, and a new partner) it would happily change into
something else.]
This then is the CO2 acceptor and, when offered carbon dioxide in the
presence of the enzyme RUBISCO, it happily embraces the carbon dioxide and
immediately splits into two new 3-carbon compounds. Thus, in arithmetical terms
we have:-
C5 + C1 → 2C3
Eqn. 5.1
(the acceptor) (the CO 2 ) (the product)
88
This is a process of “carboxylation” because the carbon dioxide joins to the acceptor (ribulose 1,5-bisphosphate or
RuBP for short) in such a way that a new carboxyl group is formed. Indeed, as a result of the addition of the carbon
dioxide and the splitting of the 6-carbon intermediate so formed into two C3 compounds, two new carboxyl groups
are produced, in the shape of two molecules of 3-phosphoglycerate.
Fig. 5.1 Light and Dark Events in Photosynthesis The first product of photosynthetic carbon assimilation is 3-
phosphoglycerate (PGA) a three-carbon acid. This is converted to a corresponding three-carbon sugar phosphate called
glyceraldehyde 3-phosphate (G3P) in a reductive process which consumes two thirds of the ATP and all of the NADPH2
generated by the photochemistry. The rest of the ATP is utilised in the regeneration of the CO2 acceptor, ribulose 1,5-
bisphosphate (RuBP) in a process in which five 3-C compounds (triose phosphates) are rearranged to give three 5-C
carbon compounds (see text). The “assimilatory power” (ATP + NADPH2) generated by photochemical events in the light
is consumed in the “dark biochemistry” - so called because none of the biochemical reactions involved have an absolute
requirement for light even though, in a photosynthetic context, they normally occur only in the light. Triose phosphates
not used in regenerating the CO2-acceptor undergo subsequent transformations to starch, sucrose etc. (Section 5.3).
These newly formed molecules of 3-phosphoglycerate (3PGA, or PGA, for short) are now reduced and it is at this
stage that all of the NADPH2 and most of the ATP which is consumed, by the Calvin cycle, is used. Once the PGA
has been reduced (to triose phosphate - i.e. to a sugar phosphate containing 3 carbons) the next trick is to generate
a 5-carbon acceptor molecule from 3-carbon precursor. Arithmetic demands that, if you wish to make 5-carbon
compounds from 3-carbon compounds without loss, you must convert five threes into three fives
5 C3 → 3 C5 Eqn. 5.2
and this is precisely what is achieved in the regenerative part of the cycle. In essence, therefore, we have
carboxylation, reduction and regeneration. The latter may seem a little involved at first because it involves two types
of reaction. The first joins (or condenses) two C3s to give one C6. This is a so-called aldol, condensation i.e.
aldehyde + alcohol. It is catalysed by an enzyme which is therefore called aldolase.
C3 + C3 → C6 Eqn. 5.3
The second type of reaction transfers a C2 fragment from the top of the C6 to a C3,
thereby forming a C5 and a C4
C6 + C3 → C4 + C5 Eqn. 5.4
and another aldol condensation, this time involving a 4-carbon sugar phosphate
C3 + C4 → C7 Eqn. 5.5
This is followed, in turn by a second reaction catalysed by transketolase in

which a C2 unit is transferred (from the top of the newly formed C7 sugar) to a C3,
to give two C5s
C3 + C7 → C5 + C5 Eqn. 5.6
As stated above, the principal function of this repeated sequence (of condensation
and transfer) is to rearrange five C3s to form three C5s.
CO2
CO2
CO2
ATP ADP
5
ATP ADP
5 5 5
ATP ADP
7
5
4 5
3 3 3 3 3
3
6 ADP 6 ATP
6 NADP 6 NADPH 2
Fig. 5.2 The Calvin Cycle in outline showing how three molecules of CO2 give rise
to one molecule of 3-carbon product and how five C3 molecules are rearranged to give
three C5 acceptors. The piece transferred is a 2-carbon ketose unit and the transfer
is catalysed by an enzyme therefore called transketolase.
In striving for simplicity, emphasis has been put on three prime features of
the Calvin cycle, i.e. carboxylation (of the acceptor), reduction (of the product) and
regeneration (of the acceptor). The complete sequence is, however, just a shade more
complex (Fig. 5.3) and includes aspects of equal importance.
As noted above, the second sequence of condensation and transfer (Fig. 5.3)
(again catalysed by aldolase and transketolase respectively) involves the addition of
a C3 or triosephosphate to the C4 molecule (erythrose 4-phosphate) created in the
first sequence. The alert reader will already have noted that whether we condense
two molecules of triosephosphate (two C3s), or one C3 and one C4, the end-product
90
THE CALVIN CYCLE
Ru5P Ru5P
R5P Xu5P
S7P
Pi
3ATP 3H 2 O
H 2O
3ADP 3Pi
CO 2
SBP
E4P Xu5P 3RuBP + 3CO 2 + 3H 2O
6PGA
6ATP 6H 2 O
F6P G6P G1P 6ADP 6Pi O2
Pi
starch 6DPGA +
H 2O 6NADPH + H 3O2
FBP 6Pi
6NADP 6H 2 O
G3P DHAP G3P DHAP G3P 6G3P
DHAP
feedback
product 3CO 2 + 2H 2 O + Pi CH 2 OH.CO.CH 2 OPO(OH) 2 + 3O 2
Fig. 5.3 Calvin Cycle in more detail. (c.f. simplified version in Fig. 5.2) In this
version, the intermediates are named. Thus the triose phosphates are dihydroxyacetone
phosphate (DHAP) and glyceraldehyde 3-phosphate (G3P). The tetrose phosphate is
erythrose 4-phosphate (E4P), the pentose monophosphates are xylulose 5-phosphate
(Xu5P), ribose 5-phoshate (R5P) and ribulose 5-phosphate (Ru5P); the hexose
monophosphates are fructose 6-phosphate (F6P) and glucose 6-phosphate (G6P) and
the heptose monophosphate is sedoheptulose 7-phosphate. Finally, the bisphosphates
are 1,3 diphosphoglycerate (DPGA) which is also more properly called glycerate 1,3-
bisphosphate (GBP), ribulose 1,5-bisphosphate (RuBP), fructose 1,6-bisphosphate
(FBP) and sedoheptulose 1,7-bisphosphate (SBP) respectively. All of the left-hand
side of the sequence is concerned with the regeneration of the CO2 acceptor as 5C3s
are converted to 3C5s. The reduction of the CO2 fixation product (PGA) occurs at
bottom right and is shown in still more detail in Fig. 5.4.
will, in each case, be a bisphosphate (in these particular circumstances, a C6 and a

C7 bisphosphate - i.e. C6 and C7 sugars, respectively, with a phosphate group at each
end). Before the C2 transfer can follow, a phosphate group has to be removed from
the end of the molecule which is to receive the C2 unit. This is accomplished, in each
case, by a hydrolysis catalysed by the appropriate bisphosphatase e.g:-
fructose 1, 6 - bisphosphate + H 2 O →
Eqn. 5.7
fructose 6 - phosphate + inorganic phosphate
91
and
sedoheptulose 1, 7 - bisphosphate + H 2 O →
Eqn. 5.8
sedoheptulose 7 - phosphate + inorganic phosphate
At first glance, these are relatively trivial reactions but they have an
importance in regulation and they also constitute two points in the cycle at which
inorganic phosphate (Pi) is released. A further six molecules of Pi are released in the
reduction of PGA to triose phosphate so that, in the Calvin cycle as formulated in
Fig. 5.3, eight molecules of Pi are released in all. Moreover, and this is of crucial
importance, only five of the six molecules of PGA created by the initial
carboxylation of three molecules of ribulose 1,5-bisphosphate
3C5 + 3 × CO 2 → 6C3 Eqn. 5.9
are consumed in the regeneration of the acceptor (Eqn. 5.2). The remaining C3
constitutes product. (Figs. 5.1 & 5.2)
As already noted, the “dark biochemistry” of CO2 fixation owes its name to
a classic demonstration by Arnon, Whatley and others that isolated chloroplasts can
be made to generate ATP and NADPH2 in the light and that these two compounds
can then be consumed, in darkness, in biochemical reactions in which CO2 is
incorporated or “fixed”. This is not to say that the reaction of carbon fixation
normally occur in the dark. On the contrary CO2 fixation by the Calvin cycle is a
process which normally occurs in the light and many of the enzymes involved are
“light-activated” i.e. they work better in the light than in the dark because of
regulatory processes. Many of these are themselves reductive in nature and involve
ferredoxin, a compound reduced by photosystem I in the light (Chap 4).
5.3 End Product and Autocatalysis
What happens to the C3 product of the Calvin Cycle ? As we have seen, two
C3s can be condensed to give a C6 (a hexose). Similarly, after some alteration, two
C6s (essentially fructose and glucose) can be condensed to give the disaccharide
sucrose. This C12 compound, which we all know simply as “sugar”, is one of the
most important compounds in plant metabolism because it is a transport metabolite,
i.e. it is in this form that most of the carbon (in most plants) is transported from the
leaves to the stems, roots, flowers, fruits, storage organs and so on. At these sites
it is this compound which is then used to provide the organic carbon component of
all other plant products - amino acids, proteins, lipids (fats), structural materials such
as cellulose and lignin (wood) etc., etc.
Some C6 units also undergo condensation reactions of various types to form

straight-chain or branched-chain polysaccharides - such as starch which is composed
of many C6 units. Starch (see starch pictures, Section 3.12) is an important,
temporary (overnight), storage product in chloroplasts and a more permanent storage
product in stems, roots, tubers, etc. In chloroplasts it is formed directly from C3s (via
C6s). In other places (roots, tubers, fruits, seeds, etc.) it is formed from C6s released
(by hydrolysis) from sucrose translocated to those sites from the leaves where it is
formed.
92
END PRODUCT AND AUTOCATALYSIS
This then, is what carbon dioxide fixation or carboxylation is all about. The
function of the Calvin cycle is to combine carbon dioxide with an acceptor molecule
to form a product and, at the same time, to regenerate the CO2-acceptor so that the
cycle might continue to turn. It will be evident, either immediately or on reflection,
that this is not enough. If the cycle only regenerated as much acceptor as it used there
would be no capacity for growth. The Calvin cycle is, and must be, “a breeder
reaction” with the capability of producing more CO2-acceptor than is present in the
first instance. This is called “autocatalysis” - a way of pulling yourself up by your
own bootstrings. It works very simply because the C3 compounds which go on to
form hexoses, sucrose or starch are precisely the same as those used to regenerate
the C5 CO2-acceptor (ribulose 1,5-bisphosphate). Of course the leaf can not get
something for nothing. If it deflects potential C3 product into C5 acceptor it will be
left with less to export from the chloroplast. Fortunately, “doubling up” is
arithmetically very sound (or equally disastrous depending on circumstance).
[There is the familiar fable of the king who sought to reward one of his
subjects by offering him half his kingdom. The man, no doubt a greedy
mathematician, asked instead that the king should give him a chess board with
one penny on the first square, two on the second and so on, thereby emptying
the Treasury. There is an equally “infallible” system” for betting on horses
- if you lose the first time simply put twice as much stake on a horse in the
next race and so on. Perhaps you will not tire of the arithmetic before I did
but even doubling up on the first 32 squares of the chessboard would increase
the original one unit stake by six orders of magnitude.]
The Calvin cycle can, if it deflects all of its products into new substrate,
double its RuBP for every 5 turns of the cycle. This is the basis of plant growth, and,
indirectly, the basis of all animal life. “All flesh is grass” and all plants depend upon
the autocatalytic aspect of the Calvin Cycle in order to grow.
5.4 The Reduction of PGA
Having looked at the cycle as a whole, we can now take a second look, in
more detail, at some of its salient features. Much attention was paid in Chapter 1 to
the nature of oxidation and reduction as the source of biological energy. The
reduction of PGA, the C3 compound formed from RuBP by carboxylation, is the
only reductive step in photosynthetic carbon assimilation. The hydrogen donor is
the NADPH2 formed as a result of linear transport of electrons from water (Chap 4)
so that, in effect, the hydrogen from water is passed, via NADP, to PGA in order
to produce a chemical compound which is basically a form of CH2O. The reduction
of PGA (Fig. 5.4) occurs in two stages. In the first stage PGA is phosphorylated at
the expense of ATP to give diphosphoglycerate or, more properly, glycerate 1,3-
bisphosphate (GBP)
PGA + ATP → GBP + ADP Eqn. 5.10
This reaction is energetically unfavourable and is pushed, as though uphill, by the

free energy of hydrolysis of the ATP molecule, by the 7 Kcal or so of energy which
would have been released had the ATP been hydrolysed to ADP and Pi (Chap 4).
Once the worst is over, once GBP has been formed, the second stage of the reaction
(the actual reduction) is energetically downhill as the newly formed GBP is reduced
to glyceraldehyde 3-phosphate (G3P)
GBP + NADPH 2 → G3P + NADP + Pi Eqn. 5.11
93
It should be noted, in passing, that this reaction, like those catalysed by the
bisphosphatases, is one which releases Pi. In fact, since all six molecules of PGA
(produced by the carboxylation of three molecules of RuBP in Fig. 5.1) are reduced
to G3P, six molecules of Pi are released at this stage in the cycle. Together with one
Pi from each of the two bisphosphatase reactions, this makes a grand total of 8
O O
C C
OH OPO(OH) 2
HCOH HCOH + ADP
Mg ++
CH 2 OPO(OH) 2 + ATP CH 2 OPO(OH) 2
3-phosphoglycerate 1,3- diphosphoglycerate

(PGA) (DPGA)
O O
C C
OPO(OH) 2 H
HCOH + NADP H 2 HCOH + H OPO(OH) 2
+ NADP
CH 2 OPO(OH) 2 CH 2 OPO(OH) 2
1,3-diphosphoglycerate glyceraldehyde 3-phosphate

(DPGA) (G3P)
Fig. 5.4 Reduction of PGA to triose phosphate (Equations 5.10 and 5.11 in more
detail). This reduction is also shown at the bottom right of Fig. 5.3.
molecules of Pi. On this basis we can start to see what goes in and out of the cycle,
in terms of energy and molecules and what additional implications should be
considered.
If we represent the Calvin cycle as we have in Figs. 5.2 and 5.3 we see that
3 molecules of RuBP are joined to 3 molecules of carbon dioxide to form 6
molecules of PGA, all of which are reduced to G3P. Of these, 5 are used to
regenerate the CO2-acceptor, RuBP (Eqn. 5.2) and, in this process, 3 molecules of
ATP are consumed in the final stages in which 3 molecules of ribulose 5-phosphate
(Ru5P) are converted to RuBP
3Ru5P + 3ATP → 3RuBP + 3ADP Eqn. 5.12
This again is an example of how energy is utilised or transferred. The conversion

of Ru5P to RuBP is a “winding-up” process. The free energy of hydrolysis of ATP
(Section 4.6) is, in a sense, consumed in a process in which the relatively stable Ru5P
molecule is twisted into the relatively unstable RuBP configuration. This makes
RuBP ripe for carboxylation and a return to stability (by way of stable end-products).
Of the nine ATP molecules used in the Calvin cycle (as represented in Figs. 5.2 and
5.3), three are used for this purpose and six in the phosphorylation of PGA to GBP,
94
THE REDUCTION OF PGA
prior to its reduction to G3P; a reaction (Eqn. 5.11) in which all six molecules of
NADPH2 are consumed.
5.5 Energy Inputs
The ways in which ATP and NADPH2 (Arnon’s “assimilatory power. -

Section 4.8) are consumed in the Calvin cycle are outlined above. We can also take
the opportunity to do a little arithmetic along these lines. Fig. 5.3 portrays the Calvin
cycle in a way which makes it easier to follow the “sugar phosphate shuffle” in which
five molecules of C3 product are converted into three molecules of the C5 sugar
phosphate which is the CO2-acceptor. Represented in this way, Fig. 5.3 calls for the
consumption of three molecules of carbon dioxide (fixed and converted into CH2O).
We can put values on the energy inputs involved but it should be noted that the
values used here are approximate rather than precise because we are seeking to arrive
at “ball-park” figures, and that precision, in these regards, depends on detail which
is not readily available to us.
[We can burn sucrose in a calorimeter and arrive at a precise value of the heat
released but fuel consumption by a vehicle is vastly influenced by the way
it is driven and by external conditions such as head winds. Similarly free
energy changes in metabolism depend on things like the prevailing Mg++
concentration etc.]
With these provisos in mind, we can put a figure of 7 Kcal or 29 Kjoules on

ATP and 52 Kcal (or 218 Kjoules) on NADPH2 (Fig. 4.2). This gives us a total of
125 (3 × 7 + 2 × 52) Kcal or 523 Kjoules for 3ATP + 2NADPH2. In terms of our
energy approximation, this offers reasonable agreement in the sense that we can
ascribe a value of 672/6 = 112 Kcal or 470 Kjoules to CH2O on the basis of calorific
burning of glucose, C6H12O6 (which gives us 672 Kcal or 2822 Kjoules). In other
words, the Calvin cycle is consuming about 125 Kcal or 525 Kjoules in order to
produce one molecule of product (G3P) with a structure not too different from CH2O.
Any attempt to look into this more closely would take us down the path illuminated
by C.P. Snow (Section 1.8) into the esoteric world of entropy which is largely beyond
the scope of this book. We can, however, find comfort in the fact that the Calvin
cycle is not only energetically feasible but also extremely efficient in terms of energy
locked into product per unit of energy used in synthesis.
5.6 Stoichiometries
This is a difficult word to spell and indeed, one which is impossible to spell
to the universal satisfaction of scientific journals in both the U.K. and the United
States. Its meaning is less difficult. The stoichiometry of a reaction is simply the
numerical relationship between the number of molecules involved. For example, in
the reaction:-
A + B ⇔ C + D Eqn. 5.13
there is a one-to-one stoichiometry, i.e. one molecule of A reacts with one molecule
of B to give one of C and one of D. Conversely, two molecules of NADP are
2NADP + 2H 2 O → 2NADPH 2 + O 2 Eqn. 5.14
95
involved when NADP serves as an oxidant in the Hill reaction in order to bring about
the release of one molecule of O2 from two molecules of water.
In Figs. 5.2 and 5.3 the overall stoichiometry is as follows. First of all, in order
to generate the necessary assimilatory power (6 molecules of NADPH2 + 9 molecules
of ATP) we have
6NADP + 6H 2 O + 9ADP + 9Pi →

Eqn. 5.15
6NADPH 2 + 9ATP + 9H 2 O + 3O 2
This equation immediately poses problems which require explanation. It follows

from Eqn. 5.15 that six molecules of water need to undergo photolysis in order to
provide the hydrogens for the reduction of the NADP. This will release three
molecules of oxygen. The source of the nine molecules of water on the right of the
equation is less obvious until it is remembered that the condensation of ADP and Pi
releases one molecule of water per ADP esterified (Eqn. 5.16). The assumption,
implicit in Eqn. 5.15 that linear electron transport (of 6H2) from water to NADP can
produce nine molecules of ATP is only an assumption. Measurements put this
particular stoichiometry at between one and two ATP per 2e- (or, in present terms,
2H) transported but, in fact, the stoichiometry or the coupling might be “flexible”
within these limits. Stoichiometry in a strictly chemical reaction is invariable. A
molecule of water is comprised of 2 hydrogen atoms and one oxygen atom (i.e.
1/2 of an oxygen molecule, O2). There is no way that more or less could be
accommodated. Conversely, if we can picture ATP formation from ADP and Pi as
driven by a proton gradient, discharging through an ATPsynthase, the situation is
somewhat different. The stoichiometry of the reaction:
ADP + Pi → ATP + H 2 O Eqn. 5.16
remains invariable but how much ATP is formed by the discharge of a given number
of protons through the ATPsynthase might conceivably be as flexible, within limits,
as the amount of electricity generated by the discharge of water through a turbine.
We are no longer talking solely in terms of chemical stoichiometry but more in terms
of mechanical efficiency. Burning a litre of a given sample of petrol (gasoline) in
a calorimeter will produce a precise number of kilocalories. Burning the same fuel
in an internal combustion engine will produce a smaller amount of mechanical work
depending upon the efficiency of the engine and the nature of the coupling (the
transmission) between the engine and what is being driven by the engine. If we think
in terms of motor vehicles, the number of miles travelled per unit of fuel consumed
will also depend to some extent upon the driver, i.e. on the way in which the
operation of the machine is regulated. In biological situations, the efficiency of
energy transduction, will also vary, within thermodynamic limits, according to
regulatory mechanisms within the cell.
If we can accept that Eqn. 5.15 is both accurate in regard to its chemical
stoichiometry and reasonable in regard to how much ATP can be generated by the
linear transport of two electrons from water to NADP, we can proceed. As we see
in Eqn. 5.17,
3CO 2 + 6NADPH 2 + 9ATP →

Eqn. 5.17
1G3P + 6NADP + 9ADP + 8Pi
the conversion of three molecules of carbon dioxide into one molecule of G3P
96
STOICHIOMETRIES
requires the utilisation of nine molecules of ATP and six of NADPH2. If we now
add Eqn. 5.15 and Eqn. 5.17 together, and cancel terms which appear on either side
of the new combined equation, we ought to arrive at the overall equation for
photosynthesis (Eqn. 5.22). In that equation, however, we have used CH2O to
described the product and the real product of the Calvin cycle is a triose phosphate
rather than a triose (C3H6O3). To make things balance, for the purpose of this
exercise, we therefore need to introduce a hypothetical hydrolysis of our triose
phosphate to yield free triose:-
G3P + H 2 O → C 3 H 6 O 3 + Pi Eqn. 5.18
Adding all three equations together (and cancelling) we would now arrive at
something quite unsatisfactory, i.e.
3CO 2 → C 3 H 6 O 3 + 3O 2 + 2H 2 O Eqn. 5.19 CH 2 OPO(OH) 2

+
CO 2 C O
In this nonsense equation, we have three molecules of water too few on the left and
two too many on the right. The two on the right are easily disposed of because we
have neglected to add the two molecules of water to the left-hand side which were HCOH
needed to hydrolyse the two bisphosphates (Eqns. 5.7 & 5.8) during the regeneration
of the CO2-acceptor. What is worse, we have also forgotten that the actual HCOH + H 2O +
carboxylation also consumes water and should be written
CH 2 OPO(OH) 2
3RuBP + 3CO 2 + 3H 2 O → 6PGA Eqn. 5.20
RuBP
With a sigh of relief we can therefore add five molecules of water to the left hand
side of the combined equations so that, on cancelling, we now arrive at the more or
less respectable CH 2 OPO(OH) 2
3CO 2 + 3H 2 O → C 3 H 6 O 3 + 3O 2 Eqn. 5.21 HCOH
which, on dividing by three gives C OOH

+
CO 2 + H 2 O → CH2 O + O 2 Eqn. 5.22 COOH
although we should bear in mind that, while this is stoichiometrically correct, it HCOH
carries unfortunate implications (see 4.1) which can be avoided by adding a molecule
of water to both sides to give CH 2 OPO(OH) 2
2 x PGA
CO 2 + 2H 2 O → CH2 O + O 2 + H 2 O Eqn. 5.23
No doubt there will be those amongst my readers who find this playing about with
equations somewhat trying and perhaps out of place in a simple description of carbon
assimilation. If, however, we are to accept that photosynthetic carbon assimilation
is indeed brought about by the thirteen reactions of the Calvin cycle (not all of which
have been mentioned here), it is important that these partial reactions actually do
add up to the overall equation for photosynthesis. They do, i.e., if we were to repeat
this exercise in full detail (by adding up all the equations in Fig. 5.3) we would arrive
at precisely the same end point. We can, therefore, conclude that the Calvin cycle
is an adequate representation of this aspect of carbon assimilation and that the
arithmetic concerning its energy requirements (2 NADPH2 + 3 ATP per CO2 fixed,
as in Eqn. 5.17) is soundly based.
97
PHOTORESPIRATION
5.7 Oxygenation
The reason for the italics in the last sentence, on page 97, is that this is not,
by any means, the whole story. If, instead of having the situation in which
C5 + CO 2 → 2 × C3 Eqn. 5.24
we have
C5 + O 2 → C3 + C2 Eqn. 5.25
both the overall stoichiometry and the energy requirements become quite different.
When this happens a molecule of RuBP is consumed (by oxygenation) thereby
denying the possibility of carboxylation of this particular molecule and giving rise
to a C2 compound (phosphoglycolate) which is obviously not part of the Calvin cycle
as we have represented it in Figs. 5.2 and 5.3. For this reason we sometimes prefer
more complex figures (Fig. 5.5) which seek to illustrate both processes occurring
side by side.
5.8 Virtue or Necessity?
Oxygenation is the first step in a very complex series of reactions which are
collectively referred to as “photorespiration” but, before we plunge headlong into this
morass, into this slough of despond, perhaps we can pause and ask what, in broad
terms, is happening. What now seems to be the most credible story is this. Before
the Proterozoic Era, the global atmosphere contained ample carbon dioxide but little
Fig. 5.5 Photorespiration. In C3 species in normal atmosphere the Calvin Cycle is

depleted when oxygenation of RuBP gives rise to phosphoglycolate. Some of the
carbon which leaves the Calvin Cycle as phosphoglycolate is “scavenged” and
returned as PGA but this involves loss of carbon dioxide and of ammonia.
or no oxygen (Fig. 8.3). The evolution of green cyanobacteria and other plants
containing the Calvin Cycle, with RUBISCO at its heart, changed all this.
98
VIRTUE OR NECESSITY?
Carboxylation proceeded apace, about one fifth of atmospheric nitrogen was

gradually displaced by oxygen and vast quantities of CH2O were locked away as coal
and oil. Oxygenation of RuBP (Eqn. 5.25) during periods of high atmospheric CO2
would have been relatively trivial because oxygen competes only poorly with carbon
dioxide for the attention of RUBISCO and indeed is largely suppressed in high
concentrations of carbon dioxide or if the oxygen concentration around a leaf is
(experimentally) decreased to about 2%. That oxygenation occurs at all, seems to be
an inevitable consequence of the nature of the enzyme and the reaction. Whether or
not photorespiration serves an essential or a useful purpose is still a matter for
argument and conjecture. There is little doubt that it is not entirely deleterious and
a number of researchers have been quick to draw attention to possible or probable
advantages but, at the same time, it unquestionably diminishes the rate and extent
of carbon dioxide fixation on which the plant depends. Although the plant may have
(in an evolutionary manner) contrived to make a virtue out of a necessity, many
plants grow faster if photorespiration is suppressed by high carbon dioxide or low
oxygen. In other words, even if photorespiration serves some useful purpose in
normal circumstances it is clearly not essential in more favourable conditions.
5.9 A Necessary Evil
Of course we do not live in a perfect world. In low oxygen or high carbon

dioxide, photorespiration is diminished and growth proceeds a pace. There is no
doubt that, in the absence of other constraints, plants grow better if they are not
allowed to photorespire. Seen from this stand-point oxygenation of ribulose
“Plants cannot move into the shade....”
bisphosphate can be regarded as an inevitable consequence of the characteristics of

RUBISCO. But there may be more. In their natural environment plants are more
often under stress than not and one sort of stress can lead to another. Drought is
commonplace. Stomata close in response to water deficit. Closed stomata limit water
loss by transpiration. At the same time closed stomata limit free diffusion of carbon
dioxide. High light, combined with low carbon dioxide, is one of a number of
conditions which can lead to photoinhibition and there is much contemporary
preoccupation with mechanisms which facilitate safe dissipation of excitation
energy. Plants can not move into the shade if they are uncomfortable although some
99
do their best by adjusting the inclination of their leaves in order to intercept less light. Failing
this, and failing safe dissipation of excitation energy, the initiation of electron transport which
is unable to bring about “useful” work (carbon assimilation) can result in destructive
photoinactivation of the photochemical apparatus. Heber argues that photorespiration serves a
useful function in these circumstances by allowing a degree of linear electron transport (Section
4.4) to NADP. This in turn generates a useful proton gradient and poises cyclic electron transport.
All of these combine, in ways not properly understood, to contain photoinhibitory damage.
“As early as 1972, Osmond and Bjorkman have suggested that photorespiration is involved
in the protection of the photosynthetic apparatus against photoinactivation. Light absorbed by
the pigment system of chloroplasts can give rise to the formation of highly reactive chemical
species, if its energy is not used to reduce NADP or to form a transthylakoid proton gradient.
Particularly under high intensity illumination, production of oxygen radicals and similarly
dangerous species needs to be checked in order to enable available scavenging and detoxification
mechanisms to protect the photosynthetic apparatus. For this reason, NADP needs to be
available as a highly competitive electron acceptor under all illumination conditions to prevent
or reduce the formation of oxygen radicals and singlet oxygen. In proper balance with NADPH,
it poises the electron transport chain so as to facilitate cyclic electron flow which increases the
transthylakoid proton gradient under high intensity illumination. The proton gradient has
different functions. It permits synthesis of ATP controls photosystem II activity and initiates
reactions
capable of rapidly degrading excess light energy into heat thereby contributing to protection
of the photosynthetic apparatus. Thus photorespiration is protective by permitting the formation
of a large proton gradient and by preventing the accumulation of NADPH particularly when
stomatal closure limits the diffusion of atmospheric carbon dioxide into leaves, as it regularly
does under water stress. There is the question how the increased proton gradient made possible
by photorespiratory carbon turnover controls photosystem II activity and facilitates non-
destructive dissipation of excess excitation energy. In this area, we know little
100
about molecular mechanisms. Future research will have to concentrate on this
aspect of photoprotection. So far, however, it is clear that photorespiration must be
considered, from a human point of view, as a necessary evil. The emphasis is on
‘necessary’. In C3 plants, photorespiration decreases productivity. This, however,
appears to be a small price if weighed against the protection it provides when plants
are exposed to excess irradiation particularly during periods of water stress” -Heber
5.10 All is not Lost
Carnegie, Gulbenkian, Rockefeller and Nuffield are renowned for their

philanthropy but there are rich people who are better known for their meanness and
it can be argued that only the mean can become wealthy in the first place. Plants have
little choice. In a highly competitive world they can not afford to squander hard-won
riches. Faced with a loss of newly fixed carbon by oxygenation of ribulose
bisphosphate it seems that evolution favoured the development of a scavenging
system which claws back carbon which would otherwise be lost as carbon dioxide.
Indeed understanding of this process came, in part, from experiments with inhibitors
which blocked steps in the glycolate pathway and from mutants which lacked key
steps. These it might be supposed would have been beneficial but, instead, they were
deleterious. The reason is not hard to see (Figs. 5.7, 5.8). What causes the damage
is the oxygenation of RuBP. Thereafter a scavenging process comes into operation
which converts a significant fraction of carbon (which would otherwise be lost) into
a form in which it can re-enter the Calvin Cycle. Phosphoglycolate which is formed
Fig. 5.7 Production and Utilisation of Glycolate. Oxygenation of RuBP produces

one molecule of PGA and one molecule of phosphoglycolate (whereas carboxylation
of RuBP gives rise to two molecules of PGA). A complex scavenging mechanism (see
also Fig. 5.8) can convert half of the phosphoglycolate back to PGA but this
conversion involves loss of carbon dioxide and ammonia
by oxygenation of RuBP contains only two carbons unlike the phosphoglycerate

formed by carboxylation which contains three. Reactions which occur outside of the
101
chloroplast, in mitochondria and peroxisomes, contrive to avoid total degradation of

these 2-carbon molecules, ensuring that two molecules of phosphoglycolate (C2)
eventually give rise to one molecule of 3-phosphoglycerate (C3) which can once
again participate in the carbon flux of the Calvin Cycle i.e.
2 × C2 → 1 × C3 + CO 2
Oddly enough, the conversion of two C2 compounds to one C3 and one CO2 is even
more complex than the conversion of five C3s to three C5s in the Calvin Cycle.
However, while the complete photorespiratory cycle starts and finishes in the
chloroplast, some of its reactions occur in other organelles and some of the
intermediates may be diverted into other metabolic pathways. One very important
aspect which should not be overlooked is that amino groups are first of all introduced
(in the conversion of glyoxylate to glycine) and then removed (in the conversion of
serine to hydroxypyruvate). These transaminations (catalysed by transaminases or
aminotransferases) simply involve transfer of amino groups in and out of the
pathway, but if you look carefully at Fig. 5.7 you will see that two amino groups
come in (as two glyoxylates becomes two glycines) but only one goes out (as one
serine becomes one hydroxypyruvate). CO2
CO2
CO2
ATP ADP
5
ATP ADP
5 5 5
ATP ADP
7
5
4 5
2
6
2
3 3 3 3 3 ATP
ADP
6 ADP 6 ATP
6 NADP 6 NADPH 2
Fig. 5.8 Maximal oxygenation of RuBP in the Calvin Cycle (c.f. Fig. 5.2 which
shows no oxygenation). The above situation occurs only at the carbon dioxide
compensation point (e.g if a leaf has been placed in a closed chamber and allowed
to photosynthesise until it can diminish the surrounding carbon dioxide no further).
C4 species can take the carbon dioxide concentration down to near zero but, because
of photorespiration, C3 species can only diminish the carbon dioxide to about 50 ppm.
At this point there is no net product, two out of every three molecules of RuBP are
oxygenated (because the carbon dioxide concentration is so low that it cannot offer
more competition) and release of newly fixed carbon dioxide from glycine (Fig. 5.7)
maintains the carbon dioxide concentration at this low steady-state level.
This leaves one amino group unaccounted for and, in fact, it is released as
free ammonia as two glycines become one serine. Accordingly, one molecule of
ammonia is released for every molecule of “re-formed” PGA which re-enters the
Calvin Cycle. The potential loss of ammonia from the leaf is an aspect of
photorespiration which is of considerable significance.
102
C4 PLANTS
C4 PHOTOSYNTHESIS
Fig. 5.9 C4 Photosynthesis This stark figure is an attempt to encapsulate the

essentials of C4 photosynthesis. This is a process of carbon assimilation which
embraces the Calvin Cycle but also involves additional reaction and a requirement for
a specialised physical structure (Kranz anatomy). The three boxes represent this
structure in which, in actuality, the mesophyll and bundle-sheath compartments are
arranged in more or less concentric circles around the central vascular tissue or
“bundle” (c.f. Fig. 5.10). Carbon dioxide enters the mesophyll via stomata and, in the
cytosol of these cells, is fixed by PEP carboxylase, creating a four-carbon acid called
oxaloacetic acid (OAA) from CO2 and the three-carbon phospoenolpyruvate (PEP).
Following reduction to malate, or transamination to aspartate (neither shown in this
outline diagram), the newly formed C4 acid is physically transported into the inner
bundle-sheath compartment where it is decarboxylated, releasing CO2 and another C3
acid. Depending on the species, this C3 acid is either PEP or pyruvic acid. In either
case these are transported back to the mesophyll and, if pyruvic acid is involved, this
is converted back to PEP in a curious reaction, catalysed by pyruvic phosphate
dikinase, consuming ATP and releasing AMP and inorganic pyrophosphate (PPi).
Putting aside these details, the entire process constitutes a CO2 pump in which this
complex sequence of carboxylation, decarboxylation and transport creates a living
CO2 enriched greenhouse. Within this environment, the Calvin Cycle works to
advantage.
5.11 C4 Plants
C3 plants (such as wheat, potatoes and most other temperate crop species and
members of the native temperate flora) fix carbon dioxide in the light almost
exclusively by the unaided mechanism of the Calvin Cycle (Fig. 5.2, 5.3). They are
called “C3 plants” because the product first formed, by the carboxylation of ribulose
1,5-bisphosphate (RuBP), is 3-phosphoglycerate (PGA), a molecule containing 3
atoms of carbon. There is, however, a second major category of higher plants (C4)
in which acids, containing 4 atoms of carbon are the initial products of carbon
103
dioxide fixation (Fig. 5.9). It should not be supposed that these plants (such as sugar
cane, maize and many sub-tropical grasses) somehow contrive to manage without the
Calvin cycle. On the contrary, they are also entirely dependent on it but they have
an extra piece of metabolic and structural machinery which makes them more
effective in certain circumstances.
Just as the names of Benson and Calvin will always be associated with the
carboxylation of RuBP and the reaction which lead to the regeneration of RuBP, so
are the names Hatch, Slack and Kortschack linked to C4 photosynthesis. The first
observations were those of Kortschack, in Hawaii, although it should be noted that,
at about the same time, there was independent work (by Karpilov and his colleagues)
in the Soviet Union which was almost entirely overlooked in the West and which
did not lead, as did Kortschack’s, to final elucidation of the pathway involved.
Kortschack worked for the Hawaiian Sugar Planters Association and, in the 1950’s,
attempted to repeat, with sugar cane, the same sort of experiments that Calvin and
his colleagues had carried out with Chlorella. To be precise, he exposed leaves of
sugar cane to radioactive CO2 (14CO2) for short periods of time in the light and then,
after extraction, ran two-dimensional paper chromatographs of the products of 14CO2
fixation. To his surprise, although 3-phosphoglycerate (PGA) appeared in a relatively
short time, the very first products were four-carbon acids (malate and aspartate).
These he correctly assumed to be both derived from a common four-carbon
precursor, oxaloacetate. News of this striking difference between the behaviour of
sugar cane, Chlorella, and those higher plants which Benson, Calvin, Gaffron and
others had worked on in the United States, soon travelled to the Colonial Sugar
Refining Company in Queensland, Australia where Hal Hatch and an English
colleague, Roger Slack, were persuaded, by Kortschack’s results, to look more
deeply into the underlying biochemistry. Over the next few years Hatch, Slack and
their colleague Hilary Johnson made a number of very important contributions which
led to the concept of “C4 photosynthesis”. As in the work by Benson and Calvin on
Chlorella, initial suggestions were made which subsequently proved to be untenable
but, by 1970, when a seminal conference on this subject was held in Canberra,
everything had more or less fallen into place and the main aspects of the C4 pathway
had been defined. One important technique employed by Hatch and Slack was the
“pulse-chase” experiment. This involved a brief exposure to 14CO2 followed by a
longer period of illumination in which the 14CO2 was flushed from the reaction
chamber and replaced by 12CO2 When this was done, radioactivity (which initially
appeared in malate and aspartate) soon left these compounds only to reappear in
substances, such as sucrose, which are regarded as typical end-products of
photosynthesis. Accordingly, it seems clear that the transient appearance of
radioactivity in malate and aspartate must involve a process of carboxylation,
decarboxylation and refixation. Hatch and Slack identified several enzymes of this
novel C4 pathway and provided preliminary evidence for the distribution of these
enzymes between different compartments in the leaf. They also showed that several
other species, such as maize, behaved in a broadly similar way to sugar cane.
5.12 Greenhouses Within Plants
Before we go further into the subject of C4 photosynthesis, we might well ask

what it is all about. This touches on many aspects of carbon dioxide metabolism
which we have considered in other chapters and in other sections. There we have
seen that primaeval atmospheres contained high concentrations of carbon dioxide and
little oxygen. Photosynthesis, as it evolved, changed all of this. Carbon dioxide was
taken from the atmosphere and replaced, on a molecule to molecule basis, by oxygen.
104
GREENHOUSES WITHIN PLANTS
In consequence, contemporary global atmospheres contain about 21% oxygen and

very small quantities of carbon dioxide (although carbon dioxide taken up from the
atmosphere must have been constantly replenished by equilibration with oceanic
reserves and by volcanic activity etc). Within recent history, carbon dioxide has been
even lower in concentration than it is at present but although the concentration is
continuing to rise remorselessly, as a result of Man’s activities, it is still far too low
(in the 1990’s) to saturate photosynthesis. The relationship between carbon dioxide
concentration and rate of photosynthesis is broadly similar to the relationship
between light intensity and rate of photosynthesis (Chap 6). Although near saturation
is reached at low concentrations of carbon dioxide (below 1000 parts per million),
atmospheric carbon dioxide still lies well within the linear part of the relationship.
In other words if, in an experiment, we double the concentration of carbon dioxide
surrounding a plant we might expect something like a doubling in the rate of
photosynthesis. Indeed, if we were to carry out such an experiment with a C3 plant
this is what we would observe (Fig. 8.8). If, on the other hand, we used a C4 plant
we would find very little response to augmented carbon dioxide (i.e. to increases in
carbon dioxide above the ambient concentration of about 350 ppm - Fig. 8.8). For
many years, tomato and cucumber growers in Western Europe have used carbon
dioxide enrichment to increase the productivity of these glasshouse crops. C4 plants,
it turns out, had the idea first in the sense that they have their own internal carbon
dioxide-enriched greenhouses in which C3 photosynthesis can proceed at an
enhanced rate. As we have already noted, C4 photosynthesis is not an alternative to
C3 photosynthesis but rather an addition to it. What is added is, in effect, a carbon
105
dioxide-enriching mechanism which captures carbon dioxide at low concentrations

in an outer compartment (the mesophyll compartment) of C4 leaves and releases it,
at a higher concentration, in an inner compartment (the bundle sheath compartment)
which houses the Calvin Cycle. This, of course, smacks a little of alchemy and
tampering with the laws of thermodynamics. In actuality, C4 plants do not get
something for nothing, any more than the rest of us. Their carbon dioxide enriching
mechanism requires an energy input and, for this reason, C4 plants are less efficient
in terms of energy usage, than C3 species. Nevertheless, this additional expenditure
of energy brings obvious advantages in its wake and others which will become more
clear as we look into this process more deeply (Section 5.16). Even so, you may
already have begun to wonder why, if one carbon dioxide-fixing mechanism proves
to be inadequate, tacking on an additional carbon dioxide-fixing mechanism (as part
of a carbon dioxide enriching system) can make the whole process more effective.
The answer lies in the intrinsic characteristics of the enzymes concerned. Ribulose
bisphosphate carboxylase (Rubisco), the carbon dioxide-fixing enzyme at the heart
of the Calvin cycle, evolved during a period in geological time when oxygen was
virtually absent. The nature of the enzyme and the reaction is such, however, that
both carbon dioxide and oxygen will serve as substrates (Section 5.7). The two gases
compete for an active site on the enzyme. If carbon dioxide wins, two molecules of
PGA are formed and then consumed in the subsequent reactions of the Calvin cycle
and in the eventual production of sucrose and starch. If oxygen wins, i.e. if
oxygenation of RuBP occurs (Section 5.7), one molecule of PGA and one molecule
of phosphoglycolate are formed. Such oxygenation constitutes the first step in
photorespiration (5C). In C3 plants, in atmospheres containing normal concentrations
of carbon dioxide and oxygen, a significantly large fraction of RuBP is consumed
in oxygenation rather than in carboxylation. In the internal, carbon dioxide-enriched,
greenhouse in C4 plants this first step in photorespiration is largely suppressed. To
the extent that the reaction catalysed by Rubisco is susceptible to oxygenation it is
an inefficient carboxylating mechanism. In contrast, the carboxylating enzyme which
plays the essential role in the carbon dioxide enriching system in C4 plants (Eqn.
5.26 is not affected by oxygen and becomes saturated at very low levels of carbon
dioxide. This enzyme is called phosphoenolpyruvate (PEP) carboxylase. It is a
widely distributed enzyme which is present in C3 as well as C4 plants and one which
is responsible both for dark fixation in Crassulacean Acid Metabolism (Section 5.12)
and an important feature of “dark respiration”. First described by Axelrod and
Bandurski in the 1950’s, it carboxylates one molecule of phosphoenolpyruvate to
yield one molecule of oxaloacetate and one molecule of orthophosphate.
“extremely high affinity”
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GREENHOUSES WITHIN PLANTS
stoma
spongy
mesophyll
bundle
sheath
Fig. 5.10 Kranz Anatomy C4 photosynthesis is based on both biochemistry and

structure. The preliminary carboxylation by PEP carboxylase occurs in the mesophyll
cytosol. The Calvin cycle is restricted to the bundle-sheath chloroplasts. The term
“Kranz” comes from a wreath, worn on the head, which the concentric layers of tissue
in C4 leaves were thought to resemble. In this transverse section through a leaf the
vascular tissue at the centre is surrounded by the bundle sheath which contains large
chloroplasts. This, in turn, is embedded in a spongy mesophyll containing many small
chloroplasts.
In C4 plants, this enzyme with its extremely high affinity for carbon dioxide,is
situated in an outer (mesophyll) compartment of the leaf (Fig. 5.10). Now we can
begin to see how the whole thing functions and how the whole system depends on
enzymes with different characteristics housed in different compartments. PEP
carboxylase captures carbon dioxide from the atmosphere in the outer, or mesophyll,
compartment of the leaf. The immediate end product of this carboxylation
(oxaloacetate) gives rise to malate and aspartate. Either, or both, of these acids are
translocated into an inner compartment of the leaf where they are decarboxylated.
The inner, or bundle-sheath compartment (the carbon dioxide enriched greenhouse),
is not readily permeable to carbon dioxide. The internal carbon dioxide concentration
is therefore increased, thus facilitating RuBP carboxylation and the reactions of the
Calvin cycle (Figs. 5.2, 5.3).
CRASSULACEAN ACID METABOLISM
5.13 Came you not from Newcastle?
It will have become readily obvious that this is a book which takes a great
many liberties with style and form and opinion. It will, therefore, come as no surprise
that it can also be blatantly self-indulgent so, if you wish to avoid an exercise in
personal nostalgia (intertwined with a little of the history of Crassulacean Acid
Metabolism), now is the time to skip quickly to the next section where you will find
the substance of that aspect of photosynthesis. Otherwise, you will have to endure
the fact that I am entirely incapable of writing about this particular subject without
going back to my youth and, what is worse, sharing it with you.
107
As one of a number of research students (at Newcastle in the 1950’s) I did

my Ph.D on the enzymic basis of Crassulacean Acid Metabolism without even
knowing what CAM achieved. Such an awful lack of understanding is not entirely
without precedent amongst research students but, in my own defence, I should hasten
to add that none of us, at that time, knew what it was about. Even so, we had flocked
to study it in some numbers, because CAM was the main area of interest of our
Professor, a famous, and gently eccentric Welshman, called Meirion Thomas, who
made such an impression on his students that very few chose to do anything other
than CAM for their research. So I was not to turn to photosynthesis, or so I thought,
until I first met my Ph.D. examiner in 1956. This turned out to be Robert Hill, of
chloroplast fame, and it was he who was to steer me in that direction. But surely,
you might ask, is not Crassulacean Acid Metabolism a form of photosynthesis ? And,
of course, you would be right but we did not regard it as such at the time because,
often quite literally, we were working in the dark. We were interested to know more
about a process in which certain plants fixed carbon dioxide into organic acids in
the dark. Many, but not all of these, were members of the family Crassulaceae.
Photosynthesis was not our concern and indeed, precious little was known about it
at that time. Calvin and his colleagues were scarcely embarked on their work, Arnon
and Whatley’s classic experiments (Section 4.8) were yet to be done. The Z-scheme
(Section 4.3) and C4 photosynthesis (Section 5.10) were still undreamed of. It was
Meirion Thomas (along with students, then unknown but soon to become renowned,
like Harry Beevers, Stan Ranson, John Brown and Bill Bradbeer) who clearly
established that the accumulation of malic acid, during “dark acidification” in CAM
plants, involved carbon dioxide fixation. In other words, carbon dioxide in CAM
plants was as much a substrate by night as it was in C3 and C4 species by day.
The discovery of dark acidification by Benjamin Heyne came long before. He

tasted a CAM plant and found it more acid in the morning than in the evening. He
wrote the following in 1813 but sadly failed to say why he had ever felt inclined to
taste these unlikely leaves in the first place or to repeat this unpleasant experience
later in the day.
A.B. Lambert, Esq., Vice President of the Linnean Society.
Dear Sir,
I had an opportunity some time ago of mentioning to you a remarkable,

deoxidation of the leaves of a plant in day-light. As the circumstance is in itself
curious, and throws great light on the opinion of those celebrated philosophers who
have written on the subject, I will state it shortly in this letter, which if you please,
you may in extract, or in any other way you think proper, lay before the Society.
The leaves of the Cotyledon calycina, the plant called by Mr. Salisbury
Bryophyllum calycinum, which on the whole have an herbaceous taste, are in the
morning as acid as sorrel, if not more so. As the day advances, they lose their acidity,
and are tasteless about noon; and become almost bitterish towards evening. This is
the case in India, where this plant is pretty generally cultivated in our gardens and
it remains to be seen if the same takes place in the hot-houses in England, where
it has been lately introduced.
I have seen this plant but once in this country, and that was at Mr. Loddiges’,
at Hackney, about twelve o’clock in the day-time, when I found it quite tasteless. The
distance of that place from my habitation has hitherto prevented me from attending
“Der Kaktusliebhaber”
to it at an earlier hour in the morning, I have, however, but little doubt it will be
- with acknowledgements to Spitzweg
found as acid as I have described it to be in India.
108
CAME YOU NOT FROM NEWCASTLE?
I need scarcely observe, that the acidity which these leaves possess in the
morning cannot be ascribed to anything else than to the oxygen which the plant has
absorbed during the darkness of the night, or which has been transferred from other
constituent principles of the plant during that period. I think it has been absorbed,
as it is so loosely united at its base, that even the light of day has an immediate effect
of disengaging it again.
Both Priestly and Ingenhousz have concluded, from numerous experiments,

that all plants exhale vital air in the day-time, and fix air or carbonic acid gas during
the night; but these conclusions have been called in question by some, from the
various results of experiments since made on this subject. What I have now related
is therefore not destitute of interest, as it seems incontrovertibly to establish the
theory of these celebrated philosophers.
I was in the hopes of learning something new or pertinent on this interesting

subject in Sprengel’s work on the Structure and Nature of Plants; but, to my great
disappointment, there is nothing to be found but what has been advanced by the two
109
philosophers mentioned, and by Saussure and Sennebier in later times. Sprengel

expatiates much on the exhalation and absorption of carbonic gas, and only once
mentions oxygen, when he notices Sennebier’s observations; according to which,
more carbonic gas is exhaled by plants during the night in close vessels, than there
is oxygen disengaged in sunshine.
I beg leave to further observe, that the plant above treated of is, in my opinion,
truly a species of Cotyledon, with which it perfectly agrees, in habit and generic
characters; the only difference being in the number of the parts of fructification
which in Cotyledon calycina are one-fifth less than in the other species of the genus,
a difference, however, that according to the principles of the Linnean System, does
not form a sufficient grounds for separation.
I have the honour to be, etc.
20th April, 1813.
Benjamin Heyne
And then there was the eminent French scientist, de Saussure, who once
uttered the immortal words “l’acide carbonique, est elle essentielle pour la
vegetation? “ Here was a plant physiologist whose phenomenal contributions have
been sadly neglected. His studies of respiratory quotients (mass of carbon dioxide
evolved divided by mass of oxygen taken up) are far too many to consider here even
though they were immensely informative. (Try asking how a castor bean can respire
vigorously for many days without losing weight). In 1804 de Saussure referred
briefly to an experiment in which he
LIGHT DARK LIGHT DARK “placed raquettes of the cactus Opuntia in CO2 enriched atmospheres and
found that CO2 and oxygen were absorbed simultaneously”
The implication, with hindsight, being that respiration occurred as usual but that, not
STARCH only was the CO2 so produced not released but, together with CO2 absorbed from
the environment, was incorporated into some metabolite (the amounts too large to
be accounted for by solution in the abundant sap within the leaves). Imagine
pH
Thomas’s chagrin in 1947 when he first came across de Saussure’s observations in
an obscure journal having himself independently re-discovered CAM some 143 years
later. It was a measure of his stature that he was quick to acknowledge de Saussure’s
prior work as soon as he was aware of it. Nevertheless, it was Thomas and his
colleagues, not de Saussure who, as I have already noted, firmly established the
TOTAL ORGANIC formation of malic acid from carbon dioxide by night and “de-acidification” by day.
ACIDS
In Thomas’s own words:-
“The experimental methods were not so refined as those which could be used now;
but there was a general agreement in the pattern of the results obtained, by Beevers
in the late spring and summer of 1946 for Bryophyllum and Kalanchoë leaves and,
later, by Ranson during several CAM seasons for succulent organs of these and other
genera of the Crassulaceae and of genera, including the cactus Opuntia, belonging
MALIC
to other families”
It was also Thomas who gave me, as a late-comer to his team in the early
CITRIC
1950’s, the task of finding, if I could, the enzyme responsible for acid formation.
110
CAME YOU NOT FROM NEWCASTLE?
This, I might add, at a time when Ochoa’s malic enzyme (Eqn. 5.30) was the only
known enzyme which might conceivably fix carbon dioxide. Moreover it was in a
laboratory with no experience of enzymology, no spectrophotometer, no cold room,
no refrigerated centrifuge and a pH meter which put pH measurement into the same
class as finding water with a forked hazel twig. Here, when I needed NADP (or TPN
as it was then called) I could not buy it from SIGMA (a supplier of fine biochemicals
of great renown) but went instead to the local abattoir in search of freshly killed pig
hearts and embarked on a long and arduous process of extraction; bucket
biochemistry at its most basic. Thomas, of course, said that it was most unlikely that
I would ever find anything and even told me that he had a more mundane problem
in reserve, to give me when I admitted defeat. But luck was on my side. Some time
later Axelrod and Bandurski described an enzyme, from wheatgerm, which they
called PEP carboxylase. It seemed an ideal candidate for the task of fixing carbon
dioxide in CAM and, buoyed up by what I had learned by then at Harry Beever’s
elbow in far off Indiana, I set about fishing it out of Kalanchoë. In the end, I
succeeded but that, like “How the Elephant got his Trunk”, is quite another story.
Fig. 5.11 Crassulacean Acid Metabolism (CAM) was a term first employed by the
late Meirion Thomas, in whose Newcastle laboratory much of the early work on this
type of photosynthesis was done. CAM is typical of (but not restricted to) the family
Crassulaceae and it involves the accumulation of malic acid - hence the name. Like
C4 photosynthesis, it involves preliminary fixation of CO2 by PEP carboxylase,
subsequent decarboxylation of malic acid and refixation of CO2. Indeed C4
photosynthesis was once flippantly referred to as “CAM mit Kranz” and, however
inadequate this description, it does remind us of the fact that in C4 photosynthesis
preliminary fixation and refixation occur in separate compartments whereas, in CAM,
these processes are separated in time. CAM is basically an adaptation to water
shortage. CAM plants conserve H2O by keeping their stomata closed by day, when
high temperatures normally bring about high water loss by transpiration. Behind
closed stomata the Calvin Cycle proceeds happily in a CO2 enriched atmosphere
produced by decarboxylation of malic acid (itself resulting from carboxylation of PEP
during the preceding night when the stomata were open). Many CAM plants show
a degree of succulence, related to the storage of malic acid which is a necessary feature
of this process. Opening of stomata by night and closure by day is the converse of
the stomatal behaviour of C3 species.
5.14 Dark Acidification
It was once said, half jokingly and half seriously, that C4 photosynthesis was
“CAM mit Kranz” . Certainly it cannot be disputed that C4 and CAM have some
features in common but it should be noted that CAM plants lack the “Kranz
anatomy” (Fig. 5.10) which is as much a part of C4 photosynthesis as the metabolic
processes that go on within their mesophyll and bundle-sheath compartments. What
might be regarded as the closest and most important common feature is that both C4
and CAM plants join carbon dioxide to phosphoenolpyruvate (to form oxaloacetate)
prior to decarboxylation and refixation of CO2 in the Calvin Cycle. But, as we shall
see, there are all-important differences in the time and place in which these processes
occur. This first carboxylation, or pre-fixation step, is catalysed by PEP carboxylase
PEP + CO 2 + H 2 O → oxaloacetate + Pi Eqn. 5.26
Phosphoenolpyruvate, like RuBP, is a high-energy substrate in the sense that the

addition of carbon dioxide to it, which gives rise to the formation of oxaloacetate
and orthophosphate leads to a large decrease in free energy. In round terms, about
6 Kcal (25 Kjoules) is needed to drive the carboxylation but the decrease in free
energy associated with the overall reaction is sufficiently large to give a net change
of about -7 Kcal. Accordingly the equilibrium position of the reaction is such that
it is (like the reaction catalysed by RUBISCO - Section 5.2) virtually irreversible.
Once fixed, the carbon dioxide stays fixed.
[It should, perhaps, be noted again here (c.f. Section 1.1) that energy is always
required to break bonds and released when bonds are formed. A carboxylation
involves joining carbon dioxide to an existing molecule. This implies bond
formation but other bonds have to be broken in this process which requires
a net energy input of about 6 or 7 Kcal - roughly equivalent to the free energy
of hydrolysis of ATP to ADP. The fact that PEP like RuBP has been
previously “wound up” (energetically) into an “uncomfortable” configuration
ensures that it welcomes the opportunity to slip into something more
comfortable. This sort of metabolic device ensures that reactions of this sort
go to completion in the desired direction and that, for substrates to be
carboxylated, the low carbon dioxide concentration in the atmosphere offers
no impediment. PEP carboxylase also has a very high affinity for carbon
dioxide so both the ability of the catalyst to work well in low carbon dioxide
concentrations and the favourable equilibrium position combine to favour
effective carboxylation.]
Oxaloacetate, the end-product of the reaction (Eqn. 5.26) is unstable and

readily decarboxylates, given half a chance, to yield pyruvate and carbon dioxide
oxaloacetate → pyruvate + CO 2 Eqn. 5.27
but it doesn’t normally get the chance to hang about. As in C4 photosynthesis, it is

either reduced to malate or transaminated to aspartate. Reduction to malate
predominates in CAM plants because it is in the form of malate that the initial
product of CO2 fixation is stored (mostly in the vacuoles) throughout the night. The
reduction is catalysed by malic dehydrogenase and again the equilibrium is such that
the reaction goes largely to completion in the direction indicated (Eqn. 5.29).
oxaloacetate + NADH 2 → malate + NAD Eqn. 5.28
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DARK ACIDIFICATION
I’m just going to slip into something more comfortable
[Throughout these descriptions “oxaloacetate”, “aspartate”, “malate”, etc.,

have been preferred to “oxaloacetic acid”, etc., (implying a more or less
neutral pH). In many circumstances this is not only convenient shorthand but
a reasonable reflection of the hydrogen ion concentration (see Section 1.7) of
the cytosol in which many of these reactions occur. In CAM plants, however,
it needs to be remembered that such large quantities of malic acid (and some
other acids) accumulate in the leaves that the process of dark acidification can
be followed by taste and measurement of “titratable acidity”.]
The formation of aspartate involves an amino donor such as glutamate and

an enzyme described as a “transaminase” or an “aminotransferase”
oxaloacetate + glutamate → aspartate + α - oxoglutarate Eqn. 5.29
Although malic acid and aspartic acid are the most important contributors to
“dark acidification” and although malic acid predominates and accumulates in large
quantities in the vacuoles of CAM plants during the period of darkness, it should not
be supposed that these are the only metabolites derived from PEP. All are important
compounds in so-called “intermediary metabolism” sometimes lying at, or near,
metabolic cross-roads which lead in many other directions. Similarly, not all CAM
plants are the same and, for example, isocitric acid, almost invariably a product of
dark fixation, occurs in relatively large quantities in some species.
113
Whatever the precise mixture of acids which results from dark acidification
we can, because of easy inter-changeability, regard the accumulated acid as being
predominantly malate, (as it so often is) and ascribe to it the function of a temporary
carbon dioxide storage product. We must not forget that, as a consequence of
forming malate from PEP (Eqn. 5.26 and 5.27) the leaf has not yet made a permanent
gain or acquisition. The substrate (PEP) is derived from starch or sucrose by
glycolysis (the same sequence of reactions which most living organisms, including
other plants and Man, employ in “dark respiration” prior to the “Krebs Cycle” which
is responsible for the closing stages). In other words, PEP formation is a “catabolic”
(breaking down) rather than an “anabolic” (building up) process. In the normal
course of events, most of the PEP which is formed during dark respiration (by
organisms other than CAM plants) is consumed, via the Krebs Cycle, giving rise to
other building materials and to ATP.
[Some PEP carboxylation is a general feature of plant biochemistry. It is

needed to replenish key intermediates, such as oxaloacetate, which occupy a
central position in intermediary metabolism.]
It is clear then, that in CAM plants as well as C4 plants, the substrate (PEP)
for the initial carboxylation is formed at the expense of previously formed
photosynthetic products. In C4 metabolism the PEP is carboxylated in an outer
compartment of the leaf (the mesophyll); it is spatially separated from the
carboxylation catalysed by RUBISCO which is responsible for the net gain in carbon
just as it is in C3 and C4 species. In CAM the two carboxylations are separated in
time rather than in space as they are in C4 species. PEP is carboxylated during
darkness, malate accumulates in the vacuole. During this period the stomata
(“pores”) which allow carbon dioxide to enter the leaf are open, the converse of the
behaviour of C3 stomata which open by day and close by night. CAM plants are able
to conserve water in this way because loss of water vapour through open stomata
occurs under conditions in which evaporation, and therefore transpiration, is
minimal. If C3 stomata behaved in this way they would not only diminish
transpiration loss but also succeed in bringing photosynthesis to a halt because of
daytime closure. CAM plants, on the other hand, can happily photosynthesise in a
carbon dioxide enriched atmosphere behind closed stomata as malate is
decarboxylated (Eqn. 5.30) to pyruvate and carbon dioxide. At this stage it is the
conventional Calvin Cycle which takes over and it is this “normal” photosynthetic
process which allows CAM plants to accumulate organic carbon (including the starch
which will give rise to PEP) so that the whole cycle can be repeated during the
following night.
CAM plants are not generally noted for high rates of photosynthesis although
there are some (e.g. pineapple) which are obviously a commercial proposition.
Mostly they occupy arid parts of the environment (such as walls and outcrops of
stone in otherwise favourable environments which are untenable for most species)
or deserts. Cacti are some of the more spectacular CAM species. Many CAM plants
are “succulents” i.e. they have fleshy leaves or stems but there are those which are
not succulent and if the degree of succulence can be manipulated by growing plants
under different conditions it can also be shown that this does not necessarily affect
their CAM function. Succulence, in fact, appears to be more directly related to water
storage than to CAM metabolism as such, although it may facilitate malate
accumulation. There are also some “facultative” CAM species such as
Mesembryanthemum crystallinum which behaves like a C3 plant if well watered and
like a CAM plant if kept dry.
[The archetypal CAM plant is a member of the family Crassulaceae, hence
114
DARK ACIDIFICATION
the name but there are many CAM species (most notably members of the
Cactaceae) which belong to a range of families including those which are
predominantly comprised of C3 species.]
5.15 Light Deacidification
“In 1804 De Saussure reported that, even in the absence of an external supply
of carbon dioxide, illuminated branches of Opuntia can produce oxygen. He
suggested that the plant itself, by consuming its own substance, gives off carbon
dioxide, which is then used in carbon assimilation” ....Thomas (1949)
This really says it all and, in retrospect, it is remarkable that it took so long
to arrive at our present understanding of CAM i.e. that daytime photosynthesis,
behind closed stomata in a CO2-enriched atmosphere (which largely precludes
photorespiration) supplies the plant with its requirements for organic carbon and
leads to starch accumulation. At night, starch breakdown leads to the formation of
a CO2-acceptor (PEP) and carboxylation of this acceptor to the formation of malate,
which accumulates. By day, in turn, the malate is broken down and CO2 released for
photosynthesis.
Malate is decarboxylated by “malic enzyme”. Before PEP carboxylase was

discovered, malic enzyme was once regarded as a serious candidate for
carboxylation, although its unfavourable equilibrium position and low affinity for
CO2 did not favour this idea. Working as a decarboxylase these characteristics are
not a problem:-
Malate + NADP → pyruvate + CO 2 + NADPH 2 Eqn. 5.30
All three products of this decarboxylation are then available for re-assimilation. The
CO2 of course, is used in photosynthesis but there is still uncertainty about the
precise fate, or site of utilisation, of the other two. Some CAM plants use a separate
means of decarboxylation. Here the key enzyme is PEP carboxykinase which
catalyses the reaction:-
oxaloacetate + ATP → phosphoenolpyruvate + ADP + CO 2 Eqn. 5.31
Such a route offers the advantage that, unlike the pyruvate formed in reaction 5.30,
PEP can be readily converted back into starch by reversal of glycolysis. On the other
hand reaction 5.31 brings its own problems because the OAA formed from malate
by malic dehydrogenase is produced in a reaction with an equilibrium position which
greatly favours oxaloacetate reduction rather than malate oxidation:-
malate + NAD ←
→
oxaloacetate + NADH 2 Eqn. 5.32
and, as in the Krebs cycle, this reaction has to be pulled in the direction written above
(Eqn. 5.32) by very efficient removal of its end-products. Moreover, some fairly
sophisticated, but yet ill-defined, control mechanisms must exist to prevent futile
cycling because, if PEP produced by reaction 5.31 were accessible to PEP
carboxylase in an active state, it would be promptly reconverted to oxaloacetate
rather than re-assimilated to starch.
115
5.16 Energy Costs
C3 carbon assimilation, if we regard it as finishing with triosephosphate,

requires 2 NADPH2 and 3 ATP per molecule of CO2 fixed (the utilisation of
“assimilatory power” by the Calvin Cycle). Many calculations have been made of
the energy costs of C4, CAM and photorespiration and table 5.1 (from Anderson &
Beardall) summarises some of the relevant values which can be derived from this
sort of consideration. While it cannot be denied that this sort of arithmetic is perfectly
valid or that a process of carboxylation (C3) obviously costs less than carboxylation,
decarboxylation and recarboxylation (C4) the arithmetic is rather like the distance
between Frankfurt and Milan or the population of these two cities - much depends
on where you start and stop counting. For example there are grounds for claiming
that sucrose can, if anything, be regarded as the main end-product of photosynthesis
because this is the material which mainly carries newly fixed carbon to where it is
Table 5.1 Energy costs of C3, C4 and CAM (after Anderson & Beardall).
Energy inputs per CO2 assimilated
ATP NADPH
C3 3 2
C4 4/5* 2
CAM 5.5/6.5* 2
*depending on the variant in mechanism
consumed. If this is accepted it is perhaps as valid to include the costs of sucrose

synthesis (or even starch synthesis) to C3 plants as it is to include the costs of
reconverting pyruvate to starch in CAM plants. Similarly it may “cost” CAM plants
to store malate in their vacuoles and while it costs C4 plants to operate what amounts
to a CO2 pump it also costs C3 species to scavenge the consequences of oxygenation
(Section 5.7). Overall there may be little difference in real energy costs between C3,
C4 and CAM. Much the same might be said of the supposed advantages afforded
by these different types of assimilation. The water economy of C4 (water lost per
CO2 fixed) may be better than C3. CAM may be even better than C4 but, bearing
in mind differences in climate, season and age it would be a mistake to suppose that
these are anything other than evolutionary answers to environmental problems. As
I write, I can glance up at the Cheviot Hills, seven or so miles from the Scottish
border. No one thinks about growing maize at this latitude but there is no problem
about potatoes which can produce amazingly high yields despite a short growing
season. My garden wall provides a happy environment for wall-pepper (Sedum acre)
and for a species of Sempervivum which makes it patently obvious, in flower, why
(as well as the mundane “house leek”) it also carries the splendid name “welcome
home husband however drunk you might be. Sedum acre is most certainly CAM.
Sempervivum is probably CAM but both share their strange environment with a
‘That will be $350,000’
species of Dianthus (“pink”) which appears to pluck its water from the air as well
116
ENERGY COSTS
as the Spanish Moss (CAM) which grows happily on telephone wires in equatorial
America. Similarly Death Valley California (notoriously as hot and dry as might be
imagined) has, as we would expect, its fair share of C4 and CAM species but it also
has specialised C3s which do just as well. Adaptation to an environment is not simply
a matter of the underlying biochemistry. There are endless additional factors to be
taken into account, anatomical as well as physiological and biochemical. Many of
these (including water loss and the ability to resist desiccation) are only marginally
related to carbon assimilation. The stinging nettle (Urtica dioica), for example, may
owe part of its success to its ability to deter predation but it also has a remarkable
facility for consuming nitrogen, mobilising leaf nitrogen and storing it during
senescence, rather than losing it to the environment by decay.
“notoriously as hot and dry as might be imagined”
5.17 Should I compare thee to a summer’s day?
Enzymes are biological catalysts. Catalysts are, as we are all supposed to

know, materials which facilitate reactions without themselves being consumed by
such reactions. So enzymes make biological reactions go faster. In theory, they do
not permit reactions to take place which would not otherwise occur nor alter the
equilibrium position of a reaction (i.e. the extent to which a reaction proceeds).
Again, in theory, no reaction is irreversible and, if A and B react together to give
C and D, a point is reached at which the forward and reverse reactions are going at
the same rate. At this time the whole system is in balance; a state of equilibrium has
been attained. Enzymes are not, in the general way of things, supposed to affect this
equilibrium, only to speed its establishment. In practice, the theory is sometimes hard
to accept. This is because some reactions are so slow (at biologically permissible
temperatures) that, for all practical effects and purposes, they would not occur at all
in the absence of enzymes. Similarly biological reactions often occur in succession
and if a second reaction removes the end-product of a previous reaction as soon as
117
it is formed, even an unfavourable equilibrium can be displaced. The reduction of

PGA to triosephosphate (Fig. 5.4) is a good example. In photosynthesis this is a key
sequence in the Calvin Cycle, one which runs “up hill” by consuming all of the
NADPH2 and two thirds of the ATP required by this part of the dark biochemistry.
In respiration, on the other hand, it runs “down hill”, liberating energy which is
conserved as NADH2 and ATP. Whether the sequence goes forward or backwards
in this freely reversible situation is determined by the rate at which substrates are
supplied and at which end-products are removed. Other reactions are much less
susceptible to this push-pull situation. The reaction catalysed by RuBP carboxylase
(RUBISCO), for example, cannot be made to run backwards. As we have seen RuBP
is a molecule subjected to internal stresses. Once these are relieved, by combination
with CO2, not all the king’s horses nor all the king’s men can put RuBP back together
again i.e. the equilibrium position, (determined by the large decrease in free energy
associated with the formation of PGA) is such that for all practical purposes the
reaction goes into completion and cannot be reversed.
High affinity and low affinity
So, the extent to which a reaction will go, and the direction in which it will
go, are primarily a matter of thermodynamics. A freely reversible reaction is
associated with a relatively small, negative or positive change in free energy. One
which exhibits a large decrease in free energy will go virtually to completion when
circumstances (e.g. the presence of the appropriate enzyme) will permit it to occur.
One with a large positive free energy change will not occur at all, unless pushed from
behind and pulled from in front in such a way that the equilibrium position is
displaced by continuous replenishment of substrates and removal of end-products.
Reaction rates, on the other hand, are largely determined by enzymes. Thus if we
start with a situation in which a freely reversible reaction has scarcely begun, or a
reaction which would go largely to completion because of its very favourable
equilibrium position, the rate is determined by the amount of enzyme present and
how much it likes its substrate. Accordingly if we plot rate against substrate
concentration we get, at the outset, a linear relationship. Twice as much substrate
118
SHOULD I COMPARE THEE TO A SUMMER’S DAY?
gives twice the rate, so does twice as much enzyme. However, at a low substrate
concentration, an enzyme with a high affinity for its substrate will catalyse a reaction 1E
faster than one with a low affinity (clearly one with no affinity at all would not 2 (1E )
V max
accelerate the basic, uncatalysed, rate). Affinities can be measured and expressed in
terms of the amount of substrate which permits an enzyme to work at half its 1/V
maximum rate. Maximum rates are hard to measure because, as the substrate
concentration is increased, a law of diminishing returns causes departure from 1 (1E ) 2E
linearity (of the rate v substrate relationship) so that doubling the substrate no longer V max
doubles the rate. Indeed, plots of rate v substrate classically define a rectangular
hyperbola in which maximum rate requires infinitely high substrate. Using low 1 (2E )
V max
mathematical cunning, however, such a hyperbolic relationship can be converted into
a straight line by plotting 1/Rate against 1/substrate concentration. At infinitely high
substrate concentration (i.e. when 1/substrate concentration equals zero) the intercept -1/km 1/km 1/[S]
on the vertical axis of such a plot is the maximum rate and the (negative) intercept
on the horizontal axis is the substrate concentration (Ks) which gives half this rate.
Where does all this take us? At its simplest it gives us a characteristic by
which to judge an enzyme. One which requires a small concentration of substrate
to work at half its maximum rate is deemed to have a high affinity for its substrate.
Herein, lies a story. When RUBISCO was described and finally characterised it
apparently required 5% CO2 to work at half its top speed. In the absence of a CO2
concentrating mechanism, this was evidently a nonsense because atmospheric CO2
is about 0.035% and, if it is to diffuse into a chloroplast along a diffusion gradient,
the concentration at the enzyme surface would be even less. So there was a great
mystery, only to be resolved when fully functional chloroplasts were isolated and
the enzyme in them (unlike that somehow changed by purification) was found to
have an appropriately high affinity for CO2. PEP carboxylase, unlike RUBISCO, was
never a mystery in this regard although it had such a high affinity for bicarbonate
(which it utilises rather than dissolved CO2) that this was difficult to measure
precisely. All of this led to a degree of confusion. Thus C4 species were thought,
by some, to have an advantage because CO2 in their leaves was first fixed by an
enzyme (PEP carboxylase) with a higher affinity than RUBISCO. In fact the relative
affinities of these two enzymes are so similar as to be unimportant. The advantage
of having PEP carboxylase catalyse CO2 fixation in the cytosol of C4 plants resides
in the fact that, unlike RUBISCO, PEP carboxylase is not subjected to competition
by oxygen (Section 5.7). Then, as we have seen, decarboxylation of malate within
the inner, bundle-sheath compartment, allows RUBISCO to operate in a CO2
enriched environment which ensures that CO2 mostly wins the competition with
oxygen. Despite the marvellous intricacies of C4 photosynthesis it must be
remembered that, in the end, the Calvin cycle fulfils the same vital role that it does
in C3 and CAM. Ultimately PEP is derived from the Calvin Cycle and this cycle,
and only this cycle, has the autocatalytic ability to function as a breeder reaction
producing more potential substrate than it uses. Without this unique ability, plants, V max (2E )
and therefore most living organisms, would have no capacity for growth.
V
5.18 Summary
V max (2E ) V max (1E )
Carbon dioxide is assimilated by green plants in a process (the Calvin Cycle) 2
in which assimilatory power (ATP and NADPH2), generated by photosynthetic
electron transport, is consumed. Carbon dioxide is joined to a pre-existing acceptor V max (1E )
2
containing 5 atoms of carbon (ribulose bisphosphate) in such a way that two
molecules of product (3-phosphoglycerate), each containing 3 atoms of carbon are
formed. Other reactions in the Calvin Cycle are concerned with the reduction of 3-
phosphoglycerate (PGA) to triose phosphate and the regeneration of three molecules Km [S]
119
of the acceptor (RuBP) from five molecules of triose phosphate. For every three turns
of the Calvin Cycle one molecule of triose phosphate is produced which is not
needed for regeneration of the acceptor. This constitutes product and it may be stored
within the chloroplast as starch or transported to the cytosol in exchange for
inorganic phosphate. In the cytosol it is made into sucrose for transport to other parts
of the plant or consumed, directly or indirectly, in other metabolic processes such
as respiration.
Carbon assimilation which involves only these processes is described as C3

photosynthesis because the first product of fixation (PGA) contains three carbons.
Most temperate species are C3 plants. There are, however, two other groups of plants
(and others which can be loosely described as intermediate in behaviour) which have
additional mechanisms. The first product of carbon dioxide fixation in C4 species
is, as the name C4 implies, an acid, oxaloacetate, which contains four carbons. This
preliminary fixation process occurs in an outer (mesophyll) compartment in the
leaves of these plants and the oxaloacetate, having been converted to malate and
aspartate and transported to an inner (bundle sheath) compartment, is decarboxylated.
This serves to increase the carbon dioxide concentration within this inner
compartment so that re-fixation by the Calvin Cycle in the bundle sheath is favoured
and photorespiration is suppressed. This prevents the decrease in carbon dioxide
fixation which occurs in C3 species as a consequence of oxygenation of RuBP
(competition between oxygen and carbon dioxide) at the site of carboxylation. This
results, when oxygen wins the competition, in the production of one molecule of
phosphoglycolate and one molecule of PGA rather than two molecules of PGA. In
C3 species there are mechanisms for returning phosphoglycolate to the Calvin Cycle
(as PGA) but this involves the loss of carbon dioxide as two molecules of
phosphoglycolate are converted into one molecule of PGA. Ammonia is also lost in
photorespiration because the regeneration of phosphoglycolate involves, in effect, the
consumption of amino acids.
What amounts to a carbon dioxide-enriched greenhouse within their leaves

benefits C4 species in another important way because the preliminary carbon
dioxide-fixing enzyme (PEP carboxylase) has a very high affinity for carbon dioxide.
Accordingly, for a given stomatal aperture, C4 species can maintain a steeper
diffusion gradient for carbon dioxide, between atmosphere and site of fixation, than
C3 species. They, therefore, have a higher water use efficiency, losing less water per
carbon dioxide fixed than C3 species. CAM plants carry this strategy further by
separating the preliminary fixation of carbon dioxide (into oxaloacetate) in time
(rather than in space) from subsequent fixation into RuBP. Their stomata open by
night and oxaloacetate formed in the dark (by carboxylation of PEP) is stored, as
malate, until the next day. Following decarboxylation behind closed stomata, the
carbon dioxide is then refixed in the Calvin Cycle; high loss of water by day is
eliminated and photorespiration is diminished.
It must be remembered that all plants ultimately depend upon the Calvin
Cycle which is the only metabolic sequence which has an in-built autocatalytic
function which can convert product (triose phosphate) into new acceptor (RuBP) and
therefore permit growth. C4 photosynthesis and CAM are “additions” to the Calvin
Cycle, not substitutes for it.
120
CHAPTER 6 - OF PLANTS AND MEN
6.1 All Flesh is Grass
In the proceeding chapters we have seen that Man’s existence derives from
nuclear fusion in the sun. Electromagnetic radiation from this source, which arrives
at the Earth’s surface as visible light, is transduced, by photosynthesis, first into
electrical and then into chemical energy. Apart from some bacteria, all other living
organisms then utilise plants as their source of energy. Those Eskimos who still live
in the old ways are probably the most carnivorous human race and the Gauchos who
used to follow vast herds of cattle across the South American Pampas must have been
a close second. Even so, the ultimate dependence on plants is obvious. The cattle
literally grazed on grass and the Gauchos ate the cattle. The food chain which ends
with the Eskimos is larger and more tenuous but it still starts with plants in the shape
of marine phytoplankton.
If we wish to pursue this theme of energy, plants and Man we now need to
consider some related matters and questions. If we are so dependent on plants, and
because there are so many of us and we are increasing our numbers at such an
alarming rate (by about a third of a million a day), it would seem sensible to see how
many plants we need and how we are changing the environment in which we, and
they, must exist.
122
ALL FLESH IS GRASS
To start with we will attempt to arrive at some idea of how much food we
require and then we will try to grapple with the even more difficult problem of how
much land we must have in order to maintain existing populations. It will be
immediately evident that these are not matters which can be considered in a purely
scientific way. Many have little choice about what they eat but, in the West, there
is no longer the dependence on staple items of the sort which caused famine in
Ireland when the potato crop failed. Moreover, some farmers in the UK are currently
being paid to “set-aside” land (i.e. to take it out of crop-production) rather than add
to the “food mountains” which accumulate in consequence of the “European
Common Agricultural Policy”. Years ago, ships sailed into Odessa to load grain. In
order to avert famine in 1992, the West is air-lifting food into what was the Soviet
Union and what is still, by far, the largest land area (2/5 of the Earth’s land surface)
in the world; an area still fully capable of growing grain for export. Such famine was
once a normal feature of life on the Indian sub-continent. Now regular, famine of
an extensive and disastrous nature has been “permanently” averted by investing huge
amounts of energy in the synthesis of nitrogenous fertilizers. A desert in Central
China, which once advanced, year by year, is now retreating in an equally relentless
fashion for the simple reason that the farmers on its fringes have been permitted to
sell their crops for personal profit. (Conversely, the same search for profit was a
major factor in creating the dust bowl in Oklahoma in the 1930s). The Chinese also
soon hope to have many millions of additional refrigerators (for which they have
insufficient electricity) and which, because of CFCs, will add to world-wide damage
to the environment (Chapter 7 and 8). At the same time they ask, with some
justification, why they should forego modest luxury while the West is so clearly
reluctant to give up anything. In short, Man’s energy requirements do not stop with
food and Man’s energy “production” is as much a matter of economics and politics
as it is of science.
Where in all of this might we begin? Let us first consider a few basic facts
about our metabolic requirements.
123
6.2 Eating Potatoes
“Man cannot live by bread alone..”
Peanuts are reputedly the cheapest way of fending off starvation in the United
States and no one raised on peanut butter and jelly sandwiches - surely the most
awful mixture known to man, would find this too great a hardship. The British and
Australians, more accustomed to eating autolysed yeast in the form of marmite and
vegemite respectively, could only look on and marvel. If they choose to do so, or
are obliged to do so, most adults, can survive indefinitely on a totally vegetable diet.
In terms of efficiency, such a short food-chain is more effective than a long one.
Some of us would feel deprived if we were never to eat another steak but, if we were
solely concerned with not going hungry, we would be better advised to sow and eat
wheat than to raise cows. In a year, a bull might easily eat as much as 10 people
and would not, once finally slaughtered, provide food for 10 people for more than
a fraction of a bull’s life-span. An Eskimo, eating seals, will be dependent on
immensely more photosynthesis than someone eating rice, because, along the way,
the marine phytoplankton (on which he ultimately depends) might have had to
provide the energy and substance for any number of species, each eaten by the next
one in line. At every stage energy would be dissipated in movement etc., and lost
in the conversion of food to muscle, bone, or whatever. For these reasons it is very
difficult to say how many plants the Eskimo must have working on his behalf (Kelly
suggests a conversion efficiency of as little as 0.1%) but let us see what we can do
with land-based vegetarians.
How many plants, then, must a person eat in order to maintain himself or
herself in good health? Clearly the question can only be answered in general terms
because cabbages are less nutritious than peanuts and a large man engaged in heavy
manual work in a cold climate will use substantially more energy than a small
woman sun-bathing on a beach.
Table 6.1
“A loaf of bread, a jug of wine...”
A sedentary male could derive his daily calorific requirement of approximately

2,400 Kcal (2,400 Calories) as follows:-
As bread = 880 g 30oz 1.9 lb
or potatoes = 3400 g 119 oz 7.5 lb
or sugar = 620 g 21 oz 1.4 lb
or lettuce = 24000 g 848 oz 53.0 lb
or mutton = 1000 g 35 oz 2.2 lb
or beef = 1100 g 38 oz 2.4 lb
or olive oil = 271 g 9 oz 0.6 lb
or beer = 6.8 litres 14.4 pints
(Note that the “Calorie” of diet fame, i.e., Calorie with a capital C, is one thousand
calories or one “kilocalorie” (Kcal))
124
EATING POTATOES
So we shall attempt to arrive at reasonable approximations, expressed in terms

of “average” energy requirements of man, just as we shall subsequently arrive at
“average” efficiencies of conversion of light energy to chemical energy by crops
(Section 6.8). For simplicity of arithmetic we can argue that a sedentary male
requires 2,400 Kcals (approximately 10,000 Kjoules) a day or 100 Kcals (418
Kjoules) per hour. The choice of a sedentary male is not sexist. In general, women
use rather less energy than men; on average they are smaller, but a modest degree
of activity by a women would readily make her metabolically equivalent to a
sedentary male. A fit man, in his prime, undertaking heavy manual work might easily
require 6,000 Kcal (25,000 Kjoules) a day and, by the same token, the young and
active use more than the old and sedentary. Anyone, sitting quietly behind a desk,
will use 85% of their metabolic energy to maintain their body temperature but, on
a squash court, or at speed on a bicycle, the same individual will expend most energy
in mechanical work. At rest, or asleep, there is still a need to maintain bodily
functions such as heart beats.
Table 6.1, then, has to do with the man sitting behind the desk or “sitting on
the Clapham omnibus”. In that sense it is entirely realistic but, in other regards, it
is an academic exercise for the obvious reason that, while the Gaucho might have
been moderately happy on a couple of pounds of beef a day, few could even
contemplate eating 53 pounds of lettuce. Although a diet of gin and lettuce has been
suggested as one of the more pleasant ways of losing weight, there are obvious
practical difficulties in attempting this, just as there are in foregoing all solid food
CO 2
_ +
O2
(
CH 2 O
Fig. 6.1 Cycling of metabolites between plants and Man (after Laetsch). Carbon
dioxide released by animal (and plant) respiration is reduced to CH 2 O in
photosynthesising leaves using hydrogens (H+ + e-) from water. Oxygen released in
this process is made available for respiration. CH2O is transported from potato leaves,
as sucrose, to the underground tubers, where it is stored as starch. Digestive
breakdown of foodstuffs, such as starch (into simpler molecules) initially releases little
energy but in its final stages, recombination of hydrogen (H) and oxygen (O) releases
the energy used in movement, to maintain body heat and function and to support the
synthesis of new molecules and body tissues.
125
in favour of beer. The potato, on the other hand, is quite a different matter (Section
6.5 and 6.6) because, some years ago, a Danish keep-fit enthusiast lived for a year
on nothing but potatoes. He even drank expressed potato juice. At the end of this
period he was neither fatter nor thinner and judged to be as fit as when he started.
This is because the potato, totally unadulterated, really does constitute a complete
diet. In broad terms, the potato might be 75% water and 23% starch, but hidden in
these rough proportions there is, as in any living tissue, a significant quantity of
protein and amino acids (“all proteins are but permutations and combinations of
some twenty constituent amino acids”). Indeed, it may come as surprise to some, who
regard potatoes as nothing but a mass of starch, to learn that they were once regarded
as an important source of protein used in commerce.
“The subject is well worth attention because the raw materials would be
cheap compared with eggs, blood or fish-roes” ....R. Haldane, 1885 (in a procedure
for extracting albumin, a protein, from potatoes)
The uncooked potato, unlike oatmeal, contains, in addition to other vitamins,

enough vitamin C to prevent the scurvy which was common, long ago, in British
seafarers before the importance of fresh fruit or vegetables was recognised. (Hence
the term “Limey” which was applied to the seamen when limes were introduced into
their diet as a prophylactic against scurvy).
[There is an apocryphal story about a Scottish student who thought to emulate

his medieval forbears by surviving one university term on a sack of oatmeal.
Wishing to economise on effort as well as on diet, he made a huge pan-full
of porridge which he poured into a chest of drawers, breaking off a piece of
solidified oat-cake when ever he felt hungry. Soon he became ill and a
surprised Scottish doctor diagnosed the first case of scurvy in his country in
living memory. Somewhat chastened, the student thought to abandon his
experiment but his medical advisor said he would “do fine” so long as he also
ate an occasional orange.]
soul food
No one, for choice, is likely to opt for potatoes as sole food but it simplifies
the arithmetic enormously, whilst retaining credibility. In past “Imperial” parlance,
126
EATING POTATOES
half a stone (seven pounds or 3 Kg) of potatoes a day is all that it is needed to keep
body and soul together, indefinitely. This will allow us to turn to the question of how
large an area we need in order to grow a year’s supply of potatoes. The short answer
is something like 100 square metres but that statement patently requires qualification
and it also takes us into all sorts of other matters, including the efficiency of the
potato plant (i.e. the efficiency of photosynthesis -Section 6.7). In the end, all of this
has to do with energy transduction - light energy into plant material, plant material
into metabolic and non-metabolic energy. In order to put energy transduction on to
a quantitative basis we must needs have a little aside about units (c.f. Section 2.4)
but even at this stage we ought to take into account that what Man needs, in the way
of his metabolic energy requirements, is usually the least of his problems. There are
those of us (like the Eskimos, the Gauchos, the Pigmies of Equatorial Africa) who,
certainly once upon a time, had no need, or scarcely opportunity, to burn plant
material. If there are still such peoples (who get by on what they eat uncooked) they
must be very few and far between. As we progress (geographically) from Africa
northwards and westwards the additional energy requirement continues to increase
until, in North America, energy is used for almost every conceivable purpose and
even for some manipulations which are best overlooked in polite society. For this
reason the demand for non-metabolic energy rises from zero, in very primitive
societies, to about 10 kilowatts per capita in very sophisticated societies. Given
“Third World” aspirations, we ought perhaps to talk in terms of a requirement for
one to ten kilowatts. Man’s metabolic requirements on the other hand are two orders
of magnitude lower, at about 100 watts. This follows from the fact that:-
2400 Kcal/day ≅ 100 Kcal/hour
100 Kcal/hour ≅ 100 watts
6.3 Defying Thermodynamics
“I know a girl who’s mighty sweet,

big blue eyes and tiny feet
her name is Rosabelle McGee
and she tips the scales at 303” .....Hoagy Carmichael
127
During the last war, obesity was not a problem in Europe just as it is not a
problem today in most of the “Third World”. By the 50s, however, food that was
now more than adequate, together with increasing affluence, led to an increasing pre-
occupation with diet. At least in the UK this opened the flood-gates to a never ending
spate of pronouncements about “fattening foods”. Most of these took great liberties
with thermodynamics. Notable at this time was the remarkable notion that obesity
derived from eating “starchy” foods. Steaks were in. Potatoes were out. There was
also the idea, still favoured to this day, that there are some amongst us who eat almost
nothing and become immense and others who eat everything and stay lean.
The underlying biochemical fallacy in all of this is that there are a very small
number of metabolites, such as acetyl coenzyme A, which lie at the junction between
carbon, nitrogen and lipid metabolism. True, there are some things eaten which are
excreted but, whether we are talking about lipids (fats), proteins or carbohydrates we
are talking, by and large, about strings of carbons with various other bits and pieces
attached. Apart from oxygen, these bits and pieces rarely contribute much to the mass
or energy content of these compounds. Living organisms contain a lot of water, a
lot of carbon, quite a bit of oxygen but not much of anything else; even though the
relatively minor constituents such as nitrogen are absolutely essential. So we have
substances which are more oxidised and less oxidised (Section 1.2). Those which are
less oxidised are relatively energy rich because they release more energy when they
are “burned” in the body. Thus olive oil is highly reduced and packs a great many
calories per gram (like peanuts). A potato on the other hand contains a lot of water
and its dry matter, mostly starch, is much more oxidised than olive oil. Meat is also
largely composed of water and the oxidation status of what is left (mostly protein)
lies somewhere between starch and oil. This sort of consideration is the basis of why
some foods have a high calorific value and some a low value. It is also why we get
fat or stay thin. Our bodily functions require energy. If we supply more energy than
is needed, the thrifty body stores some substance away for a rainy day and we put
on weight. “Ah yes”, you might say, “but isn’t it easier for the body to make fat from
fat?” Broadly speaking the answer is “not really”. Food is digested in the alimentary
tract. Digestion involves breakdown (of starch, proteins and fats) to small molecules
which can be taken up in the blood stream. These small molecules (sugars, amino
acids, small-chain fatty acids etc.) are either oxidised to CO2 and H2O (with the
associated excretion via the kidneys of unusable nitrogen etc.) or resynthesised into
body tissues and storage products such as glycogen (animal starch) and fats. Some
amino acids derived from digested protein can be used more or less unchanged and
proteins are a necessary part of diet because they are the source of nitrogen (and
sulphur) used in new protein synthesis but, by and large, the body can convert
proteins into fat as readily as it can convert starch into fat or ingested fat into body
fat. This was nicely summarised by Hans Krebs who was awarded the Nobel Prize
for his work on the “tricarboxylic acid cycle” or “Krebs cycle” as it is so often called.
“The production of energy by the combustion of foodstuffs in living matter may be

said to proceed in three major phases. In phase 1 the large molecules of the food
are broken down to the small constituent units. Proteins are converted to amino
acids, carbohydrates to hexoses and fats to glycerol and fatty acids. The amounts
of energy liberated in these reactions are relatively small, of the order of 0.5 per
cent of the total free energy that can be released in the breakdown of polysaccharides
and proteins and no more than 0.1 per cent in the case of polysaccharides and
triglyceride fats. These quantities are not utilised, except for the generation of heat.
The reactions of this first phase thus do not yield utilisable energy: they merely
prepare foodstuffs for the energy-giving processes proper. They take place in the
intestinal tract and also in tissues when reserve material is mobilised for energy
128
DEFYING THERMODYNAMICS
production. In Phase II the diversity of small molecules produced in the first phase
-three or more different hexoses, glycerol, about twenty amino acids and a number
of fatty acids - are incompletely burned, the end-product being, apart from carbon
dioxide, one of three substances: acetic acid in the form of acetyl coenzyme A, a-
ketoglutarate, or oxaloacetate. The first of these three constitutes the greater
amount: two thirds of the carbon of carbohydrate and of glycerol, all carbon atoms
of the common fatty acids and approximately half the carbon skeleton of amino acids
yield acetyl coenzyme A. α-ketoglutarate acid arises from glutamic acid, histidine,
arginine, citrulline, ornithine and part of the benzene ring of tyrosine and
phenylalanine. The details of the pathways cannot be discussed here in full, but one
matter of principle should be emphasised: the number of steps which living matter
employs in order to reduce a great variety of different substances to three basis units
is astonishingly small and could certainly not be equalled with the tools at present
available to the organic chemist.
The three end-products of the second phase are metabolically closely inter-related.
They take part in the Phase III of energy production: the tricarboxylic acid cycle,
the common “terminal” pathway of oxidation of all foodstuffs.
As each step of the intermediary metabolism requires a specific enzyme it is evident

that a common pathway of oxidation results in an economy of chemical tools.
Surveying the pathway of the degradation of foodstuffs as a whole one cannot but
be impressed by the relative simplicity of the arrangement. The total number of steps
required to release the available energy from a multitude of different substrates is
unexpectedly small. But the economy of stages does not end here. Energy is not
released at every intermediary step of metabolism. Most though not all of the
available energy contained in the foodstuffs is liberated when the hydrogen atoms
removed by dehydrogenations react with molecular oxygen to form water. Such
reactions in which 40 - 60 kcal. are liberated per mole occur at Phase II and Phase
III. Roughly one-third of the total energy of combustion is set free at Stage II and
two-thirds at Phase III.” .....Hans Krebs.
Here, indeed, we have the final putting together again (unlike Humpty
Dumpty) of the H-O bonds broken by the photolytic process in the early stages of
photosynthesis (Chapter 1).
And what about these fat people who eat like birds? To put it starkly, there
were no fat prisoners in Belsen. Some people have a propensity to become more fat
than others but this, is largely because they have a tendency to eat more and exercise
less. If they are not ill, people have a body temperature of 36.9 °C. Hot bodies radiate
more heat than cold bodies but the possibility that one sedentary human can loose
much more energy, as heat, than another, is obviously limited in normal human
society. If we were to walk naked in the cold we could eat more without getting fat
but we don’t. In all of these matters, as Einstein has told us, energy and mass are
interchangeable. The only way that we can dissipate energy, other than by radiation
or by work, is by using it in bodily functions. At rest, people of equal size use very
similar amounts of energy for this purpose. When not at rest it is a matter of how
much mechanical work they are engaged in. Of course, in this sense, work has to
be carefully defined. Some can sit with very little movement. Others, lean and active,
never seem to be at rest, even when relaxing.
Obviously every movement counts but these inadvertent body movements do

not add up to a great deal. A lean and nervous individual may stay as thin as a rake
while consuming 6,000 kcal a day but not while sitting all day at an office desk and
129
every evening in front of a television. Such an individual would stay thin only by
engaging in very hard labour for long periods, or perhaps in activities which might
invite very hard labour for long periods.
“Give me men about me that are fat

sleek-headed men that sleep o’ nights
yon Cassius has a lean and hungry look
such men are dangerous” .....Shakespeare (Julius Caesar)
Having now at least a rough idea of how much energy Man needs, and how
much he would currently like to have at his disposal for non-metabolic uses, we can
go on to ask how much energy there is available (as light) and how effectively plants
can transduce light energy into the chemical forms of energy (food) which we can
utilise. But before we go any further into this we should define a few more units
(please also refer to Sections 2.4 and 2.5)
6.4 Rods, Poles and Perches
In the U.K. at least, school children are no longer expected to be familiar with
traditional units of length such as rods, poles, perches, chains etc. Even hands and
feet are becoming unfashionable despite the fact that we always carry these about
our person. However, in the United States and Britain, and some other English
speaking countries, correspondingly archaic units of area are still in every day use
(see also Chapter 2). The most persistent of these is the “acre”, an area of 4,840
square yards. Anyone who has not even given this a second thought may be startled,
on reflection, to find that 4,840 does not have a square root in whole numbers. In
( other words, we have here a measurement of area which is a rectangle rather than
a square. This is because the acre derives from the British feudal system in which
ten acre fields were divided into 10 rectangular strips each 22 yards wide and 220
yards long. These relate in turn, of course, to the mile (one eightieth and one eighth
(
of a mile respectively). More than that, the width of the single acre strip is the length
of a cricket wicket and, therefore, more or less guaranteed to persist into the
foreseeable future. The French, who are demonstrably more practical and less
romantic than the English, use the “are” rather than the “acre”. The “are” is ten times
ten metres and the term “hectare” (100 ares or ten thousand square metres) is now
widely used as a measurement of area in the metric system. One hectare is
100 m
hectare approximately two and a half (2.471) acres and one acre about two fifths (0.467) of
a hectare.
acre 220 yds
10 m In passing, since we will soon be considering mass as well as area, we ought
_ +
to take a quick look at the ton. In the British or Imperial system the ton is 2,240 lbs
+
are 10 m
) (each lb equalling 453.59 grammes). In the United States, there is also the short ton,
_
equal to 2,000 lbs. Happily the metric ton or “tonne” is not too different from either.
The tonne is 1,000 kilograms (equals 1.1023 short, American, tons and 0.9842 long,
Imperial, tons). In considering plant yields we can regard all of these as
approximately equivalent and acres and tons (or hectares and tonnes) are convenient
units when we are considering crops. Light, on the other hand, is best expressed as
µmole quanta.m-2.s-1 and this is consistent with modern instrumentation. In terms of
Man’s energy requirements, however, it is easier to think of light-energy delivered
in watts per square metre. Once we are aware of how much light energy arrives each
)
day at the surface of the Earth and we know how much of this energy can be
_ + converted, by plants into food, we can begin to calculate how many plants each of
22 yds
us needs to have photosynthesising, desperately, on our behalf.
130
RODS, POLES AND PERCHES
2.0
Irradiance (w/m 2 /nm)
1.0
400 700 1000 2000

l(nm)
Fig. 6.2 Photosynthetically active radiation (PAR). Shown (shaded) as a fraction

(400-700 nm) of total solar irradiance. (Troughs above 700 nm are caused by
absorption by CO2, H2O vapour etc.)
6.5 Sunbeams into Cucumbers
“lux et veritas”
Until quite recently, light (i.e “light intensity”) was measured in foot candles
or the metric equivalent (metre candles or “lux”). As the name implies, this is the
light given out by one standard candle and perceived at a distance of one foot. A
standard candle emits 4π lumens (1 candle power) and, if placed at the centre of a
sphere of 1 foot radius, produces a luminous flux at its surface equal to 1 lumen/
sq. ft. If the radius is increased to 1 metre the same light is spread more thinly, the
flux decreasing according to the square of the distance. Since there are 3.2808 feet
to the metre and since 3.2808 squared = 10.8 it follows that one foot candle (1 lumen/
sq. ft.) = 10.8 lux or metre candles (1 lumen/sq. metre).
The human eye is a very good device for comparing the intensity of weak
light sources, but very poor for determining absolute intensity values. This is because
the iris diaphragm closes in bright light, so protecting the retina. Accordingly we tend
to overestimate the intensity of light if we enter a well-lit room on a dark night. The
light intensity in such a room is unlikely to be more than 200 ft. candles, whereas
in full sunlight it may be as much as 10,000. For accurate measurements, the human
eye was replaced by instruments such as photographic light meters. A contemporary
131
“light meter”, however, is much more likely to be a quantum sensor. This, in

principle, is like the photosynthetic apparatus, i.e. one quantum (“parcel”) of light
energy) causes one photochemical event (c.f. sections 2.8 & 9.11). In the instrument
this generates an electric current which is made to display the number of quanta. In
full sunlight, at noon, at sea level near the equator, the reading might be as high as
4000 µmole quanta.m -2.s -1 but only half of this would be visible light or
photosynthetically active radiation (the two are more or less equivalent). The
remainder (Fig. 6.2) is ultra-violet (below about 400 nm) and infra-red (above about
700 nm). This is fine, so far as it goes, but it does not help our calculations too much
if we are thinking in terms of how much solar energy we can convert into cucumbers
or potatoes. At the equator the sun only shines half of the day and indeed, averaged
over the year, this is true of any part of the globe. Generally speaking early morning
light and evening light is less strong. So what we need is the mean annual irradiance
i.e. what reaches the surface, averaged over 24 hours a day, 365 days a year. It is
also helpful for this purpose to think in terms of watts/square metre. Full sunlight
(about 4,000 µmole quanta.m-2.s-1) is equivalent to 1 KW/square metre, but in major
crop growing areas such as the wheat fields of N. America this falls to 200 watts/
square metre (mean annual irradiance) of which only about half is photosynthetically
active. Even so, if photosynthesis were 100% efficient this would be enough to meet
the energy requirement of one man. Indeed a fully autotrophic green man would be
almost feasible, given this impossibly high efficiency of conversion of light energy
into chemical energy. This follows from the fact that the sedentary male can also be
rated at 100 W, i.e. such a man consumes, on a continuous (albeit fluctuating) basis,
as much energy as a 100 W electric light. Thus:-
2400 Kcal / day = 100 Kcal / hour

100 100
100 Kcal / hour = Kcal / min = Kcal / sec
60 3, 600
= 24 cals / sec
24 cals / sec = 24 x 4.128 = 100 joules / sec ( approx.)
100 joules / sec = 100 watts.
Unfortunately, photosynthesis is not 100% efficient and, as will be seen in

Section 6.7, the maximum efficiency of a crop is unlikely to exceed 5% and the
corresponding minimum “land equivalent” would be about 20 square metres in the
UK and about 11 in the USA (Fig. 6.3). Under some conditions, nearly 5%
conversion of light energy to chemical energy is actually achieved by close stands
of vegetation, but the reader would be rightly sceptical if he or she were asked to
accept that one man (in the UK) could produce enough food on a piece of ground
10 metres long by 2 metres wide (16.5 feet x 13 feet) to maintain him for one year.
What is possible can be derived from the experience of our Danish “keep-fit”
enthusiast who lived for a year on a diet of potatoes (Section 6.2).
A calorific requirement of 2,400 Kcal/day (100 Kcal/ hr), can be met by about
7 lb of potatoes a day or approximately one ton/year (7 lb x 365 = 2,555 lb). It is
not difficult to grow 12 tons of potatoes to the acre in the UK and the highest reported
yield (in exceptional agricultural practice) was 88 tonnes/hectare (about 36 tons/
acre). So, in the U.K., it has proved possible to grow enough potatoes on 1/36 part
of an acre (i.e. on 6 x 22 yds or approximately 112 square metres) to feed one person
for one year (Fig. 6.3). Turning to the unexceptional, it was not unusual for an Irish
farmer and his wife, to raise a family of five and maintain several milking cows and
a couple of horses, on a thirty acre farm as recently as the early 1960s.
132
SUNBEAMS INTO CUCUMBERS
practical
0
x4 +
feasible
1
x1 +
x2 possible
_ _ _
_ 10m +
Fig. 6.3 Land areas needed to feed one person. Theoretically 20 sq metres would
be sufficient to grow 1.2 tons of potatoes. Best recorded crop would have called for
an area of about 110 sq. metres and 300-400 sq. metres would be required in practice.
There are 14 million acres of arable land in England and Wales alone and
even at the very modest yield of 10 tons of potatoes/acre this would support a
population of 140 million. (The present population is nearer 60 million). This
disregards many more millions of acres which could be used for sheep-rearing etc.
The principal reason that the UK is not currently self-sufficient (despite the fact that
it already produces enough grain to meet the calorific requirement of its entire
population) is that most people prefer to get their calories second-hand. A man is
rated at about 100 watts, a cow at about 1 KW. Feeding grain to beef cattle may lead
to something more palatable than bread alone but it is hardly the best way to use
declining energy resources. Cattle, sheep and pigs require about 7 calories of plant
product for every calorie of meat and fat they produce.
Countries like the United States have much higher populations than the U.K.
but, proportionately, much more land per head of population. The United States is,
therefore, still capable of producing much more grain than it requires for domestic
use, although this is largely attributable to mechanisation and the development, in
the 1950’s of selective herbicides which did so much to free the prairie wheat fields
of weeds. The fact that the erstwhile Soviet Union failed to emulate the United States
in this regard is more a matter of inadequate harvesting, storing and distribution than
a basic inability to grow more. This, in turn, is largely attributable to political
interference.
[Following an infamous visit to the United States, Kruschov is reputed to have

insisted on major introduction of maize (corn, Zea mays) into Soviet
agriculture (climatically much better suited, on the whole, to producing
wheat) thereby causing wide-spread famine.]
No matter how we look at this subject we come back to two simple and
irrefutable facts. The first is that, if we take a small densely populated island in the
northern hemisphere, much of it bleak moorland, unsuitable for growing arable
crops, and subjected to relatively cold winters, we find that it is still capable of
133
growing enough food to support 2 or 3 times its present population. The second, and
more sobering thought, is that this is only made possible by the extensive use of fossil
fuels. If the U.K. had to depend for all of its energy on renewable biomass, the
feasible population would fall, by two orders of magnitude, from round about 150
- 200 million to 2 or 3 million (Section 8.11). This, of course, is in accord with
population levels before the industrial revolution and the wide-spread use of fossil
fuels.
6.6 Oil into Potatoes
While there is no doubt that even a tiny and highly populated country, like the U.K.,
could readily maintain itself on potatoes and sheep, it is equally true that much
Table 6.2 Potatoes made of oil
Budget for one acre of maincrop potatoes
ENERGY INPUTS
(From Fossil Fuels) Kcal/unit MCal
Fertiliser N 151 lb 7,350 1,110

P 151 lb 900 136
K 210 lb 1,000 210
1,456
Tractors 25 hrs. (45-50 hp) 42,000/hr. 1,050

Other machinery 1,290
Sprays 331
Sundries 271
Irrigation 500
TOTAL TO FARM GATE 4,898
ADD TRANSPORT TO CITY 500
GIVING TOTAL INPUT OF 5397
Assume Yield of 13.25 tons

Deduct, for seed 1.03 tons
Net Yield 12.22 tons
Assume that daily calorific requirement of 2400 Kcal (for a sedentary male) is met
by 7.5 lbs of potatoes, then 12 tons would feed 10 people for 1 year (7.5 × 356 × 10
= 27.375 lb = 12 tons)
Utilisable calorific content ∴ equals 2400 × 365 × 10 = 8760 Mcal
NET GAIN 8760 - 5379 = 3363 (38%)
This balance sheet shows that, although an acre of potatoes can feed 10 people for one
year, most of the energy (about 60%) comes from the sun via fossil fuels rather than
by direct utilisation of sunlight.
134
OIL INTO POTATOES
[One kilocalorie (Kcal) is 1,000 calories or 4,180 joules; one megacalorie

(Mcal) is 106 calories or 4,180 Kjoules. Note that the Imperial “ton” is so
similar to the metric “tonne” that either could be used here without
significantly altering the conclusions.]
intensive agricultural practice is little more, energetically speaking, than a somewhat

inefficient means of converting fossil fuels into foodstuffs. Table 6.2, which is based
on work by Leach but makes slightly different assumptions, shows a net gain of
about 40% when the use of fossil fuels is offset against light energy “conserved” as
chemical energy in the form of edible carbohydrate. In the western world, the energy
subsequently spent on packaging, marketing and cooking, converts this modest gain
into a substantial loss. It has been calculated that, on average, approximately 5
calories are expended for each calorie of food made ready for consumption. If fuels
are not used to produce fertilisers and herbicides and to drive farm machinery, the
crop is likely to be much smaller. But it would be a mistake to suppose that an
advantage would necessarily derive from a reversion to past, more primitive,
practice. It is true that a horse doesn’t run on fossil fuels but neither can it be
switched off, like a tractor, when not in use. For this reason its total energy
requirement during a year (as much as that of ten people), is likely to exceed that
of machines used to perform comparable tasks.
Considerations of this sort highlight the dilemma which man must face as his
stocks of fossil fuels decline. It is no longer enough to seek the best possible yield.
It is also necessary to attempt to achieve the maximum net energy gain. In many
circumstances this may be synonymous with ‘best financial return’ but normal
market forces may be distorted by subsidies and intervention of a political or social
nature. Such problems have created the simultaneous existence of European “food
mountains” and starving Ethiopians.
6.7 Photosynthetic Efficiency
“In a perfect nature photosynthesis is perfect too” ....Otto Warburg
At this stage we might wish to determine how efficiently plants convert light
energy into chemical energy and even ponder the possibility of improvement. If we
know how much light energy is put in and how much chemical energy we get out
we have a measure of how well a plant can convert one form of energy into another.
Of course there are plants and plants and, if we are not careful we could get into some
rather uncertain ground. It could be a bit like asking what time a man might take
to run a mile. In my youth there were two barrel chested Swedes called Arne
Anderson and Gundar Hague who, if my memory is not at fault, took the time for
the mile down to about 4 minutes 6 seconds. Four minutes seemed unattainable until
Roger Bannister achieved the impossible and, thereafter, sub four minute miles
became unremarkable, even commonplace. That is not to say there is no limit to how
fast a man might run over a given distance. Some gifted human physiologist might
come up, if pressed, with a realistic estimate. We could ourselves, remembering that
10 seconds is a very good time for 100 yds (and that there are 1,760 yds in a mile),
declare it unlikely that anyone will ever run the longer distance without flagging and
thereby suggest that anything close to 3 minutes is unlikely in the extreme. If we
apply the same sort of crude arithmetic to plants we would probably settle for
something like 10% (conversion of light energy to chemical energy) as the equivalent
of the three minute mile and something closer to 5% for a reasonably safe bet
(perhaps equivalent to a slightly lower time for the mile than our best runners can
manage now).
135
Let us have a look at this in more detail and examine some of its many
implications. It is after all an important subject - one on which lives may ultimately
depend.
In Chapter 2 we invoked a hypothetical carbohydrate with a formula CH2O.
There are a number of real carbohydrates with the formula C6H12O6 and if these are
burned in a calorimeter they release about 672 Kcal (2,822 Kjoules). Clearly we
cannot get out more heat than it cost (in terms of light energy) to join together six
molecules of carbon dioxide (to form C6H12O6) in the first place. On this basis, to
form CH2O from one CO2 must have cost at least 672/6 = 112 Kcal (470 Kjoules).
In Section 2.3, moreover, we learned that red light (at 680 nm) had an energy content
of about 42 Kcal (175 Kjoules) per quantum mole (Avogadro’s number of photons).
So, if we only had this crude energy balance sheet to contend with, we could make
one mole of CH2O at the expense of only three quantum moles (3 x 42 Kcal) of light
energy. One thing is certain; there is no way that we could get under two quanta of
red light per molecule without breaking the laws of thermodynamics and they are
notoriously difficult to break. Similarly nothing that we know, at least when we get
into the chemical end of things, seems to work without some frictional losses, so four
photons (per molecule of CH2O formed, carbon dioxide fixed, or oxygen evolved)
might seem more realistic.
Otto Warburg, a Nobel laureate and German biochemist of great distinction

(the man who discovered NADP, pioneered the use of spectrophotometry in
biochemistry and gave us “Warburg manometry”) thought that photosynthesis was
perfect and claimed that his data put the quantum requirement (the number of
photons needed per CO2 fixed, or O2 evolved) at between 3 and 4. Robert Emerson,
a young American who did his Ph.D. in Warburg’s laboratory in Berlin took a
different view and put the minimal requirement at 8. A great controversy developed.
The debate was passionate, even bitter. Chlorella was the preferred species. It was
necessary, so it seemed, to grow it in special ways. A north-facing window and
Berlin spring or well water seemed to confer some remarkable advantages.
Measurement of light was as difficult as ever and the present generation of photon
counters were yet to be invented. Warburg manometry was used to monitor gas
exchange and refined to the nth degree, with flasks rectangular in cross-section and
horizontal microscopes to detect minute changes in the level of manometer fluid. As
always, the measurement of photosynthetic oxygen evolution was bedevilled by
respiratory oxygen uptake. Whether or not respiration continues unchanged in the
light was a question as impossible to answer with certainty at that time as it is now.
Warburg travelled to the United States to repeat his experiments in Emerson’s
laboratory. It took him months to organize apparatus and algae, eleven or twelve
hours to make each determination of quantum requirement. He was unable to repeat
his Berlin results, at least not in Emerson’s presence. Warburg blamed inadequate
algae. The following letters, from Otto Warburg and Robert Emerson to F.C. Steward
(reproduced here, verbatim, by kind permission of Geoffrey Hind), gives some
inkling of the underlying currents at the time. Emerson, soon to die tragically in an
air disaster, lamented the years wasted in futile argument, ironically attributing his
differences with Warburg to a failure by the great man to recognise an inadequacy
(a lag) in manometry. It can be scarcely doubted, given Emerson’s many other
important research contributions, that his preoccupation with this controversy cost
photosynthesis dear.
Urbana/Ill. South Coler Avenue 801 January 2nd, 1949

Dear Professor Steward !
Some months ago Dr. Robert Emerson asked me if I possibly could lecture
in your institute on the yield in photosynthesis. Thus I suppose that you are interested
136
PHOTOSYNTHETIC EFFICIENCY
in this problem.
As you know I found a requirement of 4 quanta in 1923 and the same
requirement in 1945 when I repeated my experiments considering all the objections
of Dr. Emerson. The university of Illinois invited me to decide here in Urbana which
value is the right one, 4 or 12 quanta.
The first thing I did here was a to simplify the procedure. I devised a chemical
radiometer for the visible part of the spectrum so that it is now possible to measure
quanta intensities manometrically (photo-oxidation of thiourea sensitized by
chlorophyll or porphyrin, dissolved in pyridin. This quantum yield is under suitable
conditions one).
The determination of the yield in photosynthesis is now extremely simple.
First you give in two vessels the same amounts of cells, but different volumes of acid
culture medium and measure the pressure changes in both vessels, in dark and light.
Thus you get for every period the oxygen development and CO2 absorption or the
reverse.
Then you put in the same light beam in the same position the radiometer
vessel (of the same dimensions), and measure the oxygen consumption in light for
the same time.
A few days ago I got cells to measure the yield in this way and I found, in
the presence of two impartial observers, 4 quanta per molecule oxygen. Proceeding
in exact [sic] the same way the next day two assistants of Dr. Emerson found for a
different culture about 20 quanta per molecule of oxygen. So I came to the conclusion
that the Chlorella cultures of Dr. Emerson are not suitable or at least unequal and
I declared here that I could continue the experiments only if I had the control over
the cultures of the chlorella.
This is a long story. If here in the US you wish to decide the problem finally
it seems to me necessary that I show in an impartial institute how to get four quanta,
being able of course to cultivate the chlorella myself. If on the other hand I go now
back to my institute in Dahlem and repeat it there I have no opportunity to show the
yield to other people and the situation remains as it is.
Is there a possibility to do these experiments in your institute or in the institute
of the Eastman Company? I have here a lecture at January 19 and would then be
free for about two months. The trouble is that I must be paid because it is not possible
to change german money in dollars.
It would not be advisable to ask Dr. Emerson about this plan, But Dr. Tippo,
the head of the department of Botany in Urbana is acquainted with the problem and
the situation.
I have manometers and vessels and a prisma to produce red light. The
required intensities are 0,3 to 3,0 micromoles of quanta per 10 minutes, (630 to 660
nm) or better if possible monochromatic red light.
Do not answer this letter if you see no possibilities.
I am yours sincerely
Otto Warburg.
Professor F.C. Steward January 28th, 1950

Botany Department
University of Rochester
Rochester 3, New York.
Dear Mr Steward,
I appreciated receiving your account of Burk’s performance in New York. One of

our graduate students was there, too, and gave us his impressions, but the field is
so new to him that he couldn’t give us as full an account as you do. We are amused
137
that Burk had no time for discussion of results with scientific colleagues, but had
plenty of time to spill a big story for newspapers reporters.
As I may have suggested in my last letter to you, we are now pretty sure that the
major cause of error in the Burk-Warburg work is their assumption (stated in
Science Sept. 2nd and reiterated in the Meyerhof Festschrift of Biochemica et
Biophysica Acta) that there was no “Physical lag” in their manometric system. On
the basis of this unsupported assertion (which we find to be strictly contrary to fact),
they based most of their photosynthesis measurements on 10-minute exposures to
light, alternated with 10-minute intervals of either darkness or unmeasured light.
This does not lead to correct values of photosynthesis in either phosphate or
carbonate buffers. However, there are additional factors in their work which are still
obscure, and we shall not be satisfied until we can give a quantitative explanation
of all the major inconsistencies. We do make progress toward this objective, but it’s
disappointingly slow.
Yes, Burk gives one this impression that he is making an intentional effort to confuse
issues, rather than to clarify them. I’m inclined to agree that an ethical problem is
involved, as well as a question of scientific fact. I’ll appreciate advice on how to deal
with the ethical issue, but I’m inclined to let it go until we have settled the facts.
With best wishes,
Sincerely
Robert Emerson.
So why did it take so long to distinguish between 4 and 8?
[The Z-scheme (Section 4.3), of course, demands 8 photons but, at that time,
it was still to be proposed and authenticated].
The answer is really quite simple. Given the techniques available it was
extraordinarily difficult to measure either the light absorbed or the oxygen evolved.
It should also be borne in mind that the highest yields only occur in low light, i.e.,
when the changes to be measured were at their smallest. Moreover, photosynthetic
organisms respire like any others. How to make an appropriate allowance for dark
respiration, relatively large in relation to photosynthesis in these circumstances,
could pose problems. In the long-run everything gradually happened together.
Techniques improved, the Z-scheme was proposed and relentlessly authenticated,
four photons (per carbon dioxide fixed) became untenable. These days the actual
quantum requirement for leaves, following work by Demmig and Bjorkman, is put
at about 9 and many species, provided that they are in good conditions and not
stressed give values close to this figure. Why 9 and not 8? A quantum requirement
of 8 (i.e. a quantum yield of 1 ÷ 8 = 0.125 molecules of carbon dioxide or oxygen
per photon) is probably the real underlying value because that is what the Z-scheme
demands and the Z-scheme has become increasingly unassailable. The rest is down
to measurement again. These are still very difficult to get exactly right and are biased
to more (rather than to less) because it is not yet possible, in a leaf, to measure
photosynthesis per se without inputs from other associated processes (e.g. sucrose
synthesis). Also many sorts of stress will increase the apparent quantum requirement
a little. Real stress such as photoinhibition (Sections 5.9 and 6.9) can increase it a
lot. In short, hydrogen transport from water to NADP (Chapter 4) cannot be easily
measured in leaves without inadvertently measuring a few energy requiring reactions
138
which push up the apparent quantum requirement. The consistency of the

requirement for about 9 photons is also very striking. It is as if a wide range of
species have gone as far as thermodynamics will permit. If this is so, there is little
or no possibility of increasing quantum efficiency (the reciprocal of quantum
requirement). In this regard, at least, green plants may be as efficient as it is possible
to be. (Section 6.4)
Where does this leave us in the present context? If we wish to measure

photosynthesis, as a function of light intensity, in a sensible fashion we should do
it at near-optimal temperatures in saturating CO2 i.e. under conditions in which light,
and only light, is thought to be limiting. In such circumstances the relationship is that
shown in Fig. 6.4. At low photon flux densities the initial slope is linear, the graph
only departing from linearity at PFD’s above about 75 -100 µmole quanta.m-2.s-1.
Given Bjorkman and Demmig’s consistent values of near 9 for quantum yield this
means that at (for example) a photon flux density of 80 µmole quanta.m-2.s-1 most,
if not all green plants, will give rates of about 0.76 µmoles m-2.s-1 (O2 evolved or
CO2 fixed). In other words, in the absence of stress or other complicating factors,
all plants photosynthesise at the same rate in low light. (Section 6.8).
20
18
16
-1
mmole .s
14
-2
12
10
OXYGEN
8
6
4
2
86 172 258 344 430 516 602 688 774 860

PHOTON FLUX DENSITY mmole quanta m -2 -1
.s
Fig. 6.4 Rate of photosynthesis as a function of light intensity (PFD). At first the
rate increases, with increasing light (PAR), in a linear fashion. At relatively low PFDs
(about one twentieth of full sunlight - see Table 2.2) the relationship departs from
linearity because of metabolic constraints. The maximum (quantum) efficiency is
calculated from the initial slope. In this light-limited region the theoretical maximum
is 0.125 molecules of O2 evolved (or CO2 fixed) per photon (a quantum requirement
of 8). At a PFD of 400 µmole quanta.m-2.s-1 (PAR), equivalent to one fifth full
sunlight, the rate of photosynthesis is already close to its maximum. This particular
figure was derived from computerised measurements undertaken with a Hansatech
“leaf-disc electrode”
[In the rate v PFD plot the initial slope is a measure of quantum requirement.
Thus for a PFD of 80 and a rate of 0.76 the quantum yield would be 80/0.76
= 9.3]
Let us look again at the overall efficiency of energy transduction with this in
mind. For a value of 112 Kcal (for CH2O) we would have, for electron transport from
water, through the Z-scheme, to CO2:-
139
112
× 100 = 33%
8 × 42
i.e. 8 photons, each worth 42 Kcal (175 Kjoules) would be consumed and a product
worth 112 Kcal (468 Kjoules), when burnt in the calorimeter, would be produced.
Here, you might suppose we are being generous in the extreme so let us see if, and
how, we might come nearer to reality. First of all, even very modest photoinhibitory
stress (Fig. 6.5) may decrease the initial slope of the rate v PFD relationship to an
extent equivalent to a quantum requirement of 12. These values relate to red light
and saturating CO2 and if we put a value of 112 Kcals/mole on CH2O and 42 Kcals/
mole photons on red light at 680 nm, the efficiency of conversion (light-energy into
chemical energy) becomes:-
112
× 100% = 22%
12 × 42
But only half of sun-light is photosynthetically active radiation (PAR) and 50 Kcal
per quantum mole a more realistic value than 42, given the spectral composition (Fig.
6.2) of sun-light. (On sunny days we have blue skies rather than red, and blue light
carries more energy per photon than red). On this basis the above arithmetic would
become:-
112 1
× × 100% = 9%
12 × 50 2
Then we have photorespiration (Section 5.7) and dark respiration. Quantum

requirements of 9 come from measurements in saturating CO 2 , in which
photorespiration is believed to be totally suppressed. In air, C3 plants photorespire.
C4 plants do not photorespire but then they have greater quantum requirements
B
RATE
PHOTON FLUX DENSITY
Fig. 6.5 A degree of photoinhibition. Rate v PFD showing slight photoinhibition.

Measurements were made in the light-limited, (linear) range, before (A) and after (B)
5 minutes exposure to high light in CO2 -free air. This treatment decreased the initial
slope (i.e. it decreased the quantum yield and therefore increased the apparent quantum
requirement) indicating a degree of photoinhibitory damage to the photochemical
apparatus. A further 15 minutes exposure (C), to high-light in CO2 free air, decreased
the initial slope still further and also increased the rate of dark respiration (the negative
intercept on the vertical axis). This type of photoinhibition is fully reversible and may,
in itself, afford a degree of safe dissipation (Section 6.10).
140
anyway because of the energy costs of their CO2 pumps (Table 5.1). To what extent
photorespiration decreases net carbon assimilation is arguable but few would
question an additional correction factor of 0.6 to take care of photorespiratory and
respiratory losses. In addition, leaves reflect and transmit light (mostly green), which
is therefore not used in photosynthesis, and absorb light in ways which also make
no contribution to carbon assimilation. A further correction of at least 0.85 must be
invoked to cover these losses. These two additional corrections take us down to a
final round figure of 4.5%.
This estimate (4.5%) is absolute tops. The correction factors put into the
arithmetic are, to be frank, educated guesses at best. Moreover, in the field, maximal
quantum yields, are rarely approached. At high light intensities (high PFDs) the
quantum efficiency (Section 6.6) falls, particularly in C3 crops (such as wheat,
barley, rice, sugar-beet and potatoes) rather than in C4 crops (such as sugar-cane,
maize, sorghum etc). Nevertheless there are rare, highly favourable, circumstances
in which stands of natural vegetation (Section 6.8) come close to our calculated
maximum, allowing us to conclude that 4.5% is not a complete nonsense. For
example, Cooper notes that a closed canopy of Pennisetum typhoides grown in
Katherine, W. Australia, with a daily solar energy input of 5,100 Kcal/sq.metre
(PAR), showed a daily dry weight increase of 54g/sq.metre (some 4.5% efficiency).
However, it should not be forgotten that Pennisetum typhoides is a C4 species and,
as such, much less readily light-saturated than most C3 species.
6.8 Efficiency of the standing crop
Although the various losses listed above diminish the return from a theoretical
33% to a practical 4.5% the farmer would be delighted if he could approach the
maximum of 4.5% even on rare occasions. This is because the crop in the field is
much less efficient than the plant in the laboratory and the estimates based on high
quantum yields only apply to light-limiting conditions. The average C3 crop species
will photosynthesise at near maximum rates at about one fifth of full sunlight (Fig.
6.4). Thus, at PFDs above about 800 µmole quanta.m-2.s-1, most of the incident light
has to be dissipated, as heat, (Section 6.9) rather than utilised in carbon assimilation.
In most types of agricultural practice, the crop does not cover the available ground
throughout the growing season and obviously irradiation of bare earth adds little to
the balance sheet, apart from soil warming. Conversely, as the season advances
efficiency will be diminished as the upper leaves begin to form an unbroken canopy
which shades those leaves below it. In areas removed from the equator or at high
altitudes, there will be periods when the temperature is too low to support appreciable
photosynthesis, and at temperatures above 30°C, photorespiratory losses will become
increasingly important. Water shortage will limit growth as will deficiencies in
essential and trace elements. Indeed, availability of water is often the most important
limitation in agriculture. Carbon dioxide, at about 0.03%, i.e. 300 parts per million
(ppm), will frequently be a limiting factor (particularly in C3 species which may
photosynthesise two or three times more rapidly in augmented CO 2) and this
limitation may be aggravated locally, by active photosynthesis in still atmospheres.
Photorespiration will take its toll. To all of these must be added the usual agricultural
hazards such as disease, damage and loss. These will frequently combine to decrease
yields to much less than 1%.
The maximal dry weight yield can be calculated for any country at any level
of efficiency. For example, the UK receives sunlight at 100 joules/sq. metre/sec. on
a continuous basis. At 4.2 joules/cal this equals about 24 cals/sq. metre/sec.
141
24 × 3600 Kcals / sq. metre / hr

=
1000
= 86 Kcal / sq. metre / hr.
Five per cent of this value is 4.3 Kcal and, at 4.25 Kcal/g dry weight, it may be
calculated that:-
1.0 g/sq. metre/hr. = 1.0 x 365 x 24 g/sq. metre/yr.

= 8.8 kg/sq. metre/yr.
= 88 tonnes/hectare/yr.
= 36 tons/acre/yr.
This allows some very rough comparisons to be made. It is difficult to obtain

accurate figures of total yield (as opposed to crop yield) but the best ever reported
potato crop in the UK was about 36 tons (fresh weight, tuber) per acre (88 tonnes/
hectare). Very similar yields have been reported from the United States.
Dry weight measurement of a total potato crop (including leaves and roots)
has been only rarely attempted. However, values obtained by Lorenz put the total
dry weight at a little less than one quarter of the fresh weight of the tubers and this
would suggest a maximum dry weight yield of approximately 9 tons/acre (22 tonnes/
hectare). This is equivalent to 25% of the theoretical maximum, or 1.25% conversion
of light energy to chemical energy. The average potato crop is perhaps one third of
the maximum. These values would have to be recalculated for each crop to be
considered but the values cited in table 6.3 could be taken as a first approximation.
Table 6.3
Percentage Conversion of Light Energy to Chemical Energy

(i.e Dry weight yield of potatoes, given different efficiencies
of photosynthesis at the crop level)
YIELD
% conversion Total dry Fresh weight

of light to weight in of potatoes
chemical tons/acre in tons/acre
energy or (tonnes/ or (tonnes/
hectare hectare)
Possible Max. 5.0 36 (88) 144 (352)
Feasible 1.25 9 (22) 36 (88)
Average 0.4 3 (7) 12 (29)
It will be seen that in this Table there is a four fold difference between “possible” and
“feasible” whereas in Fig. 6.3 the difference is 5.5. It should be noted that this discrepancy
relates only to the nature of the crop and to the assumptions made about its calorific content
and fresh weight/dry weight ratio.
142
ROOFS AND CEILINGS
6.9 Roofs and Ceilings
As light increases in brightness, i.e. as the rate at which photons strike a leaf
increases, the rate of photosynthesis increases. Accordingly, if we plot rates of
photosynthesis against light intensity (or more properly, photon flux density or PFD)
we get straight lines at low intensities (e.g. Fig. 6.5) which reflects this direct
relationship between (quantum yield) the arrival of photons at the leaf surface and
the photosynthetic output. At higher PFDs however, this linear relationship is lost
(Fig. 6.7). This initial slope (the roof) gives way to a curve which gradually
approaches a new, biological, limitation (the ceiling). This is analogous to a man
frying eggs. At first the rate at which he can fry eggs will be limited, in part, by the
rate at which he is handed eggs to fry but, very soon, the biological limitations of
his handling capacity will dictate how many he can fry. He will soon have reached
his own biological ceiling.
As well as horizontal ceilings, most houses have pitched roofs. The ceiling
is biological and variable and has to do with the ability of the leaf to utilise incoming
photons. The maximum slope or pitch of the roof (quantum yield) is a
thermodynamic constraint, governed by the light energy required to evolve one
molecule of oxygen or reduce one molecule of carbon dioxide. Each photon entering
each photosystem (Fig. 6.6) raises one electron to a higher energy level. Since there
are two photosystems, and since four electrons must be transferred in order to satisfy
the equation:-
2H 2 O + CO 2 → CH2 O + O 2 Eqn. 6.1
this means that eight photons are required per molecule of oxygen evolved or carbon
dioxide fixed.
We can measure the efficiency of a motor vehicle in terms of fuel consumed

per mile travelled or from the initial slope of a graph in which the rate of fuel
143
consumption is plotted against the speed of the vehicle (left). The initial, linear, part
of the rate of photosynthetic oxygen evolution v PFD plot allows us to derive
photosynthetic efficiency in a similar way but, in terms of µmoles of oxygen evolved
per µmole of photons used rather than miles per gallon or kilometres per litre.
60 Surprisingly, many diverse species display very similar photon requirements if they
Rate (m.p.h.)
are allowed to photosynthesise under good conditions. The implication, yet to be

proved, is that many, or possibly all, species have acquired the ability to utilise light
as well as is thermodynamically possible. If this is correct, molecular biologists are
unlikely to be able to improve the maximal photosynthetic efficiency of plant species
30 (the roof) not least because they will have no genetic variability to draw upon. The
roof (the initial slope in Figs. 6.4 - 6.8) is already pitched as steep as the Z-scheme
permits and, if not stressed, most plants may operate close to this limit. Raising the
ceiling is quite another matter because here the constraint is biological rather than
thermodynamic and there is wide variation amongst species and varieties. Even the
1 2 3 same species grown in a different environment exhibit something like a tenfold
Fuel used (g.p.h.) difference in maximal photosynthetic rate. Even so, this ceiling may not be of over-
riding importance. If a driver is required to observe a rigorously applied speed limit
of 70 m.p.h. it will not be to his advantage to have a vehicle capable of 100 m.p.h.
unless it also possesses other attributes such as better acceleration and stability.
Moreover, a rally driver will consistently drive the same vehicle faster than a
university professor because he or she will have driving skills (i.e. skills in
regulation) which the professor is unlikely to possess. Similarly, plants are always
beset by environmental constraints and may differ widely in metabolic regulation.
For example, take two varieties of plant with identical roofs and ceilings and suppose
PS I
PS II
+
+
+
+
e- e- e- e-
CO 2
( ( ( (
+
+
+
+
+
4H
+
+
+
+
( ( ( (
_
_
photon e- CH 2 O
4 photons
+ H2O
4 photons
_
_
_
_
e- e- e- e-
2 H 2O
_
_
_
_
e- e- e- e- 8 photons
( ( ( (
+
O 2 + 4H
_
_
( 2H 2 O + CO2 + CH 2 O + O2 + H 2 O)
Fig. 6.6. The Z-Scheme. Yet another version of Hill & Bendall’s classic
representation of electron transport (c.f. Fig. 4.2). This time stripped of detail to
emphasise the manner in which 8 photons combine to transport 4 electrons from H2O
to CH2O. Protons (H+) separated from hydrogens (H = H+ + e-) at the beginning of
this process, as water is split (releasing O2) in photosystem II, are restored to CH2O
(via NADP) after electrons have passed through PSI. In leaves, a small fraction of
excitation energy is dissipated as fluorescence emission from PSII (left). As the light
intensity increases, an increasing amount of excitation energy is dissipated as heat
(Section 6.2) and the quantum yield (0.125 molecules of O2 per photon at maximum)
falls accordingly.
144
ROOFS AND CEILINGS
that one can convert 10% more of its photosynthetic product into new leaves than
the other. The new leaves would also photosynthesise and as arithmetic will show,
within 8 weeks, the plant with the leaning to investment would have grown to twice
the size of the other. In this instance the ability to convert more photosynthetic
product into new photosynthetic machinery could be much more important than
modest differences in photosynthetic rate. Thus increased productivity might be
found more readily, in improved regulation of metabolism and development, than in
faster photosynthesis. This is not to say that there is no room for improvement. Many
years ago, a famous Cambridge biologist called Blackman took the view that the roof
gave way to the ceiling abruptly rather than in a continuous curve (Fig. 6.7) as
limitation by light gave way to limitation by the ability of the leaf to utilise light
effectively. Contemporary measurement (particularly when it is based on
illumination from above) does not often show such an abrupt change, not least
because there are usually several layers of photosynthetic tissue within a leaf, each
layer with somewhat different characteristics and each lower layer inevitably
receiving less light than the leaf-surface. Nevertheless, the extent to which the rate
CEILING
RATE
OF
RO
PHOTON FLUX DENSITY
Fig. 6.7 Roofs and Ceilings. The initial slope of the rate v. PFD relationship (i.e. the
quantum yield) is a thermodynamic constraint unlikely to be steepened. The ceiling
is determined by enzymic complement and regulation and might well be raised by
genetic manipulation.
v PFD relationship (the continuous curve in Fig. 6.7) can approach the
thermodynamic and biological constraint of the perfect Blackman relationship (roof
plus ceiling) may well prove to be an important indicator in the assessment of plant
performance. Molecular biologists have acquired a magic wand in the sense that, at
least in principle, they are now able to create entirely new plants; to move parts of
metabolic machinery from one plant to another or to introduce new completely novel
features. Their problem is that they need guidance about what to do. It may prove
less advantageous to raise the maximum rate of photosynthesis than to seek to ensure
that they function as close to existing roofs and ceilings for as much of the time as
145
possible. Resistance to environmental stress and speed of recovery from stresses such
as photoinhibition could be crucial in this regard. These are features of a plant which
an experienced plant breeder now recognises intuitively when he or she talks about
“vigour”. It is these that give some species, such as barley, the versatility to grow
in widely different environments. As the breeders traditional skills are replaced by
the new wonders of genetic engineering, “vigour” and “versatility” will need to be
quantified and assessed. Such assessment will undoubtedly involve the application
of new techniques to the evaluation of the old Blackman concept of roofs and
ceilings and the extent to which crop species will be able to approach these limits.
SAFELY DISSIPATED
6.10 The need for dissipation
Plants are rarely able to move out of the sun and yet are quite unable to use
all of the light-energy that may arrive at their leaves. This is particularly true of
circumstances in which carbon assimilation is constrained by other factors, such as
low temperatures or drought which may induce stomatal closure and consequential
“Where we might soon have fainted in that Enchanted Ground

but now and then a cluster of pleasant grapes we found”
CO2 deficiency. There is, therefore, a need for safe dissipation of excess excitation
energy. To an extent, modest reversible photoinhibition i.e. damage caused by light
to the photochemical apparatus (Fig. 6.5), may constitute a safety mechanism but
clearly irreversible photoinhibition would serve no useful purpose. Recent research
indicates that there are additional safety valves that dissipate excess excitation energy
as heat (rather than fluorescence or carbon assimilation). In some circumstances
reduction of O2 (the Mehler reaction - See Fig. 4.3) may be involved.
If not stressed, most species photosynthesize in low light, at close to the same
rate but the linear relationship between PFD and rate is lost progressively more
quickly by leaves grown in shade than by leaves grown in full sunlight (Fig. 6.8).
146
SAFELY DISSIPATED
At first sight, this may seem to be more of a problem for shade leaves than for sun
leaves in the sense that they can usually (but not invariably) utilize only a much
smaller fraction of full sunlight than their sun counterparts. In Fig. 6.8 the
percentages of incident red light used by shade and sun Helionia (in the range of 0-
800 µmole quanta.m-2.s-1, and assuming a quantum efficiency of 9) were about 20%
and 40% respectively. In full sunlight (2,000 µmole quanta.m-2.s-1 in the 400-700 nm
PAR range capable of being absorbed by chlorophyll) these values for
Sun
RATE
Shade
100 1,000
PHOTON FLUX DENSITY
RATE
LCP
LCP
100
DR
PHOTON FLUX DENSITY
DR
Fig. 6.8 Rate v PFD in sun and shade leaves Above. Comparison of the rates of
photosynthesis displayed by sun and shade leaves of Helionia over a photon flux
density range of 0 to 1000 µmoles quanta/sq. metre/sec. Below. Detail of above
emphasising the fact that the initial slope (and therefore the quantum yield and
requirement) are the same in a sun and shade leaf. The fact that the latter had a lower
light compensation point (LCP), i.e. the light intensity at which photosynthetic oxygen
evolution and dark respiratory oxygen uptake are in balance, results from the lower
rate of dark respiration (DR) shown by the shade leaf. [Data from 10th UNEP/UWI
Training Course on “Photosynthesis & Productivity in a Changing Environment”
(Barbados, 1991)]
147
utilization could be diminished by almost two thirds. This constitutes a problem in

safe dissipation. Some plants, such as species of Oxalis, can alter the inclination of
their leaves in order to minimise light interception. Most species have to rely on
biochemistry rather than mechanics. They are not always successful. It is certainly
the case that shade leaves are more likely to be damaged by unwonted exposure to
high light than sun leaves but, by the same token, in the normal course of events,
they are less likely to experience bright light. Damage by excess light, once described
as “solarization” and now termed “photoinhibition” seems to be more common than
was once thought and there is evidence, for example, that crop species, like wheat
and barley, may suffer from the combination of cold and high light which they almost
invariably experience during some periods of their life cycle in temperate climates.
Similarly, horticulturists, conscious of the costs of heating glasshouses, have more
to fear from cold bright days than cold overcast days. Photoinhibition (Section 5.9)
is too large a subject to be considered here in detail but is may be noted that much
evidence suggest that the photochemical apparatus (in particular the D1 protein in
PSII) sustains more or less continuous damage and undergoes more or less
continuous repair, the more effective in sun leaves. However, plants have also
learned that prevention is better than cure. Botanists have conjectured for many years
about the possible protective role of carotenoids. The fact that pigmentation of leaves
is often an indicator of stress (e.g. drought or cold) is something familiar to
gardeners. More recently this has been put on a more substantive basis and there
seems little doubt that the “zeaxanthin or xanthophyll cycle” constitutes one
mechanism based on carotenoids which contributes to the dissipation of excess
excitation energy in PSII. Both the formation of zeaxanthin (which can accumulate
in high light) and its proposed mode of action (zeaxanthin appears to amplify
dissipation rather than to initiate it) are favoured by high ∆pH. The full picture,
however, is extremely complex and much is still to be clarified. Hydrogen ion
concentration, or more specifically, the transthylakoid hydrogen ion gradient ∆pH),
undoubtedly plays a major role.
6.11 Acid bath technology
The transthylakoid proton gradient (∆pH) results from electron transport

(Chapter 4) involving all or part of the Z-scheme. Some of the electron carriers
involved can only accept electrons, others require hydrogens (i.e. electrons plus
protons). Thus electron transport involves taking up and discarding protons and the
distribution and behaviour of carriers within the thylakoid membranes of the
chloroplast is such that protons are taken up from the outside of the membrane and
put down on the inside. Accordingly the stroma of an illuminated chloroplast
becomes more alkaline, the thylakoid compartment more acid. Protons discharging
through the ATPsynthase in the thylakoid membrane bring about ATP formation by
condensation of ADP and inorganic phosphate, according to Mitchell’s
chemiosmotic concept. Isolated thylakoids, “coupled” to ATP formation, transport
electrons more rapidly than they do in the absence of ADP and phosphate. Similarly
“uncouplers” (agents which, for example, effectively puncture the membrane) also
speed electron transport because they (like ADP + Pi) facilitate the discharge of the
proton gradient which otherwise creates a “back-pressure”. (Simplistically, it is
energetically more difficult to discharge a proton into a space already full of protons
than into a space containing few protons and, since electron transport involves
vectorial movement of protons from the outside of the thylakoid to the inside (Fig.
4.7), this also becomes more difficult). Thus the role of ∆pH in regulation of electron
transport at the site of the cyt b/ƒ complex has long been recognised. More recently,
however, it has become increasingly clear that ∆pH plays more than one role. Thus
it not only affects electron transport between the two photosystems but within PSII
148
ACID BATH TECHNOLOGY
and PSI and beyond PSI. Moreover, all of these sites of pH-related regulation tend
to interact with one another to a small or larger extent. For example the relatively
alkaline environment of the stroma (pH 8.5 or thereabouts) favours carbon
assimilation and therefore ATP consumption. ATP consumption regenerates ADP
which, in the presence of Pi, discharges the proton gradient through the
ATPsynthase. For this reason, removal of CO2 from the atmosphere surrounding a
leaf causes an almost immediate increase in ∆pH In turn, increased ∆pH regulates
electron transport. As just noted, one site of regulation lies between PSII and the cyt
b/ƒ complex but, within PSII, there are all manner of additional possibilities, with
∆pH seen as the common feature.
6.12 The Governor
Plants cannot take shelter from too much sun by seeking the shelter of a
nearby tree. Only a few have the capability of rapid leaf movement. At a maximal
quantum efficiency of 0.125, temperate C3 species may utilize more than 80% of the
red light that they are offered in the 0-800 µmole quanta.m-2.s-1 range. The fact that
this value may fall below 20% in shade species or shaded leaves is a matter of
photosynthetic capacity (enzyme complement) not efficiency. Whether shade or sun,
there is a clear need to dissipate the excess excitation energy safely. Safe dissipation
can be visualised as analogous to the mechanical “governor” beloved of Victorian
engineers. Here a revolving shaft developed centrifugal force in two masses of steel
or iron spinning about a centre, opposite to one another. The greater the energy input,
the further the two masses would swing apart and, in so doing, would increasingly
disengage the driving force from the machinery being driven. The objective was
protection. The machinery had a capacity for work which could not be exceeded
without damage. The governor ensured that this safe limit could not be exceeded.
In photosynthesis, electron transport creates a ∆pH which discharges through an
ATPsynthase to form ATP from ADP and Pi. If these components are not recycled
149
rapidly enough, because carbon assimilation is constrained by inadequate capacity

or unfavourable environmental factors, ∆pH (the governor), disengages the driving
force. Horton et al. propose that this disengagement results from an aggregation of
the major light harvesting complexes, induced by protonation of the surface of the
thylakoid lumen and promoted by the presence of zeaxanthin. While there is no life
for a leaf without excitement, too much excitement can lead to decreased efficiency
and photoinhibitory damage. Acting as a safeguard, against all but the worst
excesses, the governor exerts a calming influence.
6.13 Summary
All metabolic energy and much of Man’s fuels are derived from
photosynthesis. Photosynthesis involves the utilisation of light energy in breaking H-
O bonds; energy is derived from the products of photosynthesis when these H-O
bonds are re-established by respiration or burning. Within chloroplasts the
transduction of light-energy into electrical energy and then into chemical energy can
proceed at the remarkably high efficiency of 33% but the optimal conditions
necessary for maximal efficiency do not obtain in nature and a variety of factors
(including photorespiration, dark respiration, incomplete interception of light and
decreased efficiency at high light intensities) combine to decrease the maximum
efficiency of conversion to about 5% in leaves. Even for standing crops, or swards
of natural vegetation, 4.5% is only rarely approached. In general agricultural practice
the figure is well below 1%. Even so, large human populations could be maintained
by modern agriculture - populations much larger than currently exist. Such intensive
agriculture is, however, only made possible by investing very large amounts of fossil
fuels into fertilisers, herbicides, machinery, transport etc.) so that, in the end, modern
agricultural practice constitutes a very inefficient way of converting the products of
primaeval photosynthesis into contemporary photosynthetic products. Primitive
agricultural practice is not necessarily less energy-intensive and is certainly much
less productive.
While plant breeding may enhance plant productivity by improving the

versatility of crops it seems unlikely that the fundamental efficiency will be enhanced
in this way. Most C3 species seem to operate, under optimal light-limited conditions,
close to the maximal quantum yield of 0.125 permitted by the Z-scheme. At low light
intensities there is no difference in photosynthetic efficiency between “sun” and
“shade” plants. In all leaves the photochemical apparatus accommodates mechanisms
which allow safe dissipation of excitation energy in excess of that capable of being
used in carbon assimilation.
In the present context, the most important “take home lesson” from all of this
is that the “civilised” world we see about us has been made possible by long past
photosynthesis. In the first instance this gave us the air we breathe and the food we
eat but, since the Industrial Revolution and the advent of modern agricultural
practice, it is the extensive use of fossil fuels that has permitted the relentless and
continuing expansion of world population. In the remaining chapters we will
examine the consequences of this in more detail. For the moment we can simply
conclude that present trends cannot be sustained indefinitely on the present basis.
Increasingly, fossil fuels will become too scarce and therefore too expensive to use
widely in the manner that we use them now and sole dependence on contemporary
photosynthesis would demand ten-fold reduction in population. In the short term our
insistence on returning carbon dioxide to the atmosphere in quantities which it took
millennia of photosynthesis to remove will, in itself, have major impact on our
environment.
150
CHAPTER 7 - DOOM AND GLOOM
PREDICTION, SCEPTICISM, OPTIMISM AND PESSIMISM
7.1 Noah and the Ark
“The optimist proclaims that we live in the best of all possible worlds the
pessimist fears this is true” ....James Branch Cabell
The story of Noah and the Ark exemplifies some aspects of human thought
and emotion which must always have been with us. There are those who tend, like
the grasshopper, to live for the day. There are others, perhaps more pessimistic, or
better informed or (like Noah) with inside information, These have always viewed
the future with a certain amount of gloom. Given the fact that, during this century,
there have been two world wars, major attempts at genocide and many “minor” wars
(including the most awful, between Iran and Iraq, in which casualties have still been
counted in millions rather than in thousands) it is difficult to deny that human
pessimism has been entirely misplaced. Until the annexation of Kuwait by Iraq the
prospect of future world war and nuclear holocaust seemed mercifully more unlikely
than at any time in the recent past. Even so, if we were now to suppose that someone
could wave a magic wand, that Arab would embrace Jew, that the Ayatollahs would
be kind to Salman Rushdie, that India would warm to Pakistan and that the Irish
Republican Army and the Basque Separatists would forgive and forget, it would still
be difficult to find grounds for endless optimism about the future of the human
condition. Yet even the most cautious and guarded expression of concern is still
likely, in some quarters, to be dismissed in the same way as Noah’s forebodings
about the forthcoming flood. Scepticism, of course, is at the heart of good science
and there are endless examples of well based predictions which have been made to
seem almost ludicrous by subsequent events. In many Western countries, for
example, population doubling once seemed inevitable by the end of this century.
Now better contraception, economic pressures, and changed social attitudes (all
closely interrelated) have combined to keep young women at work longer before they
start families. This, in turn, has decreased the number of children per family and there
is now even concern, in countries like Germany, about a future in which there might
be too few young people to sustain the older part of the population in comfortable
152
retirement. In the Third World of course, nothing is changed. World population, so

we are told, is currently increasing by the easily remembered figure of 365,000 per
day (Section 7.18).
So prediction is uncertain. There is even some encouragement to be derived

from the fact that world “experts” are agreed that it is difficult, if not impossible,
to make realistic predictions about the consumption of fossil fuels into the next
century or the fate of the arctic tundra. Some things, on the other hand, are reasonably
certain. Let us see what these are.
7.2 What is it?
“Ask Daddy, he won’t know” .....Ogden Nash
The “greenhouse effect” (or more properly the “enhanced greenhouse effect”)
is central to contemporary relationships between plants, Man’s energy requirements
and his environment. It is also central to the whole concept, now slowly but surely
50000 10000 2000 1428 1000 663 333 200 100
0.1 0,15 0.2 0.3 0.5 1.0 1.5 2 3 5 10 15 20 30 50 100

Wavelength µm
100
Ground
Absorption %
60
Level
50
H 2 O (Rotation)
40 O2
20 O3 B
CO2
0
O2 O2 O2 O2 O3 O3 O2 O2 H 2 O H 2 O CO2 HDO H 2 O O2 N 2O
N 2O N 2O CO2
H 2O H 2O
CO CFCl 3
CH 4
H 2O CO2 CFCl 2
CH 4
Fig. 7.1 Percentage of radiation passing from the top of the atmosphere to the
surface. Note the weak absorption of the solar spectrum (between 0.3 and 1.0 mm)
[from MacCracken and Luther, 1985].
being rejected, that Man could do what he wished with “his” planet without eventual
and possibly painful consequences.
[The term “greenhouse effect”, as described below, is applied loosely, in

accord with present practice, to a situation which existed long before Man and
one which allowed the advent of life on Earth. What is currently a matter for
concern is the enhancement (of this effect) which has occurred, and is
continuing to occur, since the Industrial Revolution.]
At least, in the northern hemisphere, “greenhouses” are a common feature

of horticulture. Much of Europe’s tomato and cucumber crop is grown under glass
in order to raise the temperature to one which favours these plants. Immense amounts
of fossil fuels are burned, in winter and spring, to warm these greenhouses but, even
if they are not heated artificially, they are warmer than their immediate environment.
153
This is primarily because the glass permits sunlight to enter reasonably well but at
the same time diminishes the heat loss which would otherwise occur by free
circulation of air and by convection. The analogy between such greenhouses and the
natural “greenhouse effect” (which makes life on Earth possible to Man, by raising
the mean global temperature from -18°C to +15°C) also relates to warming by the
sun and prevention of cooling but there the similarity ends. Instead of glass we have
gases. These gases do not interfere with cooling air movements, like the glass in a
man-made greenhouse, but they do decrease the rate at which heat is lost by radiation
until the temperature increases (on average by 33°C). Clearly, a new balance between
heat gain and heat loss will have to be struck because, if it were not, the world would
get hotter and hotter. Similarly, it is evident that, although the greenhouse effect
currently results in a mean global temperature of 15°C, it is very variable in its effect.
These variations contribute to the complexities of climate.
SPACE INCOMING OUTGOING RADIATION

SOLAR
RADIATION Shortwave Longwave
100 8 17 6 9 40 20
ATMOSPHERE Backscattered
Net emission
by air
by
water vapour Emission
Absorbed by CO 2 , O 3 by clouds
water vapour, 19 Reflected absorption
dust,3 O by clouds by clouds,
water vapour,
CO2 , O 3
106 Latent
4
heat flux
Absorbed by Reflected
clouds Sensible
by surface LONGWAVE heat flux
Absorbed RADIATION
40 115 100 7 24
OCEAN, LAND
Fig. 7.2 The atmospheric heat balance. The units are percentages of incoming solar
radiation. The solar fluxes are shown on the left, and the longwave (thermal infra-red)
fluxes are on the right (after MacCracken and Luther, 1985).
Those of us who live in temperate climates are very conscious of winter frosts
and their association with clear nights. The famous Scottish phrase “Its a braw,
bricht, moonlit nicht the nicht” usually presages frost. There are such things as
freezing fogs but, by and large, we know that if the stars sparkle in the winter night
it is likely to get a great deal colder than if there is thick cloud. In such circumstances,
we go to bed beneath some thick cover or blanket which ensures that we do not lose
body heat to our immediate environment. Clouds of water vapour in our skies serve
much the same purpose. Indeed, most of the natural greenhouse effect is attributable
to water vapour and, in northern climates, we are only too well aware of the
immediate chill that we can experience when the sun goes behind a cloud. In such
circumstances it is primarily incoming solar radiation which is being excluded but
water vapour is even more effective in diminishing the loss of heat to space. Even
154
HOW DOES IT WORK?
deserts, which become exceptionally hot as the sun beats down from a cloudless sky,
can become uncomfortably cold by night without a blanket of water vapour to slow
re-radiation of heat. Although water vapour is immensely important in this regard
it does not act unaided. As we shall see in Section 7.5 - 7.8 its work is supported
by other greenhouse gases of which the most important, and contentious, is carbon
dioxide.
The analogy with the “greenhouse” or “glasshouse” now becomes clear.

Unless such structures are ventilated, or air-conditioned in some way, they soon
become much warmer than their immediate environment because solar heating is no
longer as effectively balanced by heat losses of any magnitude. The Earth, of course,
is well “ventilated” but the greenhouse gases still combine to slow the loss of heat
into space.
7.3 How Does It Work?
Like most aspects of science the greenhouse effect is a great deal more
complex in detail than it is in principle but, at its simplest, the story goes like this.
Electromagnetic radiation from the sun (Section 2.2) penetrates the Earth’s
atmosphere. Some is reflected back into space from clouds of water vapour and some
from the ice caps and other snow-covered and reflecting areas. Water vapour and
other greenhouse gases are not, however, very effective absorbers of solar radiation
Radiated
out to space
Re-radiated
back to space
Reflected
back to
space
Atmosphere
Re-radiated
back to surface
Fig. 7.3 The greenhouse effect. Simplified version of Figure 7.2. Some incoming
solar radiation is reflected back into space by clouds, some is absorbed by the
atmosphere, and some (mostly visible light) reaches the Earth’s surface. In turn, the
Earth radiates heat as infra-red. Some of this is again absorbed by the atmosphere
which then radiates part of it back to Earth and part of it back into space. This raises
the current global mean surface temperature from about -18°C (the estimated steady-
state temperature at which heat input and heat lost would come into balance in the
absence of an atmosphere) to 15°C.
155
and accordingly much of the sun’s radiation penetrates to the Earth’s surface. This
is particularly true of electromagnetic radiation in the visible and photosynthetically
active band (400-700 nm). Radiation which is absorbed by the planet and its
atmosphere is also continuously re-radiated, by night and by day, in the long wave
(infra-red) part of the spectrum. If we heat an iron in a fire it becomes “red hot”,
i.e. it emits red light in the 650-700 nm part of the spectrum. At the same time it
emits infra-red radiation (at wavelengths longer than 700 nm which we cannot see)
and any object, at any normal temperature, can lose heat by radiation in this way.
Part of this long-wave radiation is intercepted by water vapour, carbon dioxide and
other greenhouse gases. These re-radiate energy in all directions thereby deflecting
some heat which would otherwise be lost, back towards the Earth’s surface. Water,
and water vapour, absorb radiation very effectively throughout much of the long-
wave spectrum (the simplest way of cooling light from a tungsten source such as a
conventional electric light is to pass it through a reasonably deep layer of water).
There is, however, a major “window” between 8,000 to 12,000 nm (8-12 µm) in
which both water and carbon dioxide absorb poorly and in which some other gases
like methane (Section 7.6) and ozone (Section 7.9) absorb strongly.
In the presence of an atmosphere (Fig. 7.3), much of the loss of long wave
radiation from a planet occurs above its surface. A planet, like Mars, with a “thin”
atmosphere radiates most of its heat from near its surface and one, like Venus, with
a dense carbon dioxide atmosphere and a strong greenhouse effect, radiates most
infra-red from well above its surface. The mean radiating height for Earth is currently
5.5 km and if greenhouse gases continue to accumulate this height will increase. The
effective radiating temperature of the planet will remain unchanged at -18°C (255K)
but the temperature of the troposphere (Fig. 7.14) and the temperature of the surface
(which are tightly coupled) will rise.
7.4 Generating Hot Air
“Does a Christ have to die in torment in each generation

to save those who have no imagination?” .......George Bernard Shaw
Emission of CO2, from
fossil fuels, by source Seen from the twentieth century, the heresies of St. Joan pale into
insignificance compared with those of Galileo but nothing so offends the current
dogma, be it secular, ecclesiastical, spiritual, ethical, or simply a matter of common
sense, than the concept that the universe does not revolve about the world. As always
it is desperately difficult for the layman, or the scientist outside of his own immediate
discipline to make objective judgements. A scientist is supposed, by vocation and
training, to be properly sceptical to be open-minded and, while working within the
confines of current dogma, to be able to step outside of existing “truths” once these
can be demonstrated to be less than true or even false. These constraints are, by
definition, in conflict with one another. Moreover, scientists are human, they can be
mistaken and misled. They can be bought. They often have enough intelligence to
see where their best interests lie. These human failings, together with very real
uncertainties have been joined together by some journalists, television producers and
politicians to create a “Green House Conspiracy”. This is seen as a self-interested
Electric Power 35% attempt by scientists, anxious for funding, to further their careers by persuading a
gullible public that there is real cause for concern about the future when they know
Transportation 30%
full well that such dangers are grossly exaggerated. Given some of the conspiracies
Industry 24% in politics and commerce which seem to surface on an almost daily basis it is,
perhaps, not unwise to discard the possibility of conspiracies in science but the
Residences 11% evidence is hard to find. So far as funding is concerned it is certainly no easier to
obtain support for work on global warming, despite its topicality, than for any
156
THE GREENHOUSE CONSPIRACY
comparable branch of science and a proposal which sought to question any of the
current dogma would undoubtedly have as much chance as one which embraced it
without reservation. So far as science itself is concerned, there is no doubt that there
have been scientific hoaxes and that falsification of results is not totally unknown
but it would be very difficult to argue that these have ever significantly changed our
perception of things. Scientists as individuals are presumably neither better nor worse
than business men, politicians, poets or market gardeners. Moreover, cheating at
science is a particularly pointless thing to do - almost on a par with cheating at
patience. In the long term, truth will out, exaggerated claims will be questioned,
charlatans will be discredited. It is very hard, therefore, to give credence to this
particular conspiracy theory; almost impossible to believe that there is a dedicated
band of greenhouse freaks, indifferent to scientific reality or moral considerations.
This is not to say that there is no room for real doubt, uncertainty, or a need to
question simple lack of understanding. It cannot be said too often, or too clearly, that
the only present certainty is that CO2 has increased and will continue to increase in
the immediate future. What impact that will have, immediately passes into the realm
of well-informed guesswork or mere speculation. It has already been noted that the
whole concept of global warming, consequent upon Man’s activities, is based on the
enhanced greenhouse effect and that if it were not for the underlying or natural
greenhouse effect the mean global temperature would be -18°C rather than +15°C.
However, Richard Lindzen, writing with all the authority of a professor of
meteorology at M.I.T., points out that this concept is “seriously incomplete” and that
“if it were a true representation of the actual greenhouse effect, the Earth would be
95°C rather than the 33°C warmer than it would be in the absence of greenhouse
gases. The reason why 77% of the actual greenhouse effect is absent is simply that
the Earth’s surface does not cool primarily by radiation: it cools mainly by
evaporation. Heat in the form of either sensible heat or latent heat (available for
157
release when water vapour condenses into rain) is bodily carried away from the
surface by air motions associated with turbulence, cumulonimbus towers, and
larger-scale meteorological systems. It is deposited at higher latitudes and altitudes
where there is much less greenhouse gas to inhibit cooling to space.”
Lindzen also points out that it could easily be inferred, from some contemporary
accounts, that current atmospheric water vapour provides 60-70% of greenhouse
warming and carbon dioxide 25%. In fact, he says, over 97% of the greenhouse effect
on Earth is due to water vapour and stratiform clouds so that all other greenhouse
gases play a “truly minor role”. Remarks such as these are particularly telling and
carry much more weight than thoughts of greenhouse conspiracies. They should
remind us all to approach this subject in the same way as did Robert Boyle when
he wrote “The Sceptical Chemist”. We must respect Lindzen’s caustic candour when
he says (of “Climate Change: The PIPCC Scientific Assessment”)
“we really have two distinct documents: a Policymakers Summary which suggests
that we are certain that serious climatic consequences will result from increasing
levels of so-called greenhouse gases, and a lengthy report which finds no evidence
for this certainty.”
340
335
CO 2 (parts per million)
330
325
320
315
58 60 62 64 66 68 70 72 74 76 78 80 82
YEAR
Fig. 7.4 Atmospheric carbon dioxide concentration as monthly mean values at

Mauna Loa, Hawaii, from 1958 to 1981. The annual “sawtooth” is believed to derive
principally from the winter decline in deciduous and evergreen photosynthesis in the
northern hemisphere Note the decrease in the rate of increase in the early 70’s which
is believed to result from steep preceding rises in the price of oil.
But, if the doubts and uncertainties are so manifestly many, why should we be
concerned at all? One obvious, and by no means trivial reason, is that it always helps
to be as well-informed as possible about any matter which has become the subject
of public debate and which we ourselves might be able to influence for better or
worse. Another is more fundamental. We know that, whatever else happens, CO2 and
methane will continue to rise because of Man’s activities. We know that these
increases will change our environment just as destroying rainforests, killing whales,
over-fishing or merely creating rubbish and sewage will change our environment. We
might then reasonably ask if we ought to contemplate continuing doing these things
at present rates without at least examining the possible consequences. Biologists, and
158
GREENHOUSE GASES
most of the public at large, almost invariably find merit in conservation.

Conservation is not compatible with carbon dioxide at twice its present level even
if this were to have absolutely no effect on global temperatures. The mere fact that
CO2 might double simply underlines the fact that we ought not to gratuitously change
the world in such a cavalier and careless fashion. What is more, there are good
economic arguments why we should not do so (Chapter 9).
THE GREENHOUSE GASES
7.5 Carbon Dioxide
“Mans’ greatest geophysical experiment” ... Rogers Revelle
Carbon dioxide, like water vapour, transmits electromagnetic radiation in the

visible range but absorbs it, very effectively in the infra-red, particularly between
12,000 and 18,000 nm (12-18 µm). An invisible and tenuous blanket of water vapour
and atmospheric carbon dioxide continuously diminishes the extent to which our
planet loses heat to space by infra-red re-radiation. Carbon dioxide and greenhouse
gases other than water (methane, N2O, CFCs, etc) currently absorb about 50% more
340
320
300
280
1700 1750 1800 1850 1900 1950 2000
Fig. 7.5 Carbon Dioxide in Glacier Bubbles.
infra-red radiation from the earth’s surface than did carbon dioxide alone, in pre-
industrial days. As a result of Man’s activities, carbon dioxide is produced on a
massive scale (5.6 billion tonnes of carbon, in 1987) mostly by burning fossil fuels,
of which, in the immediate future, natural gas will continue to be the most important.
In Section 4.1 we have seen that plants use the energy from the sun to
incorporate carbon dioxide into carbohydrates (CH2O) and that both plants and
animals consume CH2O (and derivatives of CH2O) in respiration, a process which
leads to the release of energy and the return of carbon dioxide to the atmosphere
(Section 1.3). Fossil fuels can be regarded as photosynthetic products which have
been stored for millions of years and which have been modified, as a result of
pressure etc., during storage, into oil, natural gas and coal. Moreover, when fossil
159
fuels are burned in fires, furnaces, electricity-generating plants or internal

combustion engines, the process is always roughly analogous to respiration in the
sense that a reduced compound (Section 1.2) is oxidised in a more or less controlled
5.0 G TONS 6.8 G TONS
EUROPE
EUROPE U.S.
U.S.
11% 20%
15% 25%
USSR 18% USSR 17%

12% OTHER
15%
9% 14%
18% OTHER
CHINA 26%
CHINA
LDC's
LDC'S
1986 2010
Fig. 7.6 World carbon emissions from fossil fuels.
Other 3.9% Other 6%

C.P.Asia 1.4% Other 5.2%
C.P. Asia 8.5%
Developing 5.7% C.P. Asia 5.7%
Japan, Australia Developing 8%
2.8% Developing
North North America
Japan, 12.2%
America 26.7%
U.S.S.R., North Australia
C.P, Europe 32.1%
America 4.4%
18% 44.7% U.S.S.R.,
Western C.P Europe Japan, Western
Western Europe
Europe 24% Australia U.S.S.R.,
Europe 16.5%
23.4% 20.6% 5.8% C.P. Europe
24.2%
1,618 Million Tons C 3,126 Million Tons C 5,170 Million Tons C

1950 1965 1980
Fig. 7.7 Historical carbon dioxide emission rates, by region.
fashion, and the formation of new C-O and H-O bonds leads to the release of carbon
dioxide and H2O. Respiration itself contributes to the return of carbon dioxide to the
atmosphere but respiration is of no real consequence in this regard because it only
returns to the atmosphere, carbon dioxide newly removed by photosynthesis (Section
1.3). Plants, animals, and “primitive” Man lived (and still live) in balance with their
environment because they cannot continue to release more carbon dioxide than
photosynthesis has recently fixed. Even when stretches of forest were cleared, by
burning, in the dawn of agriculture, the scale was small and the rate of progress so
160
PRIMARY ENERGY CONSUMPTION
200
Primary
Electricity
150 Gas
Oil
mb/doe
100 Coal
Wood &
Other
50
1860 1870 1880 1890 1900 1910 1920 1930 1940 1950 1960 1970 1980
Fig. 7.8 World primary energy consumption 1860 - 1985.
Fossil Fuels 62%
Hydroelectric 19%
Nuclear 17%
Other 2%
Fig. 7.9 Sources of electrical energy.
slow that the impact on the atmosphere was trivial. Currently, burning of tropical rain
forests is making a major contribution to atmospheric carbon dioxide because the
scale is so immense and it is all being done so quickly.
[Tropical rain forests (Section 9.13) do not themselves abstract as much

carbon dioxide from the atmosphere as is sometimes supposed because,
despite their massive photosynthesis, mature rain forests together with their
respiring and decaying plant, animal, insect and bacterial populations also
161
return equally massive amounts of carbon dioxide to the atmosphere. On

balance, rain forests are more beneficial in all manner of ways than the
temporary cattle ranching which so often replaces them. However, it is the
rate and extent of current burning which so adversely affects the atmosphere
rather than the continuing absence of forests once they are destroyed.]
In the same way, if contemporary Man could rely entirely on biomass and
renewable resources for both his metabolic and his other energy requirements, he
would constitute no threat to the atmosphere. This is seen very easily if we bear in
mind that it makes little difference to metabolic energy whether a man is rich or poor,
fat or thin, greedy or abstemious. He can not increase his own personal energy rating
much above 100W unless he does a great deal of physical work. (Even then we are
talking about, say, 300W whereas the rest of us, in relative sedentary occupations,
will use only about as much as a 100W electric lamp, burning continuously.)
Conversely, if we are relatively rich or profligate or simply live in a Western country
with a high standard of living and have been brought up to take cheap energy for
granted, our expenditure on food, transport and industry and what we use to warm,
cool and light our houses, may add up to 10 kW or more per head. This could be
a hundred times as much as we “spend” metabolically. Food, (Chapter 6) figures
large in these considerations because it is quite impossible, at present, to sustain
present populations without recourse to fossil fuels. We depend as much on past
Table 7.1
Per Capita Carbon Dioxide Emissions (Tonnes)*
1950 1988
Canada 3.1 4.6

France 1.3 1.6
Italy 0.2 1.7

Japan 0.3 2.2
United Kingdom 2.7 2.7
United States 4.6 5.3
West Germany 1.9 3.0
Czechoslovakia 1.7 4.1

German Dem. Repub. 2.4 5.4
Poland 1.2 3.3
Romania 0.3 2.6
Soviet Union 1.0 3.8
Brazil 0.1 0.4

China 0.04 0.56
India 0.1 0.2
Korea “zero” 1.3
Mexico 0.3 1.0
* from fossil fuel consumption, cement manufacture and gas flaring (the two latter collectively
contributed less than 4% of the total in 1988) - Source Carbon Dioxide Information Analysis
Centre, Oak Ridge National Laboratory, USA.
162
CARBON DIOXIDE EMISSIONS
200 Solids
liquids
Gasses
Flaring
150 Cement
Total
Million Metric Tons C
100
50
0
1950 1960 1970 1980 1990
Total Emissions (including source).
6
Metric Tons C per Person
0
1950 1960 1970 1980 1990
(b) Per capita CO2 emissions.
Fig. 7.10 CO2 emissions from the United Kingdom. [From “Trends ’90. A
Compendium of Data on Global Change”. The Carbon Dioxide Information Analysis
Centre, Oak Ridge Nat. Lab. Data, Greg Marland.]
photosynthesis as on present photosynthesis for what we eat. When it comes to fossil

fuels there is a measure of choice. Coal is bad because it is primarily carbon and
goes like this:-
C + O 2 → CO 2 Eqn. 7.1
and, if it contains appreciable amounts of sulphur, as it often does, then the

combustion of the sulphur (while adding marginally to the calorific value without
affecting the amount of carbon dioxide released) gives rise to sulphur dioxide which,
as acid-rain etc., damages health, buildings and forests alike.
S + O 2 → SO 2 Eqn. 7.2
163
200 Solids
liquids
Gasses
Flaring
150 Cement
Total
Million Metric Tons C

100
50
0
1950 1960 1970 1980 1990
Total Emissions (including source).
6
Metric Tons C per Person
0
1950 1960 1970 1980 1990
(b) Per Capita CO2 emission.
Fig. 7.11 CO2 emissions from India [From “Trends ’90. A Compendium of Data
on Global Change”. The Carbon Dioxide Information Analysis Centre, Oak Ridge Nat
Lab. Data, Greg Marland.]
Methane (i.e. “natural” gas - Section 7.6) is better in some regards because,
as equation 7.3 shows,
CH 4 + 3O 2 → CO 2 + 2H 2 O Eqn. 7.3
its combustion involves the formation of twice as many H-O bonds as C-O bonds.
164
CARBON DIOXIDE EMISSIONS
The former, while contributing energy (Table 7.3) only add water vapour (rather than
carbon dioxide) to the atmosphere. (Given the amount of water vapour already in the
troposphere (Fig. 7.15) and the factors which affect its equilibrium with land and
oceans, this may seem to be of no consequence, but, in fact, methane oxidation can
adversely effect stratospheric water vapour thereby reinforcing direct radiative
effects (Section 7.6).
Although a shift from coal and oil to natural gas is not, therefore, an entirely
unmixed blessing the relevant records give some indication of what might be
achieved by intelligent application of appropriate energy policies (Chapter 9). Global
emission of carbon dioxide from fossil fuels, cement production, gas-flaring etc.
were 5.65 billion (5.65 x 109) tonnes of carbon in 1987, just over 1.1 tonnes of carbon
for every person on Earth. Citizens of the United States were the most profligate in
this regard, accounting for 22% of the total or about 5 tonnes of carbon per person.
Inhabitants of the United Kingdom are not a lot better but, strangely enough, they
have not become worse since 1950 (Table 7.1). During the last forty years or so per
capita emissions from the U.K. have remained more or less constant. This is not the
result of any conscious effort. On the contrary, past indifference and lack of
Table 7.2
Heating Caused by Greenhouses Gases
Principal absorption bands.
Concentration Position Strength Greenhouse

Gas ppm cm-1 arm-1 cm-1 STP heating Wm-2
Water vapour ~ 3000 ~100

Carbon dioxide 345 667 (many bands) ~ 50
Methane 1.7 1306 185 1.7
Nitrous oxide 0.30 1285 235 1.3
Ozone 10-100×10-3 1041 376 1.3
CFC11 0.22×10-3 846 1965 0.06
1085 736
CFC12 0.38×10-3 915 1568 0.12
1095 1239
1152 836
The main absorption bands and band strengths (a measure of the probability of a molecule
absorbing a photon at the band wavelength) are shown for the less abundant gases. (see
also section 7.7)
recognition of the consequences of carbon dioxide emissions has given way in the
last decade to the philosophy of “market forces” and a government with a desperately
poor record in regard to promotion of energy conservation. Why then have outputs
of carbon dioxide per person remained constant and total emissions only 10.5%
higher in 1988, “by far the smallest increase among the top twenty nations”. Britain,
once third among the major, carbon dioxide emitting, nations has slipped to seventh
place without even trying. It is perhaps not entirely coincidental that the largest
sustained decline of 19% occurred between 1979 and 1984, the first five years of
office of the present Conservative government. “Market Forces” undoubtedly played
a part because, as oil became more expensive, natural gas (which now accounts for
20% of the carbon dioxide emitted from the U.K.) became more attractive. At the
165
same time, the massive decline in heavy manufacturing industry (particularly steel
and shipbuilding which uses large quantities of steel) must, to a large extent, have
offset the seemingly relentless rise in road-transport. Moreover, mindful of the
miner’s strike which ended a previous Conservative government, Margaret Thatcher
and her colleagues were determined to ensure that the U.K. became less dependent
on coal. It is obviously difficult to assess which of these many factors was most
telling. Different political persuasions would undoubtedly influence interpretations.
Nevertheless the record is indisputable. Whether or not the economy of the U.K. is
materially better or worse than it was twenty or forty years ago is a matter for
argument but there is no doubt that Britain’s carbon dioxide emissions have remained
relatively stable during a period (Fig. 7.10) in which global emissions and emission
from some broadly comparable countries has increased substantially (Table 7.1). In
experimental terms it seems clear that national policies have had a material influence
on the extent of carbon dioxide emissions and that wholehearted adoption of better
policies (Chapter 9) and in particular policies of conservation could lead to
substantial decreases in emissions, despite increases in population. Similar trends are
evident in Table 7.1. The growth in emissions from third world countries (see also
Fig. 7.11) is inevitable, at least in the short term, but there are remarkable differences
between western and eastern block countries (e.g. East and West Germany, Romania
and Spain) and European countries (e.g. France, Germany and the U.K.) with broadly
similar populations and standards of living.
7.6 Methane
The present concentration of methane in the atmosphere (Table 7.2) is

extremely small. We are already accustomed to thinking of carbon dioxide as a minor
1500
CH 4 Concentrations (ppBv)
1300
1100
900
700
1700 1800 1900 2000
Fig. 7.12 Concentrations of atmospheric CH4 from ice cores
constituent of the atmosphere, despite its importance. Certainly if we were to

represent each molecule of gas in the atmosphere by one inhabitant of the city of
London we would need to ask two or three thousand of its inhabitants to pose as
166
METHANE
molecules of carbon dioxide (to represent a concentration of 345-350 parts per

million). On the same basis, however, we would be only looking for ten or fifteen
London citizens to play the role of molecules of methane. Why then is methane now
regarded as an important greenhouse gas? There are two reasons. One is that,
although the concentration of methane is only about 1/200th of that of carbon
dioxide, it is 20-25 times more damaging on a molecule to molecule basis. This is
because its chemical structure makes it more effective than carbon dioxide in
absorbing infra-red and also because it is drawing down a blind across a window in
the infra-red absorption spectrum which is still largely unscreened and relatively
unaffected by carbon dioxide. For these reasons, even though it is present in such
small amounts, methane accounts for about 18% of the increases in the greenhouse
effect (Fig. 7.15). Another cause for concern is that its concentration in the
atmosphere is rising at a rate considerably faster than that of carbon dioxide. It is
only in the last decade that it has been possible to make accurate direct measurements
of global methane and these show that it is increasing at about 1% per annum. It is
also possible to look at the geological record of methane (Section 7.6) in the same
way as it is now possible to say with considerable accuracy, how much carbon
dioxide was present in the atmosphere in the relatively recent past. In both cases this
is done by sampling the contents of the bubbles trapped in arctic ice of known ages.
The records show that methane remained remarkably constant for about 30,000 years
and started to rise only towards the end of the 17th century. There was then a marked
CH 4 Concentrations (ppBv)
1800
1700
1600
1500
1980 1982 1984 1986 1988 1990
Fig. 7.13 Monthly concentrations of atmospheric CH4
acceleration at the turn of the present century such that atmospheric methane has
approximately doubled over the last 200 years. This is very strong circumstantial
evidence that this part of the increase in methane concentration is “anthropogenic”
(i.e. that it is a consequence of Man’s activities). This is based on the striking
correlation between the growth in methane concentrations and the growth in human
population. Only a little methane is generated by geological activity:-
167
“Methane is bound into lattice-like structures, clathrates, which are present

in vast quantities (exceeding all known coal reserves in the ocean sediments),
leakage of methane from the ocean floor in fact provides the main source of
carbon for some marine populations. But there is no reason to suppose that
methane production from these submarine reservoirs has increased in recent
times”.
So where is the methane coming from? Possibly as much as 30% derives from
incomplete combustion of fossil fuels. Decaying plants and animals make a
contribution. The release of methane from garbage in “land-fills” can constitute a real
fire risk. Methane is “marsh gas”. The old legend of will-o’-the-wisp came from the
spontaneous ignition of methane, flickering over bogs and marshes. It has even been
l<1000 A
300
Solar extreme UV:

Thermospere
l<3000 A
l<3000
> A
Solar UV: 2000 <
Solar visible and infrared:

200
Altitude(km)
100
Mesopause
Mesosphere
Stratopause )
Stratosphere
Tropopause
Troposphere )
0 500 1000
Temperature(°K)
Fig. 7.14 Divisions of the Atmosphere. The atmosphere can be divided into
troposphere, stratosphere, mesosphere, and thermosphere, separated by tropopause,
stratopause and mesopause respectively. The high temperature regions of the
atmosphere result from the absorption of solar radiation in certain wavelength ranges,
as shown on the right. (from Goody & Walker, 1972).
known for British students of botany, engaged in peat borings in the middle of raised
bogs in the pouring rain, to be cautioned against smoking for fear of igniting some
vast conflagration. This, of course, was always as unlikely as the possibility that
these wetlands, now rapidly diminishing as the result of draining, might be largely
responsible for increasing the methane in the atmosphere. There is, however, one
168
METHANE
such source of methane which will, quite clearly, have increased in parallel with
increases in world population. Rice production in the paddy fields of South East Asia
has undoubtedly contributed to increasing methane production.
Coal mines and oil wells have made their own contribution, both in regard
to methane inadvertently released as a result of these operations, or as a consequence
of incomplete combustion of fossil fuels. It is possible to derive some estimate of
the amount of methane in the atmosphere produced in this way. These estimates are
based on C14 measurements (C14 is a radioactive isotope of carbon). Oil and coal
reserves contain very little C14 compared with methane released in other ways. Such
estimates put the current atmospheric methane derived from fossil fuels at about
30%. In the U.K. 29% of the methane released has been attributed to deep-mining
of coal but the uncertainties in this sort of attribution are underlined by the fact that
a very indefinite 10% is related to “gas leaks” (i.e. leaks from pipes which supply
“natural gas” for domestic and industrial use).
[Leaks have to be taken into account in considering the relative environmental

impact of burning methane, which is often said to be preferable to coal and
oil because it yields less carbon dioxide per unit of energy released (Table
7.4). It can readily be seen that this advantage would be largely lost if an
appreciable percentage of methane escaped prior to burning and made its own
direct contribution as a very effective greenhouse gas. It has been claimed,
by Wallis, that leakage from North Sea Gas wells together with land-based
leakage could increase the emission of greenhouse gases by a factor of 0.5-
2.0 when it is preferred to coal in UK electricity generators.]
Table 7.3
Past and Projected Greenhouse Gas Concentrations and

Associated Changes (∆) in Greenhouse Heating (Q)
Assumed 1860 Q Estimated 2035 Estimated ∆Q

Concentration 1860-1985 Concentration 1985 - 2035
Gas ppm Wm-2 ppm Wm-2
Carbon dioxide 275 1.30 475 1.80

Methane 1.1 0.40 2.8 0.50
Nitrous oxide 0.28 0.05 0.38 0.15
CFC11 0 0.06 1.6×10-3 0.35
CFC12 0 0.12 2.8×10-3 0.69
Total 1.9 3.49
Methane is also produced in large quantities in the rumen of cattle. Although

cows are clearly herbivores in the normally accepted sense of the word they are
carnivores in another. Unable themselves to digest plant constituents, such as
cellulose, they rely on bacterial digestion within their rumens. Rotifers etc., which
in turn feed on these bacteria, are washed over a “weir”, together with other products
of digestion, into parts of the cow’s gut which can digest this remarkable brew.
Methane produced in the rumen is released from both ends of the digestive tract.
[Cattle can become bloated if they are allowed to eat some plants such as
Lucerne, (Alfalfa, Medicago sativa). This is because chloroplast lipids in
169
these plants contribute to the formation of a stable foam which prevents the
release of methane to the atmosphere.]
Table 7.4
Carbon dioxide emissions from fossil fuels*
Coal 24
Oil 20
Natural gas 14
* Approximate values in Kg carbon released

per GigaJoule of energy generated.
In the U.K., 23% of the methane released is attributable to belching and

farting cattle and 9% to sheep. Pigs, poultry, horses and people combine to add
another 1%. You and I, it seems, contribute between 300 ml and 2 litres a day in
this way.
“Some of us fart a lot and some of us fart a little but, whatever anyone tells you,
there is no-one, not even the Queen, who doesn’t fart at all.”
Fortunately (or perhaps unfortunately in some respects) such exhaust gases

are not all pure methane. One saving grace about methane is that it does not hang
around indefinitely and it is continuously undergoing photochemical oxidation by the
hydroxyl radical (OH) in the troposphere (thereby making a modest addition to less
effective carbon dioxide)
CH 4 + 8 OH → CO 2 + 6H 2 O Eqn. 7.4
Nevertheless
“If the current rate of increase is maintained, concentrations will reach 2.8 ppm in
the next 50 years contributing an additional 0.5 Wm-2 in radiative heating”.
170
CHLOROFLUOROMETHANES
Moreover, (Section 7.5) oxidation of methane may also contribute to

stratospheric water vapour, thereby reinforcing direct radiative effects.
7.7 Chlorofluoromethanes
Methane (Section 7.6) is bad enough but methane in disguise is even worse.
Methane is a simple molecule, one carbon joined to four hydrogens and, since each
of these can be substituted by other atoms, it is possible to come up with all manner
of related molecules like chloroform (CHCl3) and carbon tetrachloride (CCl4), once
used widely for removing stains from clothes and doing nasty things to people’s
livers if used unwisely. “Chlorinated fluorocarbons” (CFCs) belong to this family.
Chemically, CFC 11 is CFCl3 and CFC 12 is CF2Cl2.
“The contribution of a gas to the greenhouse effect depends on the

wavelength at which the gas absorbs radiation, the concentration of the gas,
the strength of absorption per molecule (line strength), and whether or not
other gases absorb strongly at the same wavelengths. As a consequence, one
molecule of dichlorodifluoromethane (CF2Cl2) is about 104 times more
effective in “trapping” long-wave radiation than one molecule of carbon
dioxide in the present atmosphere.”
CFCs are not only much nastier than methane itself because they absorb
infra-red in parts of the spectrum that other gases don’t reach but also because of
their notorious facility for destroying atmospheric ozone (Section 7.8), which would
otherwise prevent ultraviolet radiation (from the sun) reaching the Earth’s surface.
CFCs are released in relatively minute amounts from aerosols, air-conditioners and
refrigerators and in somewhat larger amounts from commercial installations
producing frozen foods and plastic foams. CFCs are very stable, inert molecules
which makes them ideal for this purpose but it also endows them with an
unparalleled facility for conveying chlorine from the Earth’s surface to the
stratosphere. Many other organic molecules are susceptible to the near ultraviolet
radiation which reaches the troposphere (Fig. 7.14) but CFCs are virtually
untouched. Indeed, when James Lovelock first sampled atmospheric CFCs in 1971,
he found that a substantial fraction of the CFCs manufactured at that time had
accumulated in the troposphere, impervious to breakdown by near ultraviolet light.
In the stratosphere on the other hand, far ultraviolet light degrades CFCs, releasing
chlorine which can react with ozone to give the free radical, chloric oxide.
Cl + O 3 → ClO + O 2 Eqn. 7.5
Moreover chloric oxide can regenerate chlorine
2 ClO → Cl 2 + O 2 Eqn. 7.6
so that the whole process can continue
“Rowland and Molina estimated that CFCs would have lifetimes of between 40 and
150 years before being decomposed in the stratosphere. Once that happens, each
atom of chlorine could destroy, through its chain reactions, as many as a hundred
thousand molecules of ozone. They estimated that, if the current rate of production
of CFCs continued, half a million tons of chlorine would be released annually into
the stratosphere and this would double the rate of ozone decomposition that occurs
naturally. The net result was likely to be a depletion of ozone by between 7 and 13%.
171
Chlorine might eventually take over the chemical control of the stratosphere with
very serious consequences on animal and plant life. Finally if this were not enough
to be worrying about, the effects were already ordained in some degree by the long
lifetime of the CFCs already released” ...George Porter.
Once it became clear how dangerous CFCs could be, there followed a huge
argument in the United States involving the CFC industry, the National Academy,
a Congressional enquiry and the Environmental Protection Agency, (which put a
price tag of $1.5 billion and 9000 jobs on banning CFCs). When the National
Academy concluded that the threat was real but distant, “Yale Scientific” said
“The EPA now has the proof. There is no imminent danger to the ozone layer by
CFCs. These losses will never be recouped”, and went on “We must distinguish
between scientists who present science as science and those scientists who promote
science policy decisions as scientific gospel”
“no imminent danger”
In 1985 the whole picture changed dramatically. Farman, of the British
Antarctic Survey, reported a seasonal loss of ozone over Halley Bay in the Antarctic.
“By 1987 comprehensive measurements showed that the springtime depletion

of ozone over Antarctica was the most severe yet seen. It was quite spectacular and,
occurring elsewhere, could have been catastrophic since 95% of the ozone between
altitudes of 14 and 23 km was destroyed in less than two months. The total ozone
column was reduced to 40% of its pre-1979 thickness. This was a total surprise and
a grave warning, though it was still unproven that the culprits were CFCS. But that
evidence was soon to come. The British findings were confirmed in August of that
year by reassessment of data from NASA’s Nimbus 7 satellite. This had been taking
172
OZONE DEPLETION POTENTIAL
measurements of ozone over Antarctica since 1978 - so why hadn’t they reported the
same low values? Because the computer had been told to reject exceptionally low
ozone values which were not expected. When the data were reprocessed with a less
intelligent computer they confirmed the measurements of the British team. In August
and September 1987 a large airborne American experimental campaign overflew
Antarctica and measured the concentrations of several trace gases up to altitudes
of 18 km. The results were as convincing as we are ever likely to be blessed with.
The free radical, C1O, appeared rapidly and abundantly in the late August and this
was followed by a dramatic fall of ozone in mid-September, which showed an inverse
correlation even in the smallest details. All other gases such as the nitrogen oxides
and even water, H2O, decreased with ozone; only C1O increased. The ‘smoking gun’
had at last been found and all the fingerprints were in place” ....George Porter
There are obvious lessons to be learned from the CFC story in regard to the
Greenhouse effect and global warming. Science itself, however, has to do with
“truth” and its elucidation. Of course, there are scientists who, like cabinet officers,
have been “economical with the truth” Some are given to exaggeration, others
blatantly dishonest. On the whole, however, a scientist embarked on a dishonest
approach to his subject would be like a tennis player who hit every ball out of court.
The whole exercise would be self-defeating and, in the end, such a scientist would
inevitably be discredited. Although this is manifestly self-evident, scientists who
warn about the dangers of radioactivity, or of pollution, or of inadequate hygiene,
etc., etc., are frequently attacked and denigrated by those who earn money or political
advantage by exploitation of the environment. Scientists are not infallible but “Yale
Scientific” (above) ought to have paid more heed to scientists engaged in pure
research than to the manufacturers of CFCs or aerosol valves. Attitudes similar to
those of “Yale Scientific” still abound (Section 7.4). Time, of course, will tell who
is right but, in the meantime, it might be wiser to emulate Noah than to heed
conspiracy theories put about by those with vested interests intent on becoming rich
or famous at the expense of the environment.
7.8 New CFCs for Old
The world’s chemical companies may have done much to improve our lives
but they have not been renowned for being friendly to the environment. Much
attention has been given recently to the impact of antiquated chemical plant on what,
until recently, was East Germany. Refurbishing that out-moded economy has already
cost many million DM and will certainly cost many millions more. Much of this will
be spent on cleaning up an environmental mess of a sort which would only be
tolerated by a totalitarian regime, No doubt the record is better in the West but not
so much better that it could be regarded as a course for rejoicing. Similarly there has
been a sorry record (of drugs, pesticides and herbicides which have killed and
deformed) to put along side those which have done what was intended of them
without damage. If we were to take a totally cynical point of view we could say that
industry can no longer, in a environmentally aware world, get away with so much
nor afford to totally disregard public opinion in its pursuit of profit. If we take a more
generous view, we should applaud the present attempts to present a kinder face. In
this context attempts to produce alternatives, less damaging to the environment than
CFCs, should be applauded even if the applause is muted by the likelihood that the
alternatives might not have all the virtues which are claimed for them.
CFCs are nasty because they contain halogens (chlorine fluorine or bromine).
For example CFC 12, widely used in refrigeration, releases chlorine in sunlight at
an altitude of 20-40 km and this promptly set about tearing holes in the ozone layer.
173
Moreover CFCs are stable in the lower atmosphere and are eminently suitable for
carrying the halogens to the stratosphere where they do so much harm. Currently
Table 7.5
Atmospheric Lifetimes and Ozone Depletion potential
Average values
Compound Lifetime ODP

(Years)
CFC 11 75 1
CFC 12 120 1
CFC 113 100 0.8
CFC 114 270 0.8
CFC 115 550 0.4
HFA 22 20 0.05
HFA 123 2 0.02
HFA 124 7 0.02
HFA 125 22 0
HFA 134a 19 0
HFA 141b 10 0.1
HFA 142b 27 0.06
HFA 143a 50 0
HFA 152a 2 0
CCl4 62 1.2
CH3CCl3 6.5 0.15
Estimates of lifetimes of HFAs and CFCs. This table also shows ozone depletion
potentials, defined as the potential ozone depletion arising from one tonne of the
compound compared to that of one tonne of CFC 11, over the whole of their
atmospheric lifetimes. Compounds of the methane (CH4), ethane (CH3 -CH3) series are
called “alkanes” or “saturated hydrocarbons” (because all of the carbon valencies are
saturated with hydrogen). Hence the term HFAs includes both HFCs and HCFCs
(fluorocarbons containing no chlorine or chlorine respectively). For example HFA
134a is CH3CH2F and HFA 123 (a possible substitute for CFC 11) is CH3CHClF.
there are compounds of a somewhat similar chemical nature such as methylene

chloride, trichlorethylene etc which are much less stable and would not act as
shuttles, transporting halogens into the ozone layer. Yet others contain no chlorine
and are therefore even more desirable. The chemical industry prompted by the
Montreal Protocol, has become suddenly interested in an “Alternative Fluorocarbon
Environment Acceptability Study”. This has focused on hydrofluorocarbons (HFCs)
which comprise two carbons, fluorine and hydrogen and HCFCs which are similar
but still contain some chlorine. For example it is proposed that CFC 12 (CF2Cl2),
one of the most widely used CFCs, might be replaced by tetrafluorethane
(HCF 2 HCF 2 ) in refrigeration and air-conditioners. Such compounds
(hydrofluoroalkanes or HFAs) containing hydrogen, are able to react with natural
hydroxyl radicals present in the lower atmosphere so that even those containing
chlorine (like HFA 123) have a low potential for “delivering” chlorine through the
lower atmosphere into the ozone layer.
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OZONE
7.9 Ozone
Ozone is extremely important to life on Earth and should not be regarded as

simply one more greenhouse gas. As we can see from Fig. 7.15, apart from water
vapour (not shown) the overall picture is dominated by carbon dioxide, methane and
CFCs and oxides of nitrogen (7.10). Nevertheless, stratospheric ozone owes its
additional importance to the fact that it filters out incoming short-wave radiation (ie
ultraviolet) rather than infra-red. Ultraviolet can cause skin-cancers and damage to
the photosynthetic apparatus of plants. In sufficiently large amounts, at particular
wavelengths, it can even cause genetic damage when absorbed by DNA.
Carbon Dioxide 49%
Other 13%
Nitrous Oxide 6%
CFC 11 & 12 14%
Methane 18%
Fig. 7.15 Present Contributions to Increasing Greenhouse Warming.
[Ultraviolet radiation can be classified as UV-A (above 320 nm), UV-B

(between 320-280 nm) and UV-C (below 280 nm). Most solar radiation in the
200-290 nm region is currently absorbed by stratospheric ozone but it should
be noted that artificial radiation with a maximum at 254 nm readily damages
the water-splitting facility of PSII and plastoquinone (Section 3.9).]
Anderson has recently shown that pea plants (Pisium sativum), grown in augmented
UV-B, can be damaged, photosynthetically, in several ways including adverse effects
on ATPsynthase and RUBISCO activity (Sections 4.7 & 5.2). Plants acclimatised to
high altitude growth appear to be afforded added protection by increased
concentration of phenolic compounds called flavonoids which, even in plants not
adapted to high UV-B, absorb all but a few per cent of incident ultraviolet at these
wavelengths. Caldwell, however, has drawn attention to the fact that whereas a 16%
decrease in stratospheric ozone would only increase the total UV at the Earth’s
surface by 1%, the damage to DNA would increase by nearly 50% and lower the
viability of pollen, less protected against UV than other plant cells. Kelly, who has
addressed some of these problems, points out that the known susceptibility of marine
phytoplankton to UV may be less of a problem than this might imply, because lethal
amounts of UV already penetrate the first 5 metres of ocean and a 20% increase in
UV would increase this depth from 5 to 6 metres without major attenuation of
photosynthetically active light.
175
OZONE
A somewhat more pessimistic note is sounded by Kirk,
“ A further, perhaps even more serious, consequence arises from the possible
link between oceanic photosynthesis and world climate. The phytoplankton of the
ocean fix about 30 billion tonnes of carbon per year. This takes place in the upper,
well-illuminated, mixed layer, but about 5 billion tonnes of this carbon, in the form
of zooplankton faecal pellets and aggregations of senescent cells, sinks down through
the thermocline to the deep sea. This loss, and the accompanying loss due to
precipitation of calcium carbonate derived ultimately from weathering of silicate
rocks, is made good by outgassing of CO2 from the Earth in volcanoes and soda
springs, and exchange of this atmospheric CO2 with the surface layer of the sea.
Normally a dynamic equilibrium between these processes exists, maintaining an
approximately constant steady-state level of atmospheric CO2. If, however, by
destroying the ozone layer and increasing UV-B flux into the ocean, we substantially
decrease oceanic photosynthesis, then we shall diminish one of the major sinks for
atmospheric CO2, and so in the long run may exacerbate atmospheric carbon dioxide
increase and its associated global climatic effects”.
In a way, ozone behaves a bit like clouds in the sky which reflect incoming
solar radiation into space. In addition, (Table 7.2) acting in the same way as water
vapour, tropospheric ozone (about 10% of the total ozone) absorbs long-wave
emissions from Earth into space and re-emits part of what it absorbs back towards
Earth. The lifetime of tropospheric ozone is relatively short but a 25% increase of
ozone throughout the troposphere would contribute about 0.2 Wm-2 to greenhouse
warming (c.f. Table 7.2).
[It is important to remember that heat and temperature are not the same. An
ocean of water at 12°C contains a great deal more heat than a cupful at 90°C.
Greenhouse warming tendencies (Table 7.2) can be calculated with some
certainty but it does not necessarily follow (Section 7.9) that increases in
greenhouse warming will give rise to an increase in surface temperatures.
Changes in amounts of specific greenhouse gases may enhance or ameliorate
positive and negative feedback mechanisms (for example, by affecting clouds
and precipitation). The thermal inertia of the oceans also slows down the rate
at which the temperature of the land surface and the atmosphere might
otherwise rise.]
7.10 Oxides of Nitrogen
“Laughing gas from leaky pipes” ....Oliver C. Zafiriou
Stratospheric ozone is formed (equations 7.5 and 7.6) by ultraviolet

irradiation of oxygen (the characteristic odour of ozone can be readily detected in
the vicinity of U.V lamps). Most ozone at the Earth’s surface is formed by industrial
activity and motor vehicles (which combine, in some climatic circumstances to
produce smog). Nitrous oxide (N2O) is responsible for about 8% of the greenhouse
effect. It also, like CFCs, contributes to the destruction of stratospheric ozone
(accounting for 10-20% of ozone depletion). On a molecule for molecule basis it is
200 times more effective as a greenhouse gas than CO2. It is presently increasing
at 0.2% a year (about half as fast as CO2) and resides in the atmosphere for nearly
a century. Much of this increase derives from the extensive use of nitrogenous
177
fertilizers, from burning and refining fossil fuels and from forest clearing. Although
the use of nitrogenous fertilization does not constitute a major contribution to global
warming it exemplifies the dilemma facing the Third World. In the European
Community the continuing, largely unrestricted, use of nitrogenous fertilizers does
little more than to increase agricultural surpluses, profits, pollution and political
arguments. In the Indian subcontinent it has averted or diminished the inevitability
of famine but, at the same time, it contributes to greenhouse warming many times
over because of the utilisation of fossil fuels in its manufacture, the release of N2O
in its use, and the inevitable increases in anthropogenic related greenhouse gases
associated with increases in population (from about one third of a billion in the last
century to about a billion in this).
Nitrification
}
NH 4
H 2O
O2
} NO2
-
-
N 2O NO NO3
N2
Denitrification
Fig. 7.16 Laughing gas from leaky pipes. This is a concept of Mary K. Firestone
elaborated by Oliver C. Zafiriou. Three metabolically discrete types of bacteria are
Solar involved in nitrification and denitrification. Nitrification is a process in which ammonia
(NH4+) is oxidised to nitrite (NO2-) and nitrate (NO3-). Denitrification consumes nitrate
Incoming Reflected Longwave and releases N2 back to the atmosphere. Here some of the processes involved are
represented as pipes which permit multiple pathways through which nitrous oxide (N2O,
laughing gas) and other oxides of nitrogen can be taken up and released.
7.11 Summary
(a) No atmosphere
Greenhouse gases constitute a blanket which keeps us warm. Without them

Gaseous absorption life on Earth, as we know it, would be impossible. The most important greenhouse
and re-emission gas and the one which Man influences least is water vapour but there are others such
as carbon dioxide and methane (which are increasing steadily) and a layer of ozone
(currently being torn apart) which are very dependent on human activity. By
affecting the concentrations of these gases Man is now having an immense impact
on his environment, some of the possible consequences of which are considered in
(b) With atmosphere Chapter 8.
178
CHAPTER 8 - CONSEQUENCES AND UNCERTAINTIES
CONSEQUENCES AND UNCERTAINTIES.
“One thing is certain, the rest is lies

The flower that once has blown, forever dies” .......Omar Khayam
8.1 What Might Happen
The consequences of unchecked emission of greenhouse gases can not be

defined with precision. Nevertheless, despite the many uncertainties about the
magnitude of the effect and the time-scale “the direction of future change is clear
and unambiguous”. It is believed (says Irving Mintzer, of the World Resources
Institute in Washington, D.C.) that, even if the lowest estimates are taken,
“today’s activities are propelling the planet over a period of a few decades
towards a climate that will be warmer than any experienced since the last
glaciation. Unless actions are initiated soon, to slow the rate of greenhouse
gas build-up, national economies and natural ecosystems are likely to suffer
severe consequences from this rapid alteration of the global climate”.
One of the few things that we can be reasonably certain about is that there
will be no significant decrease in emissions of greenhouse gases in the immediate
future. It is conceivable, but most unlikely, that current rates of emission might be
markedly diminished by immediate and concerted political action like the Montreal
Protocol, which seeks to put an end to the use of CFCs. On the other hand, as we
shall see, there is massive uncertainty about what might happen (and when) if we
continue to introduce greenhouse gases endlessly into the atmosphere at the going
rate. Moreover, there is no firm evidence that the increases in carbon dioxide, which
have undoubtedly occurred in the last century, have led to a detectable increase in
global temperatures. There seems to be an increase in air and sea temperatures (Fig.
8.1) but the maximum predicted increases are small, past measurements often
inaccurate, records poor, and fluctuations, brought about by other factors, very large.
180
WHAT MIGHT HAPPEN
It is, perhaps, unlikely that we shall see oxen roasted whole over bonfires on the
frozen Thames next winter but there are many still living who can remember the
misery of the bitter British winter of 1947. Climatologists attach no particular

significance to that winter or to the remarkably warm summer that residents of the
United Kingdom experienced in 1989. In scientific parlance, the noise to signal ratio
in the temperature record for the last 100 years is too large to permit unequivocal
interpretation. Whether average temperatures increase or not, there will still be
exceptionally hot summers and remarkably cold winters in the next century, as there
were in the present and the last. So we are, in the absence of proof, back to prediction
and at least, in regard to global warming, this can be done with reasonable
confidence. If greenhouse gases continue to be emitted more or less as they are now,
so that carbon dioxide (for example), doubles in the next 50 to 100 years, average
temperatures may rise by between 2°C and 5°C. This is largely a matter of arithmetic
based on the known physical properties of the gases concerned. The lack of precision
about the actual temperature changes comes from making educated guesses about
positive and negative feedback mechanisms, i.e. whether or not some possible
changes will enhance or diminish the underlying trend. For example, higher
temperatures can give rise to more evaporation and more clouds. Clouds intercept
incoming solar radiation (causing cooling) and out-going long-wave radiation
(causing warming). Precipitation, as rain, also releases latent heat of condensation.
It is difficult to predict whether these conflicting feed-back mechanisms will
reinforce or diminish greenhouse warming but current models seem to favour
reinforcement. The uncertainty about the timing relates to the equally difficult task
of relating emission to accumulation and to the almost total impossibility of arriving
at precise estimates of fossil fuel utilisation, forest burning etc., in the next century.
If we accept the arithmetic, we are offered “good” scenarios (two degrees

Celsius increases) and bad (five degrees Celsius increases) but if we attempt to look
beyond increases in temperature to the consequences of such increases we may, if
we are not careful, slide into the realms of science fiction. The truth of the matter
is that ecosystems are even more complex than economic systems and it has so far
181
been beyond the wit of governments to do a great deal about their national
economies. In addition, we shall not simply see events unfold without political
response. At present, global warming is regarded as matter for concern rather than
of impending disaster. If perceptions swing towards the latter then there would be
0.5
0.0
-0.5
1860 1880 1900 1920 1940 1960 1980 2000
Fig. 8.1 Global Warming 1860-1990 Measured as deviations from the average
between 1940-1960. A rising trend can be discerned despite major short term fluctua-
tions but it should be noted that the total change of about 0.5 degrees Celsius is small
and the possibility of error, particularly in old measurements, is large. (from CRU, East
Anglia)
a correspondingly larger response by governments and industrialists and there is no

doubt that even if some changes are inevitable their impact might be lessened if they
Ice-out in Maine come slowly rather than abruptly. As for the uncertainties themselves, they are
manifold. The climate of the U.K., for example, is dictated more by ocean currents
SIR - The folks up in northern Maine have than by latitude. Winters in New York City are incomparably more severe than they
kept an accurate record of the time of ice-
are in London despite the fact that New York is much further south, at a latitude
out on their largest lake, Moosehead Lake,
for the past 142 years. In the spring, ice out which the British would associate with winter sun in Spain. Should global warming
comes suddenly, usually in one day. deflect the course of the Gulf Stream away from the British Isles, the temperature
Moosehead Lake was the centre of the of Britain could fall, despite overall global warming.
logging industry in the late nineteenth and
early twentieth century, and ice-out in the
spring meant fresh supplies by steam-boat 8
Observed sea level
to the isolated logging camps on the Annual mean
Northeast Carry. So ice-out, like Christmas, 5-year mean
was celebrated, remembered and luckily 4
Sea level (cm)
recorded. More recently, ice-out contests

have been sponsored by the Moosehead
Lake Region Chamber of Commerce. Thus,
an exact record of the date of this event each 0
year since 1848 has been preserved. When
the dates are plotted and the best fit line
drawn, it appears that on average ice-out
occurs about 10 days earlier now than in -4
1848. Perhaps these data will be of interest
to those studying climate change, but up
here in Maine we are going to take them
seriously and start reducing greenhouse 1880 1920 1960
Year
gases. Donald G. Comb
Frost Pond,
Fig. 8.2 Increases in sea level. The rising trend of global sea level appears to follow
Maine, USA global warming (Fig. 8.1) but again the increase is small and the possibility of error
NATURE - VOL 347 - 11 OCTOBER 1990 is large. (from James Hansen/CISS)
182
CARBON DIOXIDE AS A FERTILISER
There are other uncertainties of much greater global importance. One is the
arctic tundra. This vast wilderness is largely comprised of a few millimetres of
vegetation overlying a metre or so of peat that has built up over millennia. Below
the peat there is ice, in places 5,000 m deep, depressing the earths crust by its massive
weight. This fascinating ecosystem is immense and extremely fragile. Drive across
it, in a tracked vehicle, and the tracks do not mend as they would on grass or
moorland or in forest. Instead, they persist and deepen. In twenty years time the
tracks will have become a chain of lakes. If global warming were to tip this volatile
system, from its present state into instability, the consequences could be incalculable.
8.2 Through a Glass Darkly
Inevitably, what we can learn from the past is limited. Some contemporary
politicians are quick to claim that peace in the world (by which they mean lack of
armed conflict between the “major powers”) has been maintained for the last forty
years by the threat of nuclear holocaust. Scientists, on the other hand, might question
such a conclusion in the absence of the control experiment. Paleo-ecology, like
history, is not open to experiment. We must distance ourselves from the concept that
too much can be gleaned from climatic history by way of using warmer climates in
the past as analogues for a future warmer world. Such “paleo-analogues” are “beset
with apparently insuperable problems” and these problems are made immediately
obvious if we are reminded, for example, that during the late Tertiary period (Table
8.1), some three to four million years ago, the Himalayas were about 3 km lower,
the Atlantic and Pacific were connected at low latitude, and substantial evolution of
organisms was still to occur. Accordingly, even though the late Tertiary was about
as warm as the world might be expected to become in the next century, it hardly
constitutes a credible analogue. Similarly, although the last interglacial period
(125,000 years ago) and the mid post-glacial period (6,000 years ago) were also
warmer, (at higher latitudes in the northern hemisphere) than today, they were
periods of greater net solar radiation, distributed in an uneven, seasonal and
latitudinal manner quite unlike the evenly distributed effects of greenhouse gases.
“However attractive the idea, paleoclimates cannot offer acceptable

analogues for warmer climates of the near future”.
On the other hand, the most recent paleoclimates can provide valuable
indications of the sensitivity of global climate to changes (other than changes in
greenhouse gases) and these can contribute both to the validation of global
circulation models and the mechanisms of climate change. In this context it is
arresting to learn, or to be reminded, that the most rapid change in climate
comparable to that predicted for the next century, which occurred 10 to 15 thousand
years ago, was no more than 2.5°C warming per millennia. In other words, warming
then was at least ten times slower than that envisaged for the next century. This
brings us to an important conclusion. The paleo-ecological record shows that (within
the last 12,000 years) forest trees, beetles, vertebrates and aquatic plants have
migrated across the continents in response to deglaciation and subsequent rises in
temperature during the post-glacial period. The most rapid rates of migration have
occurred, during the last two millennia, at rates of hundreds of metres per year. In
weighing this evidence it seems most unlikely that migration could occur at an order
of magnitude faster than this. Moreover, any migration which could occur would be
handicapped by barriers constituted by agricultural landscapes. Given the existence
of these barriers it is difficult to envisage migration of woodlands at a rate of 20-
30 m a month. Certainly migration of trees across Western Europe or N. America
183
GEOLOGICAL TIME SCALE
Era Period Years before Biological Features

Present
Cenozoic Quaternary 10,000-2 million First true humans; Homo erectus

Present to Tertiary 2-10 million First hominids; herbaceous
63 million plants more abundant
years ago 10-25 million
40-60 million
60-63 million First primates: prosimians
Mesozoic Cretaceous 63-130 million Angiosperms appear and
become abundant; modern
63 - 230 conifers arise
million Last dinosaurs
years ago
Jurrassic 130-180 million Gymnosperms, especially cycads,
and ferns dominate
First birds
Giant reptiles reign
PHANEROZOIC
Triassic 180-230 million Forests of gymnosperns and

ferns spread
Primative mammals and early
dinosaurs appear
Paleozoic Permian 230-270 million Conifers, cycads, and ginkgos
appear; earlier types of forests
230 - 600 wane
million
years ago Carboniferous 270-345 million First gymnosperms
Reptiles and insects appear
Devonian 345-400 million First large vascular plants
Modern groups of algae and fungi
appear
First amphibians and bony fish
Silurian 400-440 million First vascular land plants
First fish with jaws
Ordovician 440-500 million Plants begin to invade land
First vertebrates: armoured fish
without jaws
Cambrian 500-600 million First marine plants
First shell-bearing animals
Proterozoic 1000 million First living things: blue green
algae and bacteria; eukaryotic
600 million cells and multicellular oganisims
- 2.5 billion appear
years ago
1500 million
PRECAMBIAN
2000 million
2500 million
Archean 3000 million
2.5 - 4.5 + 3500 million Oldest dated rocks
billion
years ago 4000 million
4500 million Formation of the Earth
184
MIGRATION OF TREES
at 200 or 300 metres a month is unthinkable. The implications are immense and they
can be spelled out in some detail. Many ecosystems are likely to disappear and be
replaced by quite different ones. Some species will face almost certain extinction.
Conservation by Man will face entirely new challenges including artificial transport
of species unable to migrate with sufficient rapidity to ensure survival. At the
extremes there is the prospect of autocatalytic effects, the triggering of methane
release:-
“initially from the peatlands of the tundras and by melting of the permafrost,
and subsequently by decomposition of the vast deposits of methane hydrates”.
Such feed-back, if it occurred, would indeed spell global catastrophe.
8.3 Back in the Dark Days
“And God said “let there be light” and there was light” ...Genesis
Throughout this book we have been pursuing a constant theme. By and large,
Man is totally dependent on plants. Contemporary photosynthesis provides us with
food and firewood; past photosynthesis with fossil fuels. Utilisation of fossil fuels
on a large scale has changed the face of the world out of all recognition in a
remarkably short time. Look at the New York skyline from the sea and contemplate
what changes have been wrought in 300 years. Do the same from North Point
(Sydney), shrinking the elapsed time from 300 to 200 years. Go on to Hong Kong
and Singapore, marvelling and wondering all the while; marvelling at what Man can
create out of nothing in next to no time, wondering where it will all end. Clearly,
it cannot continue at this pace for long. The fossil fuels that have made it all possible
will soon be gone, other resources are fast diminishing, a finite space for agriculture
cannot support an infinitely large population. Pollution not only threatens habitats it
already shortens our lives. We can’t win, we can’t break even and we can’t stay out
of the game.
185
Table 8.2
Chemical composition of the atmosphere
Gas Volume Molecular

concentration (%) mass
Nitrogen 78.08 28.0
Oxygen 20.95 32.0
Argon 0.93 39.9
Carbon dioxide 0.03 44.0
Present (10 9 yr)

Time before
Percent of present level
100
0
Phanerozoic
Atmospheric
oxygen
Red Beds
Metazoa
1
Eukaryotes
Proterozoic
Denitrification
Aerobic respiration
and nitrification
2
organic carbon
Banded iron formations
Sedimentary
Green plant photosynthesis

Sulphate reduction
Crust differentiates
ocean accumulate
3
atmosphere and
Bacterial photosynthesis
Nitrogen fixation
Archean
chemoautotrophy
Fermentation (origin of)

4
Earth accretes
Fig. 8.3 Tentative time scale for the evolution of metabolism and of atmospheric
oxygen.
186
ESTABLISHING A TIME SCALE
To put some of these things in proportion and in context we might just take
a brief peep at the past to see where it all began. Present estimates put the formation
of the Earth’s crust at about 4,000 million years ago. Microbial life is very hard to
date but it must have appeared well before the Cambrian Era, 570 million years ago,
when fossil shells started to appear in the geological record (Table 8.1). The earliest
“micro-fossils”, which look very much like modern bacteria and blue green algae,
are now thought to have originated about 3,500 million years ago. By the
Carboniferous Period, which began about 350 million years ago, large trees (like
Lepidodendron, long since extinct) were piling up the coal deposits which have
1 N2
-2
10
CO 2
-4
10
Atmospheric partial pressures (bar)
H2
(scale unknown)
O2
Time
Chemoautotrophs
Abiotic synthesis;
Photoautotrophs
photosynthesis
assimilate H 2
assimilate H 2
Fermentation
Fermentation
Green-plant
respiration
respiration
Anerobic
Aerobic
No life
Fig. 8.4 Photosynthesis and atmosphere. Postulated evolution of prokaryote

metabolism and its effect on atmospheric composition
played such a key role in Man’s recent history. Only a handful of present day plants
like the horse tails (species of Equisetum) and the maiden hair tree (Ginkgo biloba)
have survived to the present day. Reptiles and insects abounded but mammals and
dinosaurs had yet to appear (180-200 million years ago). Flowering plants and
modern conifers did not arise until the dinosaurs were on their way out (63-130
million years ago). The first primate appeared 60-63 million years ago and the first
true humans only in the last 2 million years or so. Millions of years are hard to
envisage for organisms with the classic life expectancy of three score years and ten,
particularly when there are many occasions when an hour can seem like an eternity,
so here is another way of establishing a time scale.
“Imagine that all of time, from the moment when the earth’s crust first formed
right down to this moment, is compressed into one calendar year. Here is
what geologic time looks like on this calendar. The earth’s crust begins to
form on January 1; the oldest rocks known date from about the middle of
187
March. In May the first living things appear in the sea. By late November land
plants and animals have appeared, and in early December, the vast swamps
that formed the Pennsylvanian coal deposits have appeared, flourished, and
disappeared after four days. By mid-December dinosaurs have begun to roam
the earth; by December 26, just as the Rocky Mountains begin to rise up in
the American West, they become extinct. In the evening of December 31, the
first humanlike creatures have begun to appear. One minute and fifteen
seconds before midnight on December 31, the glaciers of the last great Ice
Age begin to retreat in America and Northern Europe. The Roman Empire
rises, flourishes for five seconds, and disappears in the waning seconds of our
year. Three seconds before midnight, Columbus discovers America.” ...Laetsch
What is the relevance of all of this to our main theme? First of all there is
the obvious point which should give us all pause for thought. On a geological time
scale, Man is a very recent event. We have been around, if you like, for only a few
hours on December the 31st. Even then it is only in the last second that there has
been the explosion in number which has taken population from a few million to 3,000
million now and probably over 4,000 million by the end of the century. That, and
all that goes with it, has only been made possible by events which took about 4-5
days early in December (i.e., 75 millions years or so in the Carboniferous Period).
Secondly there is the impact of photosynthesis on the atmosphere. Opinion

about how much carbon dioxide and oxygen there was in the atmosphere when life
started is divided and based on inference. The atmosphere itself is believed to have
“Free living chloroplasts”
resulted form “degassing” (a release of gases from the earth’s interior) a process
which continues today from volcanoes which release a great deal of water and carbon
dioxide into the atmosphere. Most of this may have occurred within 100 million
years of the earth’s formation. It has been suggested, by various authors, that:-
(a) “the water vapour and carbon dioxide contents of the primitive
atmosphere were about equal to their present values after an initial
accumulation period. Once water had started to condense and carbonate
188
FREE LIVING CHLOROPLASTS
rocks to precipitate from the oceans, continued degassing led to an increase

in the nitrogen content of the atmosphere, but caused no change in the carbon
dioxide or water vapour contents.”
(b) “that the carbon dioxide content of the atmosphere has never differed
markedly from present-day conditions”
(c) “that the ocean carbon dioxide content has probably been close to
constant for the last 3 billion years.”
but if impressions of constancy can be inferred from such statements they are not
universally agreed (Section 8.4). There is no suggestion of course, that oxygen has
remained constant since the “beginning”. Some oxygen would have been formed by
photo-dissociation of water but is not known whether this was as little as 0.001%
of present atmospheric levels (PAL) or as high as 0.25 PAL. What does seem clear
is that major changes commenced some 2,000 million years ago with the evolution
of oxygenic photosynthesis (i.e. oxygen producing photosynthesis) by organisms
capable of bringing about the photolysis of water. The organisms primarily
responsible were blue-green algae (the cyanobacteria) and it was almost certainly the
blue greens and other marine algae which increased atmospheric oxygen to
something like its present levels.
[Cyanobacteria are, in a sense, like free-living chloroplasts. They contain

chlorophyll within internal membranes just as the photosynthetic pigments in
“Free living chloroplasts”
chloroplasts are restricted to the thylakoid membranes. It is even conceivable

that green plant chloroplasts evolved from these organisms. Currently, one
group of workers finds that the closest relative of a chloroplast ancestor could
be the protist Cyanophora whereas another puts their money on the
prochlorophytes such as Prochlorothrix.]
The increase in oxygen during the evolution of the atmosphere may have been
complete before evolving life colonised the land masses from the oceans. Oxygen,
189
of course, is required for respiration but the crucial aspect of increasing partial
pressures of oxygen in the atmosphere was a concomitant accumulation of ozone in
the stratosphere. Ozone is formed in the stratosphere, and above, by the photo-
dissociation of oxygen
O 2 + hv → O + O Eqn. 8.1
followed by recombination of the atomic oxygen (O), so produced, with molecular

oxygen (O2)
O2 + O → O3 Eqn. 8.2
Ozone (O 3) absorbs ultraviolet radiation in the 200-300 nm range. DNA

(deoxyribosenucleic acid, the physical basis of heredity) is destroyed by UV
radiation (Fig. 8.5) at about 250 nm and
“contemporary micro-organisms would be killed in a matter of seconds if

exposed to the full intensity of solar radiation in this wavelength region”.
Because of the susceptibility of DNA to degradation by ultra-violet light

evolution must have gone hand in hand with oxygen evolution and ozone formation.
The oceanic cyanobacteria would have been afforded a measure of protection by
water (and perhaps by a degree of shielding by organic molecules and DNA repair
mechanisms) but there would seem to have been little possibility of invasion of the
land until the ozone layer was in place.
Today, it is commonplace to visualise the green plants that we see around us

as the source of our oxygen and it is true that oxygen consumption by animals, plants
and micro-organisms is in balance with oxygen produced by photosynthesis. These,
however, were not the plants which created the oxygen in our atmosphere, nor were
those ancient species, now extinct, which formed our coal deposits in the
Carboniferous period. All, or most, of this was done before they existed by the
cyanobacteria and other forms of marine phytoplankton. In all of this, the role of
carbon dioxide, released by degassing is uncertain. Some authorities (Section 8.4)
think that carbon dioxide may once have been much higher than today (perhaps 100
times higher) and that this would have contributed to surface warming during the
early period of Earth’s history when solar luminosity was believed to have been 30%
lower than at present. Because Earth is nearer to the sun than Mars, and further from
the sun than Venus, it avoided both the lack of accumulation of water vapour in the
atmosphere on Mars (which has left that planet frozen) or the “runaway greenhouse
effect” (which has kept virtually all of the water vapour in the atmosphere on Venus
and resulted in surface temperatures much higher than Earth). It should also be
remembered that whether or not ancient atmospheres once contained 3% carbon
dioxide or about 0.03% (as they do now) carbon dioxide must have been released
from reservoirs, such as the oceans to permit this conversion of carbon dioxide to
oxygen on a molecule for molecule basis
CO 2 + H 2 O → CH2 O + O 2 Eqn. 8.3
The total organic carbon content of the biosphere is about twenty times
greater than that in the atmosphere (approximately 3% in living organisms, 25% in
dead organic matter and 70% as coal and oil). This is still about 30 times less than
would have been needed to account for 21% O2 in the atmosphere. Moreover, oxygen
is consumed in the oxidation of reducing materials when sedimentary rocks become
190
ULTRA VIOLET LIGHT AND DNA
exposed to erosion and weathering. Some of the “missing” organic carbon is

dispersed in sedimentary rocks and it is also possible that the Earth’s crust is not
isolated from the underlying mantle and that significant quantities of material have
been exchanged between the two throughout geological time. Comparisons of the
isotopic content of the atmosphere and sedimentary rocks suggests that most of the
14
1.0 10
-1
Solar spectrum 13
10 10
at Earth´s surface
-2 12
Relative Biological Sensitivity
10 10
Photons / cm · sec / nm
10
-3
Erythema 10
11
-4 10 2
10 10
-5 9
10 DNA 10
-6 8
10 10
260 280 300 320 340 360
Wavelength (nm)
Fig. 8.5 Effects of ultraviolet light on DNA. The solid curve is the biological sensitivity
spectrum for DNA, and the dashed curve is a typical Earth-surface solar UV spectrum.
The response of human skin to sunlight (“sunburn”) is shown as the curve labelled
erythema.
organic carbon of biogenic origin in the latter had already accumulated there some
3000 million years ago. This is in accord with the fossil record because it would have
given the cyanobacteria (etc.) about 500 million years to bring this about. Even so
the oxygen content of the atmosphere did not arise to something like its present level
until about 2,000 million years ago, presumably because photosynthetically produced
oxygen was first used to oxidise iron, etc., in sea water.
[It is of interest, that paleoclimatogolists and atmosphere physicists have

usually and remarkably tended to put more emphasis on oxygen than on
carbon dioxide. Thus “We shall concentrate on oxygen as the most interesting
of the atmospheric gases, at least as far as life is concerned”.]
Of course, life as we normally think of it, depends on the presence of oxygen

and we are all aware of the physiological impact of thinning oxygen at high altitudes,
the need to pressurise high-flying aircraft and possibly even the advisability of
planning a honeymoon somewhere other than in the high Andes. Nevertheless, when
191
we come to consider the sort of fluctuation which may have occurred during the
Phanerozoic (changes in oxygen from about 0.25 to 1.5 present levels and tenfold
changes in carbon dioxide) we can scarcely discount the importance of the changes
in carbon dioxide which would, in otherwise stable environments, have profound
effects on present day organisms, quite apart from the indirect effects of carbon
dioxide on global temperature.
8.4 The Yo-Yo Concept
“ yo-yo, n. Toy (introduced in 1932) consisting of pair of discs with deep

groove between them in which string is attached and wound, rewinding itself
and returning to the hand when thrown down. ....Concise Oxford Dictionary.
What it does not say in the dictionary is that a yo-yo is supposed to go up

and down most of the time. Reading Section 8.3, or some texts about the atmosphere,
you might be left with the feeling that, after the first 100 million years or so of its
existence, the Earth’s atmosphere remained largely unchanged until the onset of
photosynthesis and thereafter the oxygen rose smartly from next to nothing (to
something like 21%) and stayed there, unchanged, until the present time. Some
authors and research workers take quite a different view however, and Fig. 8.6 and
8.7 are distinctly yo-yo like in appearance, showing major oscillations in oxygen,
methane and carbon dioxide. Sadly, this author lacks the competence to tell his
readers which climatologists to believe but the possibility that the atmosphere has
never been stable is interesting and certainly one which is relevant to contemporary
change.
Figure 8.6 comes from a book by the Russian scientists, Budyko, Ronov and
Yanshin. It shows massive oscillations in oxygen and carbon dioxide during a period
in which there were correspondingly large changes in living organisms. These
authors consider the possibility of a cause and effect relationship and pay homage
to the French scientist, Geoffrey St Hilaire, who wrote (in 1883)
“Let us suppose that, in the course of a slow and gradual advancement of

time, the proportions of different components of the atmosphere changed and
it was an absolutely indisputable result that the animal world was affected
by these changes”
Similar thinking is implicit in proposals by McLean that the dinosaurs became

extinct because of an enhanced carbon dioxide greenhouse effect (Sections 7.2 &
7.3) causing a sudden increase in global temperature, melting of the ice caps etc.
Precisely how this might have affected the dinosaurs or the other genera which
became extinct at this time (possibly as many as 75% of all of those in the Upper
Cretaceous which became extinct - Table 8.1) is highly uncertain but there is little
doubt that, either an abrupt warming, or an injection of carbon dioxide, would have
had a profound effect on ecological stability. Because the dinosaurs were so
spectacular, it is hardly surprising that their demise has attracted so much speculation
but there were changes to plants, round about this time, which were no less dramatic.
These were to have a much greater impact on Man who, while he was never to come
face to face with a living dinosaur (except in Conan Doyle’s “Lost World”), has
always been dependent on the flowering plants. These flowering plants came in (give
or take a few tens of millions of years) as the dinosaurs went out. Moreover, amongst
these plants, C4 species may well have arisen as a response to falling carbon dioxide
concentrations. As discussed in Section 5.10/5.11, C4 species have a built-in, carbon
192
RUBISCO IN HIGH CO2
dioxide enriched greenhouse. The C4 syndrome (Section 5.11) may well have
evolved more than once since the Cretaceous but the conventional wisdom is to
perceive it as a response to low carbon dioxide concentrations. According to this
view RUBISCO (ribulose bisphosphate carboxylase, Section 5.2) is an enzyme
which evolved when carbon dioxide was more plentiful and oxygen less plentiful
than at present. In such circumstances it did a better job than now, untroubled (in
its work of carboxylation) by competing oxygenation at present levels. As the carbon
mC
mC
10
mO
8
1.5
6
mO
1.0
0.5
2
0 0
500 400 300 200 100 0
m.y.
Fig. 8.6 The Yo-Yo in action. Changes in relative mass of carbon dioxide (mc) and
oxygen (mo) during the Phanerozoic (After Budyko, Ronov and Yanshin).
dioxide fell and as oxygen rose, the task of RUBISCO became harder and harder.
The C4 syndrome is seen as an evolutionary response to this situation as internal
carbon dioxide-enrichment re-established, in some respects, a working atmosphere
nearer to that enjoyed by the first photosynthesising organisms. Such propositions
are not, of course, open to verification but reference to Fig. 8.6 (itself no more
certain) gives credence to this concept in the sense that, at about the right time, it
looks as though there could have been relatively abrupt decreases in carbon dioxide
from concentrations an order of magnitude higher than those which exist now.
At the present time, mankind is concerned about much smaller increases in

carbon dioxide and the consequences that these might have on his environment.
Though much smaller, the rate of change is nevertheless very fast - so fast, indeed,
that there is no question of an evolutionary response and real doubt that even
migration might be too slow (Section 8.2) to keep pace.
Although there are major differences in scale between present and past
changes, both in regard to carbon dioxide concentrations and time, contemporary
193
changes still suffice to remind us how much life depends on climate and how much
climate depends on carbon dioxide. It was Arrhenius who, in 1908, came to the
conclusion that the oceans would be unable to absorb all of the carbon dioxide
emitted by industrial processes as fast as it was produced and that, in consequence,
global temperatures would rise and photosynthesis would flourish.
[In an early paper, entitled “On the influence of carbonic acid in the air on
the temperature of the ground” (Philos. Mag 41, 237-276, 1896) Arrhenius
credits Fourier with the first recognition, in 1827, of the possibility that rising
carbon dioxide might bring increasing temperatures in its wake.]
Depth (m)
0 400 800 1200 1600 2000
700
methane
600
500
CH 4 (p.p.b.v.)
2 400
0
300
-2 temperature
-4
DT(°C)
-6
-8
-10
300
280
carbon dioxide
CO 2 (p.p.m.v.)
260
240
250
220
240
200
220
180
160
0 40 80 120 160
Age (Kyr bp)
Fig. 8.7 Greenhouse gases and surface temperature. Changes in methane (top),
temperature (middle) and carbon dioxide (bottom) over the last 160,000 years. Based on
Vostock ice-core records. [After Chappellaz, Barnola, Raynaud, Korotkevich and Lorius
(1990)]. An age of (e.g.) 80K yr BP means 80,000 years before the present time.
194
CLIMATE FORCING BY CO2 AND METHANE
In 1938 Callender also warned of the possibility of climatic warming as a

result of burning fossil fuels but, perhaps because of the imminence of world war,
this warning also went unheeded and it is only in the last decade that the
consequences of anthropogenic increases in carbon dioxide have been taken more
seriously.
Figure 8.7 shows the Yo-Yo working like crazy in the relatively recent past
(the last 160,000 years). It illustrates fluctuations in methane, carbon dioxide and
temperature. The latter is based on deuterium content which is regarded as a good
indicator of past temperatures in central Antarctica. It depends on the principle that
heavy molecules of water (i.e. those containing deuterium) form snow more readily
than those containing hydrogen alone. In this way the amount of “heavy hydrogen”
(deuterium) in snow reflects the temperature at which it was formed.
Figure 8.7 is the work of Chappellaz et al. on the Vostock ice core (c.f. Fig.
8.1) and, although its important conclusions cannot be considered here at length, we
may note immediately that two main glacial/interglacial transitions (at 150 - 133
Kiloyears before present and 18 - 9 Kyr BP) occurred during this period and, in both
cases, the methane content rose from the lowest to the highest values recorded.
Carbon dioxide taken from the same ice core behaved in the same way i.e. the highest
and lowest values for both carbon dioxide and methane coincided with the warmest
and coldest temperatures respectively, although there were important differences in
profile which indicate that the carbon dioxide changes might have been driven by
oceanic changes and the changes in methane by factors affecting continental sources.
So what are we to make of this, particularly when we are aware that contemporary
methane is already much higher, and increasing much faster (and exponentially),
than before? Chappellaz et al. conclude that the methane (in the absence of an
anthropogenic contribution) rose when the ice melted and it was released from wet-
lands, methane hydrates etc. Thus the methane followed the temperature changes
rather than causing them. On the other hand they point out the probability of positive
feedback mechanisms, including the formation of stratospheric water-vapour from
oxidation of methane (Eqn. 7.4).
“It has been estimated that a doubling of stratospheric H2O from 3 to 6 ppm
(by mass) results in a warming of 0.6°C at the Earth’s surface”.
Together, the direct radiative effect of methane and stratospheric H2O

formation could have led to a warming of 0.15°C (about one third of the direct carbon
dioxide effect).
“The combined climate forcing of carbon dioxide and methane (about 2.3°C)
can therefore explain ~50% (~10% for methane alone) of the glacial
interglacial warming!”
There is no implication here that methane, (or for that matter carbon dioxide),
initiated climate change, simply that once initiated for whatever reason, greenhouse
gases can (and have) reinforced it. It also behoves us to believe (or at least not to
dismiss) the possibility that the atmosphere may have been no less stable in the more
distant past than relatively recently. However, when we come back to the present and
we start to think once again in tens, rather than in thousands, of years it may not
matter, all that much, whether the chicken comes before the egg or vice versa. We
are currently engaged in a vast experiment in which we are set to double atmospheric
carbon dioxide within the life-time of our children. We have not embarked on this
because we are driven by scientific curiosity but by simple greed and ignorance.
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Ignorance because, when the internal combustion engine and electricity generation
from fossil fuels first came on the scene, there seemed to be no good reason for not
using fossil fuels as fast as we could procure them (c.f. Section 9.2). Even twenty
years ago, there was more concern about what we all might do when the oil had gone
than for the consequences of burning it in so short a time. The consequences of greed
and selfishness are self-evident. I am no more willing than the next to forgo the
independence afforded by my car, to miss out on the pleasures of a full stomach, a
room that is neither too hot nor too cold. I wish to be able to travel swiftly, and in
comparative comfort, to Australia if it so suits me. I am very conscious, however,
that I do these things at some cost to my environment. Yet there are those (Section
9.5) who write, persuasively, that we can have our cake and eat it. Perhaps they are
wrong but one thing that is certain is that if the vast “cedar” forests of Australia had
not been felled to the last tree by the early settlers, these forests would still be
providing timber in large quantities. History is full of similar stories of plundered
resources and species driven to near, or complete, extinction (including the genocide
of Tasmanian man). Given a choice between conservation and terminal exploitation
there should hardly be need for prolonged debate. Add the bare possibility that the
consequences of exploitation could be incalculably nasty, even to politicians, and it
is hard to see why we should hesitate for a moment to endorse conservation.
8.5 Will it Happen?
In the words of the late lamented Professor Joad, it all depends what you mean
by “it”. For the sake of discussion we can consider a number of possibilities which,
although we can look at them separately are, in reality, inextricably linked. Firstly
there is the likelihood of continuing increases in greenhouse gases, secondly the
likelihood of global warming consequent upon the decreased emission of infra-red
radiation from earth to space and finally the possibility that global warming could
result in real, or near catastrophe.
“Life wasn’t meant to be easy.” ....English proverb
“Nichts ist schwerer zu ertragen als eine Reihe von guten Tagen” ...German proverb
The Mauna Loa record (Fig. 7.4) shows that carbon dioxide continues to rise
inexorably and present extrapolation indicates doubling in the latter part of the next
century. There is little doubt that carbon dioxide will continue to be emitted, at
something like its present rate, in the immediate future. On the other hand, there is
no reason why it should continue to be released indefinitely at present rates
(Chapter 7) except for the fact that the history of human behaviour in this century
gives us no encouragement to believe that there will be the international political
accord, and determination, to put in train those measures which would slow carbon
dioxide emissions to a manageable rate. Whether or not carbon dioxide will continue
to accumulate in the atmosphere at present rates is quite another matter and one
which will be influenced (indirectly as well as directly), by the rates of emission and
the climatic consequences of emission.
CFCs (Section 7.7) are, in this context, quite remarkable because it is not as
though refrigeration did not exist before their invention and will not continue to exist
if the Montreal Protocol really succeeds in ending their use. For this reason it is not
entirely improper, as is sometimes suggested, for the West to attempt to persuade
“underdeveloped” countries not to use them. China is a nuclear power and has a
successful commercial satellite industry. With a population of 1,000 million its
brightest and best brains are unlikely to be inferior in quality or in number to those
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CARBON DIOXIDE AND OCEANS
in Europe or America. At the same time it has recently elected to build 100
refrigerator factories (60% or more of Beijing households now have refrigerators) but
based on such inadequate technology that their CFCs pose a problem (as does the
generation of sufficient electricity to operate them). This is a problem of social
mis-management and muddled thinking, rather than Western conservationists
seeking to deprive the Third World of artefacts that they themselves enjoy. It should
also be noted, in passing, that domestic refrigerators cause little problem while they
actually function and would, in theory at least, cause none if ways could be found
to safely decommission them. Conversely, a major contemporary concern relates to
the production of frozen foods and inadequate technology which allows the more or
less continuous release of CFCs, by leakage, during the operation of factories
concerned in their production.
Methane will almost certainly continue to rise at its present rate of increase
because much of it is so clearly anthropogenic in origin and mankind is unlikely to
eat less rice or methane-producing ruminants or mine less coal (Section 7.6) in the
immediate future. Moreover, methane is an increasingly popular fuel and some will
continue to be lost on its way to fires and furnaces. When finally burnt it will also
give rise to carbon dioxide.
8.6 Down to the Sea
“I must down to the seas again, to the lonely sea and the sky” ... John Masefield
Carbon dioxide dissolves readily in water and can, according to the pH of the
solution and the presence of various other ions, enter into complex equilibria between
carbonic acid, bicarbonate and carbonate. Some carbonates (e.g. calcium carbonate)
are very insoluble, at least in waters of neutral and alkaline pH and are also used
in skeletal structures by a variety of marine organisms. Carbon dioxide is also taken
up, photosynthetically, by marine plants including microalgae which account for a
major fraction of global carbon dioxide fixation. The entire system is immensely
complex and still very poorly understood but some broad generalisations can be
made. The equilibrium, between newly generated atmospheric carbon dioxide and
oceanic surface carbon dioxide, takes less than a year to establish; that between the
surface waters (the top 70m) and the deep sea, about 1,000 years. The distribution
of carbon is thought to approximate to that in Table 8.3. This does not mean,
however, that carbon dioxide released from oxidation of fossil fuels will distribute
itself in these proportions. The equilibria between carbon dioxide, bicarbonate, etc.,
are such that only 9% of atmospheric carbon dioxide will enter the surface layers
of the oceans, the remaining 91% will remain in the air.
“in the absence of transfer to the deep sea, the ocean does not constitute a
significant sink for fossil fuel carbon dioxide”.
Transfer to deep waters does, of course, occur but the rate at which it occurs
is still very uncertain. On the basis of necessarily uncertain assumption it is believed
that about half of all of the man-made carbon dioxide now resides in the ocean. This
largely neglects the role of sedimentary marine phytoplankton and other marine
organisms which have directly or indirectly ingested photosynthetically fixed carbon
dioxide. As a result of death and decay of these organisms, soluble organic carbon
will be released, insoluble inorganic carbon will sediment. It should be borne in
mind, however, that (on a much larger timescale) sediments also affect the
complexities of CO2 → bicarbonate → carbonate equilibria. Dissolved carbon
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dioxide penetrating deep waters should, within 100-200 years, decrease the pH and
bring largely insoluble carbonates into solution. This, in turn, would increase carbon
dioxide solubility. The rates at which this might occur are highly uncertain.
Sedimentary carbonates, for example, are often “surrounded by a matrix of silicate
detritus”. In all of these matters, and in others discussed in this chapter, we can begin
to understand what infinitely complicated systems are involved and how large are
the degrees of uncertainty about our influence upon our environment.
Recent ocean models from the Max Planck Institute in Hamburg, based on
tritium measurements as indicators of the rapidity of mixing of surface and deep
waters, suggest that, if future carbon dioxide emissions could be abated, so that they
did not exceed present rates of output, uptake by the oceans could delay carbon
dioxide doubling for two or three centuries. It can also be argued that if all fossil
fuels reserves now known to be in existence were burned they would not double the
carbon dioxide content of the atmosphere over this period assuming that, as now,
only 50% of what is released would remain in the atmosphere. Of course, the
definition of a feasible reserve (i.e. one which could be recovered with due economy
and without unacceptable environmental impact) might easily change in a world
increasingly desperate for fuel but these arguments do at least underline the fact that
Table 8.3
Distribution of Carbon dioxide between atmosphere, biosphere and ocean
Atmosphere 1.5%
Oceans 94.5%
Warm surface 1.5%
Deep Ocean 70.0%
Biosphere 4.0%
even current predictions about carbon dioxide doubling cannot go entirely

unchallenged. It must not be forgotten that, regardless of what happens to carbon
dioxide, CFCs will continue to pose a threat and that methane released by Man’s
activities has trebled in this century. Nevertheless even the apparently remorseless
rise in carbon dioxide, which will remain a major concern, is still not so inevitable,
nor its rate of accumulation so soundly based on fact, that there is no room for doubt
or possibility of amelioration (Chapter 9).
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MISSING PRESUMED LOST
8.7 The Missing Sink
“Error of opinion may be tolerated where reason is left

free to contradict it” .....Thomas Jefferson
One of the many uncertainties about the greenhouse effect, perhaps the major
uncertainty, concerns the missing carbon dioxide. According to different estimates,
anything from 30-50% of the carbon dioxide released into the atmosphere simply
gets lost or, in other words, cannot be accounted for. Since most of the surface of
the globe is covered by oceans it is a good bet that this is where much of it must
finish up but how it gets there is quite another matter.
Surprisingly, the biological factor in the uptake of carbon dioxide by the

oceans is much more poorly understood than might be imagined. It is sometimes
assumed that, since the oceans cover so much of the Earth’s surface, their
photosynthetic capacity (like their capacity to dissolve and release carbon dioxide),
is commensurately large. In fact this is not so. In terms of accumulated dry matter
per year the land is twice as productive as the sea (Table 8.4). Terrestrial
photosynthesis per unit area is five fold greater than ocean photosynthesis. There are
however, some mysteries to be solved. Photosynthesis per unit chlorophyll by marine
phytoplankton is said to be six times greater than terrestrial photosynthesis although
the chlorophyll content of both groups of plants, expressed as a percentage of dry
weight, seem to be about the same. As Kelly points out there is no biochemical
evidence in support of these latter claims, based on rather dubious techniques
involving inappropriate use of radioactive carbon and possibly lack of appreciation
of the role of pigments other than chlorophyll e.g. (phycobilipigments) in light-
harvesting in marine phytoplankton (these could lead to an exaggeration of rates
expressed on a chlorophyll only basis). Many marine algae also have “carbon
dioxide-pumping” mechanisms (which do the same job as carbon dioxide enrichment
mechanisms in C4 plants but in a different way). Conceivably these also might lead
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to the accumulation of tracer in inorganic carbon reserves. Conversely, accumulation

of soluble organic carbon in surface waters recently reported by Japanese workers
could, if confirmed, lead to upward re-evaluation of oceanic photosynthesis,
expressed on an area basis.
Marine photosynthesis differs from terrestrial photosynthesis in several

important ways. Most obviously the major limitation on the land is water. This is
not difficult to see in temperate regions. In a comparison of deserts and rain forests
it is self-evident. Marine phytoplankton are not, generally speaking, short of carbon
dioxide (because of “carbon dioxide-pumping”) nor often too cold to photosynthesise
whereas coniferous forests, for example, are carbon dioxide limited in summer and
mostly unable to fix much carbon dioxide in winter. Many land plants can be made
more productive if given fertilisers. This, of course, is a central feature of western
agriculture but, as famous Rothamsted experiments have shown (Section 1.5) crops
manage quite well without. Some of the most massive accumulations of natural
biomass (rain forests) stand on extremely infertile soils. Marine phytoplankton, by
comparison, are normally desperately short of nitrogen, iron etc for the simple reason
that these essential elements are present in such low concentrations in sea water. This
accounts for the otherwise surprising productivity of cold waters which happen to
be nutrient rich and of areas in which there is a continuous upsurge of nutrients from
deep waters.
Table 8.4
Global net productivity of terrestrial and marine plants

(from Whittaker & Likens, 1975)
Production Giga tonnes

Environment dry matter.yr -1 (P)
Total %
Marine
Open ocean 42 24
Coastal 13 7
Terrestrial 118 69
[Marine phytoplankton fix significant quantities of carbon dioxide by

carboxylation of phosphoenolpyruvate. This has led to ill-informed
suggestions that PEP carboxylation (Section 5.14) could compensate for a
perceived deficit in RuBP carboxylation (Section 5.12). More knowledgeable
scientists and readers of this book will readily understand that this is a
nonsense because all carbon dioxide fixation ultimately depends on RuBP.
How else would a plant get its PEP?]
Land plants are often light limited and many grow in shade environments. On
the other hand they do not, in general, suffer the constant attenuation of light, by
water, experienced by marine algae.
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RUBBISH PAR EXCELLENCE
8.8 What Rubbish!
“A good skip, a what you like, a dolly or a pepper ......” ..Traditional
Although I do not usually get into this sort of thing (except in a perfectly
acceptable sort of way) I am told, on good authority, that Marks and Spencers now
sell knickers on plastic hangers. This scarcely merits surprise. The other day, in
pursuit of energy conservation, it took me a good ten minutes, a pair of pliers and
more patience than I normally carry around with me, to force entry into the plastic
container surrounding a time-switch. How things have changed. Screws and nails
were once dispensed by iron-mongers in paper bags (following weighing in brass
scoops which lasted for ever). Milk came in jugs (rather than fiendish micro-buckets
of plastic, pre-programmed or predestined to launch their contents over your best suit
or dress). Celery once came fresh from the earth. Am I the only one too shy to recruit
the aid of an air-hostess to help me fight my way into a plastic meal wrapped in a
plastic enclosure?
All of this is rubbish par excellence; refined trash that no one needs. This
brings us face to face with the starving in Ethiopia. Perhaps you might feel that I
exaggerate. But let me offer two examples from my own experience. Picture a scene
in Port Jefferson, Long Island. A lunch served on plates and serviced by cutlery
which would have won prizes for material and design in the United Kingdom of the
1950’s and which would still be prized possessions in many a Third World home.
What to do with these at the end of the meal? Commit them perhaps to some energy-
devouring washing machine? Not at all; “please put them in the garbage bag”. Is
this really less offensive than killing mink to wear as ornament? Of course not.
Picture the scene that meets the eye of the first-time visitor to India. What are
those tiny enclosures, wrought in hardened mud, designed to accommodate? Not
people, not people, not people? Go to the outskirts of Delhi and walk past the biggest,
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nastiest, rubbish pile that you might imagine. What covers its smoking and steaming
surface? People? What are they doing there? They are living there, it is their home.
So there is rubbish and rubbish, garbage and garbage. Even the most modest
and environmentally conscious person that ever existed generates rubbish. Even
kings and presidents and priests must shit and eventually die. There are parts of what
we buy or acquire as food which we would rather not eat. Friendly wood-fires
produce carbon dioxide and a modest amount of ash. Clothes become rags. All of
this is acceptable on a small scale. An equilibrium is established with the
environment as organic materials are degraded by bacterial action, as iron rusts.
Translate this into the context of “civilised” Western Society. We are back to plastic
shrouds for everything from onions to hardware. We can drive past mountains of
rusting cars. We are dimly conscious of comparable mountains of CO2, of SO2, and
of NO2. We curse the necessity of disposing of an immensity of Sunday newsprint,
of beer cans and wine bottles. Some of us salve our consciences with trips to bottle
banks and by the encouragement we give to Boy Scouts to salvage waste paper. How
many of us take our bottles and cans back to the supermarket? How many of us
complain about plastic wrapped vegetables, plastic wrapped pills, plastic wrapped
contraceptives? Beaches thick with undegradable plastic flotsam and jetsam is
regarded as an inevitability; how sad.
And yet there is a gleam on the horizon. Inevitably, since we are all human
and equally culpable, it is not lack of concern or high principles but often necessity
which causes us to make our contribution to the rubbish mountain. Given a chance
we don’t wish to share the fate of the garbage pile dwellers of Delhi. Self-interest
beckons us in other directions. Slowly the penny drops. Loading garbage into skips
and hawking it round the world suddenly seems a facile solution. Giving it to the
British, a nation currently prepared (at a price) to take anything from dioxins to other
people’s used plutonium, suddenly seems just a shade immoral - one jot removed
from selling it to Third-World countries, desperate to earn any sort of living.
So where do we begin? Turning to the ideas of Lovins (Section 9.1) we can

begin to see that the real alternative to
“putting diapers on dirty power stations”
is not to generate rubbish in the first place, whether it is waste carbon dioxide or
sewage. Immediately we must recognise degrees of realism. We cannot avoid
producing rubbish or waste entirely but we can embrace the principle that the polluter
must pay. It is a simple matter to make bottles, cans and used automobiles into
objects of desire for those who would wrest a living from recycling rubbish (is it any
surprise that waste vendors and recyclers are often amongst the most affluent
members of society?). Smaller vehicles using lead-free petrol can be encouraged by
governments, if they so wish. Collecting waste paper and reprocessing it is unlikely
to be without environmental impact in its own right but it certainly has the edge on
using trees for this purpose.
[“Toilet” paper, made from unbleached recycled newsprint sometimes has an

off-white colour which apparently causes no raised eyebrows in Continental
Europe but is not yet acceptable to the fastidious British regardless of what
they are just about to do with it. The time-honoured North American custom
of using Sears Roebuck catalogues in rural privies presumably went out with
the model T Ford. Perhaps the Indian custom of using a hand and water will
soon come to acquire a Green image.]
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GENERATING GARBAGE
Steps in this direction will have little real impact but they are helpful because
they diminish the sense of real frustration that many of us feel when confronted with
these problems. They also encourage thought and awareness. It is better to conserve
energy than to build new electricity-generating plant or nuclear power stations. It is
better to insulate buildings than to erode their fabric with acid rain. It is clearly better
to avoid creating “unnecessary” garbage. We are left with what is “necessary” The
only really effective way of dealing with that problem (Sections 8.10 & 8.11) is the
ultimate Green solution of making fewer people.
The fundamentals are inescapable and the logic is inevitable. If we cannot

dispose of our faeces in an acceptable manner we must produce less. Malthus is no
longer a prophet without honour (Section 8.11). Of course we deny the evidence of
our senses. People are said to be fat, not because they eat too much but because they
are of sedentary habit or hormonely imbalanced. The fact that there were no fat
people in concentration camps or amongst the starving in Ethiopia is somehow far
removed from what comprises the most effective diet. In the same way we care not
to think about the fact that there are too many of us, unless, of course, it is too many
of them. In the end, burying our heads in the sand will no longer be a solution. We
can start by banning or disapproving or taxing unnecessary garbage out of existence.
All of it takes energy (which we cannot afford) to produce and thereby puts carbon
dioxide, sulphur dioxide or whatever into our atmosphere. All of it takes space
(which we cannot afford to squander), or pollutes our environment, or both. All of
it is a literally disgusting waste of resources, both human and material. We can only
hope that apples or nails in neat plastic containers will become as socially
undesirable as thick fur coats or Semtex in radio/cassette recorders.
8.9 Will Temperatures Rise and Catastrophe Follow?
“Till a’ the seas gang dry, my Dear

And the rocks melt wi’ the sun” ....Robert Burns
Global warming is almost certainly inevitable. If it occurs it will not result

from natural causes. It will be a consequence of Man’s activities, as he rapidly
restores to the atmosphere carbon dioxide removed by millennia of past
photosynthesis. It will be because he augments this greenhouse effect with methane
and synthetic gases such as CFCs. It should also be remembered that the world as
we know it today has been largely fashioned by the use of fossil fuels and that, even
if photochemical generation of electricity (Chapter 9) suddenly became so cheap and
efficient that everyone could meet their total electrical requirements from
inexpensive panels on their roofs, there would still be a growing need to find
replacements for the coal and petrochemicals that we now use so extensively. There
is no possibility, in the short term, of preventing the release of greenhouse gases. All
that can be hoped for is that contemplation of the possible consequences brings such
a world-wide and unified determination to diminish the present rates of release that
Man will buy time to adjust to the changes which the greenhouse effect will impose.
8.10 Can Population be Maintained?
“I wish I loved the Human Race,

I wish I loved its silly face” ...Sir Walter Raleigh
Current predictions suggest that, by 2075, world population will have

stabilised at between 8 and 10.5 billion. Looking beyond that could be regarded as
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“The perpetual struggle for food and room”

.....Malthus
204
PROBLEMS OF POPULATION
foolish or simply a waste of time, given the uncertainties involved. There are,
however, related questions and facts which warrant consideration. First we might ask
why there should be any doubt that things should not go on indefinitely as they do
now. Common sense would tell us that continuing expansion is impossible. Everyone
has heard of, or might be convinced by, the intrinsic truth of the story in which a
pair of rabbits were put down on a tiny, uninhabited, but well vegetated tropical
island. Some years later, passing sailors found the island, stripped of much of the
vegetation and littered with the bones of hundreds of rabbits. Certainly it is self-
evident that life of any form depends upon the consumption of resources and if
resources are not renewable (or consumed faster than they can be renewed) there is
no possibility of a continuously expanding population. Conversely, if we look at the
population of the U.K. in the Middle Ages we find that although it was tiny by
comparison with the present, it was almost entirely self-sufficient and in equilibrium
with its environment. It had no need to import food, goods or materials from abroad.
It did not need to consume fossil fuels, the native forests could provide wood or
charcoal to meet every need. Pollution of the environment undoubtedly occurred but
not at rates that were too large to be accommodated by natural processes of decay
and erosion. That is not the present situation. We are now using irreplaceable
reserves (most obviously fossil fuels but there are others) and putting them back into
our environment, but changed in such a way that our environment itself is being
changed in ways which are not consistent with life as we would prefer to see it. Ask
a physicist or the man in the street what have been the most important scientific
advances in the last half century. The answers might range from nuclear fission to
television. Ask a biologist the same question and he might say antibiotics, selective
herbicides and the contraceptive pill but he would also undoubtedly identify the work
by Watson and Crick, which established the chemical basis of heredity, as the
discovery most likely to change life as we now know it. All of these things would
have been largely inconceivable to someone attempting to predict the future a
century ago. Moreover, the rate of advance of modern science is such that it is almost
inevitable that presently inconceivable discoveries will be made in the next century.
The optimists take refuge in this, believing that new ways (the “technical fix”) will
be found to cope with present problems. There is obviously some room for optimism
but, this is not to say that we should do nothing now and simply trust that our unborn
children will come up with hitherto undreamed of solutions. The following, based
on facts and reasoning set out as far as possible in the preceding chapters of this
book, should give us pause for thought.
8.11 Malthus Revisited
It is implicit in any consideration of the facts that the greenhouse effect results
from Man’s activities and that one certain way of bringing Man back into equilibrium
with his environment would be to reduce populations to a very much lower level.
A controlled decrease in population is not by any means the worst scenario that can
be envisaged. Populations in the western world which threatened to double within
the last half of the present century have already stabilised and there is little to choose
between stability and gradual decline. Stability was not brought about by coercion
or regulation but by the contraceptive pill, medical advances, economics and
changing social attitudes which have encouraged young women to pursue careers
rather than procreation. If every “married” couple produced only two children,
populations would eventually fall for the simple reason that disease, disaster or
famine would ensure that not every child would survive to procreate in turn. It is not
difficult to imagine many societies in which a combination of economics, self-
interest, and changed ethics could not combine to make families of more than two
205
children at least as socially unacceptable as smoking in aircraft or mugging old

ladies.
[We might also be reminded of the science fiction story about the man who
asked why an alien race was rapidly colonising the entire known universe. He
was told that it was a matter of ever-increasing population combined with the
political undesirability of controlling procreation. The man replied that if the
aliens were unable to control their breeding, someone or something might
have to do it for them. In this parable we could just as well envisage our
environment as the instrument which might control our breeding. If we
continue not only to use our non-renewable resources in a profligate manner
but also to use them in a way in which they will affect and diminish our
environment there is every prospect that our environment will turn on us and
declare itself unable to sustain existing levels of population.]
8.12 What Will Happen If We Get It Wrong?
“This is the way the world ends,

Not with a bang, with a whimper” ....T. S. Eliot
No one knows what will happen if we get it wrong. Do not, dear reader, be
persuaded otherwise. Not so long ago, Margaret Thatcher was Prime Minister of
England. (I say England, advisedly, because the Scots took a somewhat different
view even if they had to go along with the rest). She had ruled England for one fifth
of my lifetime and, if there is one thing which can be said with present certainty,
she would have liked to continue to do so for a few years more, just as I yearned
to see what life would be like with someone else at the helm. When she came to
power, inflation in the UK was a little over 10% and she consistently made the
reduction of inflation her principal aim. At the end of her term of office, inflation
was slightly greater than when she took over. Why do I say this? Well, of course,
it is not that I feel a deep affection for Maggie but I do not doubt that she would
have dearly liked to see us down to 1% inflation or that she had access to a great
deal of well informed economic advice. It is quite simply that economics is an
inexact science, entirely comparable to biology.
[In my youth I was obliged to spend two years of my life as a radar mechanic
in the “Fleet Air Arm” (Naval Aviation). I was “called up” (“drafted”) for the
period of “Hostilities Only” although, in December 1946, hostilities had long
ceased. Resenting this loss, of what might have been the best two years of
my life, I consoled myself with the thought that if I had been marginally older
it might have been six rather that two and I might never have returned to
civilian life at all. Struggling with such thoughts I was amazed to discover
that (in the Navy’s view) biologists made better radar mechanics than
physicists. The former viewed radar as they might regard living organisms,
wayward and devoid of rationality. The physicists (raised on the behaviour
of “ideal gases”) were so disappointed by the failure of radar to obey some
of the “rules” that they retreated into frustration and despair. Perhaps
economists would make good biologists and vice versa.]
So no-one, knows what will happen. All we can do is to make some very poor
guesses about what might happen. Maybe existing “evidence” is inadequate and
suspect but, if we were in a poker game, we would have to settle for the probability
of elevation in mean global temperatures by as much as 2 or 3 degrees in our
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WHATEVER HAPPENED TO THE MALDIVES?
collective life times. On this basis, climates will become even less predictable (even
given better technology and computers) than it is at present. The UK used to have
“weather” whereas continents, like America (North & South), Europe and Australia
had “climate”. England, it seems, may soon export its weather, as well as its language
to the world. Everything will become very unsettled.
Have you been to the Maldives? Flying in from Europe you see a
representative sample of the 12,000 islands. Some of these are little more than sand
spits, most of them uninhabited, few populated, none more than two metres above
the sea. The first nation in the world to disappear if the waters rise. Maldives are
about as near as we can get to the romantic concept of desert islands.
“with oval basins of coral-rock just lipping the surface of the sea,
and each containing a lake of clear water” .....Charles Darwin
There are those, quite literally, which resemble the cartoon drawings that we
all know so well. So they are very beautiful and great places for a pleasant holiday.
It would be sad to see them go but, in global terms, would it matter all that much?
Perhaps not (it all depends whether or not you take John Donne’s view of life or if
you would regret the casual destruction of one of the numerous paintings, by Monet,
of the bridge over his pond). On the other hand, if you happen to be a native of
Amsterdam, New York, London, Boston, San Francisco, Sydney, Tokyo, Singapore,
Hong Kong or Shanghai you might feel some concern because, in the words of Tom
Lehrer.
“the bomb that falls on you, will kill your friends and neighbours too”
In other words what is bad news for the Maldives is bad news for many of
the principal ports and centres of population in the world. So if the waters do rise
we can wave goodbye to the low lying areas of many major cities and to large areas
of very productive agricultural land. But, will it happen? We are back to “we don’t
know but it is possible”. If we return, for the moment, to politics we immediately
find this weird ambivalence in thinking. The United Kingdom has spent, and is
spending (despite the demise of a supposedly aggressive Soviet Union) vast amounts
of money on “an independent nuclear deterrent”. How much it has spent is hard to
say because realistic estimates would have to take into account the disguised
expenditure on establishments which were ostensibly concerned with the nuclear
generation of electricity and, in reality, with the production of plutonium for bombs.
But let us not get into arguments about whether or not this policy is laudable or
ludicrous. Let us simply assume that it has worked. Why then are we not prepared
to spend a fraction of this sum on energy conservation, knowing that what we spend
in this way could slow global warming (however marginally) and would almost
certainly make good economic sense and might even stave off global disaster?
One thing that we can be reasonably certain about, once we start to talk about
spending money or cutting down on wasteful and damaging use of fossil fuels is that,
if we are to do it at all, we had better start soon. London has recently spent a lot
of money on a barrier across the Thames which was designed to hold back the waters
when rare combinations of high-tides and on-shore winds combined to inundate large
areas of the city. Flood Street, in fashionable Chelsea earned its name the hard way.
It has all happened before.
For the moment the threat has receded but, as the sea levels rise, it will return.
Since one in four of those living in England have their homes within 25 miles of
207
Flood Street there is little doubt that money will be found but don’t count on dry
feet if you live near the Wash or in other low lying areas like Hull, New Holland
and many parts of East Anglia.
8.13 How Will Rising Carbon Dioxide Affect Plants?
Of all the many intrinsic uncertainties of the greenhouse effect this is one of
the largest, not least because it is equally to the point to ask how plants will influence
the greenhouse effect. As we have seen (Section 8.6), about half of the carbon
dioxide released to the atmosphere gets lost. If it does not remain in the atmosphere
it can only go into the oceans or the land masses and there is no doubt that
photosynthesis by phytoplankton and land plants makes the major contribution to
carbon dioxide uptake.
[In figure 7.4, for example, the annual “zig-zags” in the Mauna Loa graph of
atmospheric carbon dioxide are mostly attributable to diminished
photosynthesis by land plants in northern hemisphere winters. The tropical
forests of the southern hemisphere are essentially evergreen and temperatures
in these forests are such that there is no comparable decrease in winter
photosynthesis as there is in the coniferous forests of the north.]
It is by no means certain, however, that carbon dioxide uptake by land and

ocean will remain unchanged as atmospheric carbon dioxide concentration rises. The
biological component of uptake is unlikely to be indifferent to enhanced carbon
dioxide or to increased temperature, nor is it inconceivable that entire ecosystems
could change beyond recognition. Regrettably our understanding of the physiology
of individual plants, let alone our knowledge of the physiology of ecosystems is so
inadequate that we can do little more than speculate. Let us start, at least, from
relatively firm ground and progress as cautiously as possible into the realms of
science fiction.
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CARBON DIOXIDE AS A FERTILISER
8.14 Carbon Dioxide as a Fertiliser.
There is no doubt that some plants do better, in a lot of ways, in carbon

dioxide enriched air. It might be supposed that using augmented carbon dioxide in
greenhouses to promote plant growth came from an understanding of plant
physiology. It did not and it is a matter for regret that the world at large knows little
and cares less about the process of photosynthesis on which we all depend. So, who
knows, there could have been someone who thought that, since plants require carbon
dioxide to photosynthesise, it would have made good sense to offer them a little
more. It is even possible to find references to suggestions of such commercial
application in fairly venerable tomes like Rabinowitch’s “Photosynthesis and
Related Processes”. Sadly, it appears that contemporary carbon dioxide fertilisation
came not from earnest perusal of the scientific literature but from Dutch tomato
60
1% O2
50 21% O 2
Chenopodium album (C3)
40
Amaranthus retroflexus (C4)
photosynthesis, µmol, CO 2 m s-1
-2
30
20
10
0 100 200 300 400 500 600

Intercellular CO 2 concentratrion (C i ), ppm
Fig. 8.8 Effect of carbon dioxide on photosynthesis. Response to intercellular carbon

dioxide in Amaranthus retroflexus(C4) and Chenopodium album(C3). Data from Pearcy.
growers who burned propane in greenhouses (for heating) and found it led to better
yields than other forms of heating which did not generate carbon dioxide in the same
space as the growing plants.
Carbon dioxide fertilisation is an immensely complex business. Applied to

tomatoes it can affect many aspects of plant growth (including the number of fruit
209
per truss and their size and quality) but there is no doubt that it works in the sense
that it changes the nature of the crop for the better. In modern commercial practice
it can make the difference between profit and loss.
Similarly, there is no doubt that, if we were to compare the rate of

photosynthesis by many plants in air with those in air containing twice as much
carbon dioxide, we might expect to see about twice as much photosynthesis per unit
time. Not all plants would show such a large response. Armed with our knowledge
of C4 photosynthesis (Chapter 5) it would come as no surprise to discover that C4
plants, with their own built-in carbon dioxide concentrating mechanisms, are less
responsive to augmented carbon dioxide than C3 species (which depend upon
unaided diffusion of carbon dioxide from the external atmosphere to the site of
fixation within the chloroplast).
[In this regard, C3 species provided with additional carbon dioxide will, in
general, respond to changes in their immediate environments, such as
increases in light intensity and temperature, much as though they were C4
plants (Chapter 5). In other words, if they are provided with sufficient carbon
dioxide to suppress photorespiration and enhance photosynthesis, C3 species
will do what C4 species accomplish unaided by virtue of a combination of
leaf structure, biochemistry and internal transport.]
0.08
C3
Quantum yield, CO2 per mol photons
0.06
C4
0.04
Normal O2
30° C
0.02
0
0 200 400 600 800 1000
CO 2 , ppm
Fig. 8.9 Effect of carbon dioxide on quantum yield in C3 and C4 species. [After
Osmond, Bjorkman and Anderson (1980).]
Much also depends on the experimental conditions under which

measurements are made. If photosynthesis is limited by cold or by poor light, the
response to increased carbon dioxide will be less readily detected than if all other
external constraints have been removed. In a way this is self-evident but it has, in
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INTERACTION OF CARBON DIOXIDE AND LIGHT
the past and in the absence of experience, led to the erroneous idea that (putting to
one side debates about cost-effectiveness which have more to do with market forces
than plant physiology) carbon dioxide enrichment only helps under otherwise
favourable conditions. More importantly in the present context, it has added to
uncertainties about the consequences (for photosynthesis) of growing plants in high
carbon dioxide as compared with briefly exposing (to high carbon dioxide) plants
C4 plant
with 300 ppm CO2
C3 plant
with 600 ppm CO2
Rate of CO2 Fixation
C3 plant
with 300 ppm CO2
Light Intensity Full Sun
Fig. 8.10 Rate as a function of PFD: the effect of CO2 concentration. A C3 plant
behaves more like a C4 plant if the carbon dioxide concentration is doubled.
grown in normal atmospheres. It has been suggested that while tomatoes and
cucumbers undoubtedly do better when grown in carbon dioxide-enriched
atmospheres the same may not apply to other species which nevertheless show
increased rates of photosynthesis if grown in air and assayed in high carbon dioxide.
There may be some truth in the proposition. Plants are notoriously conservative.
Spinach grown in water culture is more susceptible to wilting at high temperatures
and in high light than if grown in pots, exposed to periodic drying, in an otherwise
identical environment. It is as though a plant with its roots permanently in water gets
the message not to make more roots than it needs. This, of course, can take us into
the dangerous realms of teleology and gardener’s folklore but that is not to say that
such aspects of growth and form are no less real because they are poorly understood.
It is not inconceivable, and there is ample evidence to support this supposition, that
a plant which finds itself in high carbon dioxide will not put so much of its resources
into manufacturing the machinery for carbon dioxide assimilation as it would in
normal air. At the same time, like Robert Boyle, we must remain properly sceptical.
211
In the Robert Hill Institute in Sheffield, where we have long experience and a vested
interest in growing good plants for experiments, we grow the best spinach in the U.K.
Our spinach photosynthesises better than our maize. Conversely, our maize, grown
at moderate temperatures and often inadequate light, compares poorly with maize
grown in the field at the Maize Research Institute near Belgrade. When plants are
grown in high carbon dioxide for experimental purposes it is therefore, important to
(A) T.oblongifolia C4
6
330 ppm
2
Ratio of Photosynthesis, µmol CO 2 m-2s-1
L.divaricata C3
0
6 (B) L.divaricata C3
1000 ppm
5
T.oblongifolia C4
0
15 20 25 30 35 40 45 50
Leaf Temperature, °C
Fig. 8.11 Temperature and carbon dioxide. Temperature dependence of carbon

dioxide uptake at (A) 330 ppm carbon dioxide and (B) 1000 ppm for Larrea divaricata
(C3) and Tidestromia oblongifolia (C4). [After Osmond, Bjorkman and Anderson, 1980.]
ask if they have been inadvertently subjected to constraints which might have been
less important in air-levels of carbon dioxide. Nitrogen supply, for example, is
immensely important in this regard and can have major impacts on the amounts of
RUBISCO in the leaf. All we can reasonably say at present is that we do not have
enough facts to go on. It may be unwise to suppose that a plant grown and assayed
in high carbon dioxide will show the same increased rate of photosynthesis as one
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WATER USE EFFICIENCY
grown in air and assayed in high carbon dioxide. It would be equally unwise to
dismiss the vast experience of commercial growers of tomatoes and cucumbers or
to suppose that only some species such as these would do better as atmospheric
carbon dioxide rises. The likelihood, if not the certainty, is that photosynthesis in
general will increase as atmospheric carbon dioxide increases and that the potential
for increases will be amplified by higher temperatures and better water use efficiency
(Section 8.15).
It should also be noted in this context that in arriving at conclusions from

relevant experiments it is important to know what to measure. Working in a facility
built in Maryland by the Carnegie Institute, Steve Long has recently shown that some
species grown over a period of three years in augmented carbon dioxide (but
otherwise in their natural environment) show the same increase in quantum
efficiency when assayed in high carbon dioxide as do control plants grown in air.
Not many leaves spend much of their time in saturating light. How they behave in
low light may be more important.
Given two plants with identical rates of photosynthesis in saturating light but
with different rates in low light (because of differences in quantum efficiency) it is
self-evident that the more efficient leaves would accomplish most photosynthesis.
Meaningful conclusions can only be drawn in such circumstances if really accurate
measurements have been made of the low rates of photosynthesis which obtain in
low light. Until relatively recently, the ability of most laboratories to make such
measurements has been seriously curtailed by inadequate techniques. Once again the
need for caution is apparent.
8.15 Increased Water Use Efficiency.
C4 plants use fewer molecules of water per molecule of carbon dioxide fixed
than do C3 species (Chapter 5). It seems probable that, in high carbon dioxide, both
C3 and C4 will be advantaged in regard to water loss.
What, you might ask, are the principles involved? C4 plants you might recall,
often do well in semi-arid conditions because they first fix carbon dioxide in an outer
compartment (the mesophyll) in a reaction catalysed by PEP carboxylase. This
enzyme has a high affinity (Section 5.17) for carbon dioxide like RUBISCO which,
in C4 species, does its work in its own carbon dioxide-enriched “greenhouse” (the
inner, bundle-sheath compartment). Because PEP is not subject to oxygenation, PEP
carboxylase works better than RUBISCO in very low concentrations of carbon
dioxide and therefore, if the stomata (“pores”) in C4 leaves are barely open (the
smaller the aperture the lower the diffusive loss of water vapour), PEP carboxylase
can still function well and maintain a steep diffusion gradient (for carbon dioxide)
between the mesophyll compartment and the external atmosphere. Obviously, C3
species do not have this advantage and are less well placed than C4 species to cope
with the inescapable fact that stomata must be opened to permit carbon dioxide entry
and that water is lost through open stomata. If external carbon dioxide is increased
then, of course, any diffusive barrier imposed by stomata which are partly closed (to
prevent water loss) will be less advantageous. Here again, the situation is probably
no way near as simple as indicated above. It used to be believed that photosynthesis
was very dependent on stomatal movement in the sense that if stomata tended to
close (in response to a water deficit or incipient wilting) the rate of photosynthesis
would decrease in a commensurate fashion. This is still not questioned but, since the
work of Cowan, Farquhar and others, it seems likely that, at least in some
213
circumstances, it is not stomatal aperture which determines the rate of photosynthesis

but rather rate of photosynthesis which determines stomatal aperture. All of this
implies some very sophisticated signalling between chloroplast and stomata but it has
been known for many years that, other things being equal, high carbon dioxide will
tend to cause stomata to close and low carbon dioxide will tend to cause them to
open.
[It should be noted that a number of other factors can be involved in stomatal
opening such as the plant hormone, abscisic acid. Actively photosynthesising
chloroplasts may also communicate with the cytosol and other cellular
compartments and organelles both by demanding inorganic phosphate and
affecting the release of inorganic phosphate from triose phosphate during
cytosol sucrose synthesis. - Figs 4.10 and 4.11.]
“sophisticated signalling”
Whatever the mechanisms involved, there is good evidence that, in many

circumstances, stomatal apertures tend to be controlled in such a way that stomata
do not open more than necessary (in the sense that a more or less constant carbon
dioxide concentration is maintained within the leaf). In other words, carbon
assimilation and its associated machinery is in balance with carbon dioxide supply
as though the leaf is smart enough to know that wider apertures will not help carbon
dioxide assimilation already limited by other factors (such as the amount of
RUBISCO, or the regeneration of ribulose bisphosphate) but it might increase water
loss to a rate which would be damaging. It could be concluded that this is yet one
more reason for supposing that photosynthesis would not increase with increasing
carbon dioxide. The plant, however, appears to know when it is on to a good thing.
No doubt it goes through the same fine balancing act (between distribution of
resources and regulation of metabolism) at 600 ppm carbon dioxide as it does at 300
ppm carbon dioxide but, in the end, it appears to finish up with a faster rate.
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SUMMARY
8.16 Summary
Are we to be optimistic or pessimistic about the Greenhouse Effect and the

prospect of global warming? In the final analysis it is anyone’s guess. But that is not
really the real issue which ought to concern us all. More to the point is that we ought
not to be indifferent to polluting our planet and depleting it of so much that makes
it a pleasant place in which to live.
“dear to the heart of politicians”
Your author is a biologist, working somewhere in the area between plant

physiology and plant biochemistry. He has laboured sufficiently hard and long in the
field of photosynthesis to feel comfortable with that subject but unable to share the
schoolboy’s confidence that he really understands it. Most certainly he is not a
climatologist or an economist but he has no doubt that all three disciplines
(climatology, economics and photosynthesis) are vastly complex subjects, all well
laced with physics and politics as well as with biology. Take economics, for example.
Like the other two, it is a subject which impinges daily on our lives and is dear to
the heart of politicians. Almost invariably they get it wrong. We may take for granted
that many politicians delight in the prospect of ordering the lives of their fellow
mortals, that they often represent sectional and vested interests and that they are no
less greedy, avaricious, or dishonest, than the rest of us. However reluctantly, we
215
must nevertheless accept that they do not get it wrong on purpose. In democracies,
at least, getting it right would presumably give them a marginally better chance of
staying in power even though we are all so prejudiced that politicians can seemingly
make the most fearful mess of things before the electors have had enough.
So what has this to do with the contents of this chapter? Let me come clean.
Having looked at the climatological evidence as a biologist (i.e. as a lay scientist in
this regard). I simply cannot say with any sort of authority, that the world will grow
warmer and that unpleasant consequences will follow. If I had spent my life working
in climatology rather than photosynthesis, I suspect that I would feel equally
uncertain. On balance, I think that there are very good reasons for supposing that
warming might occur and that, if it does, we might wish that this had not happened.
There my uncertainty ends because I can see no early end to Man’s determination
to liberate, from fossil fuels, all of the carbon dioxide which was once put there by
primeval photosynthesis. To the question “does it matter” I am bound as, a biologist,
to lament the irretrievable loss of any natural resource, (living or mineral) because
the world, as we know it, exists best in some sort of slowly changing equilibrium.
Of course it has never been stable but it is clear that biological organisms, including
Man, can accommodate to almost unthinkable change provided that change is
reasonably slow. Of all of the present uncertainties, the fate of the “missing” CO2
is one of the most perplexing. If so much of what is being released gets “lost” there
is obvious hope that given a lot more time we could lose a lot more - a sort of cosmic
“kick it around until you lose it”
What CFCs have done to the ozone layer will very probably have dire
biological consequences quite apart from any impact on global warming. Ultraviolet
radiation does nasty things to eyes and to skin and most importantly to DNA, the
very heart of the biological blue-print. Even so, growing political awareness and
realism may soon preclude their production and much of the damage that they have
done to the atmosphere will repair itself, given time. Fossil fuels, on the other hand
will not replace themselves, (once burned) on any sort of timescale that it is
imaginable to Man. This issue is inescapably linked to what has already been
discussed in chapter 7 and will be returned to in chapter 9. Man is totally dependent
on photosynthesis. Contemporary photosynthesis of the sort most important to Man
(sophisticated agriculture) is totally dependent on fossil fuels, an inefficient way of
converting oil into crops. There is a sad contradiction, not immediately evident to
an observer admiring a field of wheat, that the food industry is responsible for
releasing more CO2 than it takes out of the atmosphere, and adds more than a little
methane (via cattle and rice production) as a bonus. In my childhood the textbooks
stated, with colonial certainty, that London was the largest city in the world, with
a population of 8 million. Since then despite its own growth it has been overtaken
by Tokyo and Mexico City, and who knows where, but it is still a large centre of
population by any standards. At current rates the net increase in world population
is sufficient to produce a new London every month. Once mature, the populations
of these new ‘Londons’ embark on procreation. The rate of increase accelerates,
fossil fuels are used at an increasing rate, CO2 builds up. So this much, at least, is
very clear. This phase of world history cannot last. Moreover it is most unlikely to
come to an end in a painless manner. It may be in Man’s power to put the cork back
into the CFC bottle but there is no possibility of governments stopping CO2 release
or population increase. If left unchecked these will sooner or later stop themselves.
Fossil fuels will be spent and, even if alternative energy sources are exploited to the
full, any biological population has an upper sustainable level. What does lie within
Man’s province, as a supposedly sentient animal, is his ability to recognise the
problems as real and pressing and to do everything possible to make the last years
of the great fossil fuel bonfire as painless as possible.
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CHAPTER 9 - IS THERE ANOTHER WAY?
9.1 An Excursion into Dangerous Ground
“....could thou and I conspire

to crush this sorry scheme of things entire
and remould it, nearer to the hearts desire”
.....Omar Khayam
Conspiracy
The reader who has read this far will be one who has not wearied of a single
recurring theme - i.e. where do we get the energy which we need for our metabolism
and all additional aspects of “civilised” life, what role plants play (or have played)
in this process, and what are the implications for the future. Chapters 8 and 9 carry
the stark message that mankind cannot continue, into the foreseeable future, as it is
at present. Small populations of mammals can live in reasonable equilibrium with
their environment. Large populations create difficulties for themselves. Vast
populations, increasing in an exponential fashion, cannot be sustained. Malthus had
it right. People consume energy and create pollution. At present, most of our energy
derives from past photosynthesis. It cannot even be argued that most of our metabolic
energy comes from contemporary photosynthesis. Certainly contemporary
photosynthesis provides virtually all of our food, whether we eat plants, or animals
that eat plants, or both. But modern civilisation is mostly dependent on farming and
modern farming is mostly dependent on past photosynthesis in the form of fossil
fuels. Ergo, as fossil fuels are depleted, it will become increasingly necessary to look
for alternatives. This is the subject of this chapter but it is evident at the outset that
prevention is better than cure. “What can’t be cured must be endured” but it is
scarcely sensible to continue to add recklessly to mounting problems while
simultaneously striving to solve them. Inevitably, if we wish to address these matters
at all, we enter immediately into politics, economics, sociology and even into
religion. Naturally, I have strong convictions of my own but my purpose in writing
is not to proclaim my own values or remedies but rather to examine consequences.
If there are those who believe that there are circumstances in which the use of nuclear
weapons or germ warfare would be justified, that it is better to be “dead than red”,
that blasphemy should be punishable by death, that the clear and obvious rights of
the unborn child and of animals transcend the rights of society as a whole, that there
218
PROCREATION AND POPULATION
are political causes which justify the use of Semtex to blow apart people who only
happen to be involved by virtue of birth, accident or religion, I know very well that
no words of mine would ever give them even pause for thought. Nevertheless, there
is now some awareness, once scarcely apparent in anything other than some of the
most primitive societies, that living in harmony with the environment has potential
advantages for us all. Those already wholly or partly convinced of this might find
some profit in what follows because it is very evident that these areas of knowledge
and understanding are strewn with all manner of misinformation and economies with
the truth. Everyone knows, of course, that “truth” like “beauty” lies, at least to some
extent, in the eyes of the beholder but if “a fact” is unpalatable it is often better to
seek to challenge it, or refute it, than to be unaware of it. It is also easier to condemn
perceived ills than to offer remedies.
I am no better placed than any other scientist to offer remedies. It is easy, for
example, to say that we should all use trains and other forms of public transport
rather than our own motor vehicles but I would not wish to do that myself, I am well
aware that, despite its awful penalties, personal road transport is an aspect of
civilisation which is extraordinarily liberating and one which is now virtually
essential in Western rural communities. So there will always be a balance between
what is desirable and what is feasible, what we can do voluntarily to make things
less difficult for ourselves and our children and what is likely to happen if we allow
matters to take their own course, indifferent to the consequences. All I seek to do,
in this chapter, is to discuss some of the problems and some of the alternatives in
the belief that it is better to debate them than to stick our heads firmly in the sand
and hope that they will go away or that we can safely entrust all decisions to
politicians and bequeath all consequences to our children. At the very moment of
writing, George Bush has stated publicly and proudly, that he will not attend The
Rio de Janeiro “Earth Summit’ on the environment if, by so doing, there is any
possibility that he will be obliged to “harm” the United States economy by limiting
carbon dioxide emissions. In consequence the European Community Commissioner
for the environment will also stay away, now believing that there is no real point in
going, his Indian counterpart suggests that the Rio conference will be little more than
a lovefest for ecologists, others that it will be “a monumental fiasco.” Evidently we
can not look to governments for a lead until disaster is almost upon us. In the present
context all politicians have a limited life. Understandably, tomorrow’s elections
mean more to today’s politicians than what is going to happen to the unborn. Urban
deprivation is all around us now but here again the tendency is for the politicians
to fiddle as Los Angeles burns and for the rest of us, if we are able, to distance
ourselves as far as possible from the ghettos and to build bigger and better stockades.
9.2 Procreation and Population
“The biggest threat we face is our own success as a species” ....C. Tickell
If we go back to the apocryphal island stripped of vegetation and littered with

the skeletons of rabbits (Section 8.10) we can see a possible but unlikely future for
the human race. Perhaps, more realistically, we could look to the garbage mountain
dwellers of Delhi (Section 8.8), eking out an unenviable existence in an entirely man-
made environment of fearful squalor. Common sense tells us that, as sentient beings,
we would never let things become that bad. But where then do we find comfort?
Certainly not in the Holocaust, the genocide in Tasmania, the murder of three million
Chinese by the Japanese, the more recent events in the Middle East, Jugoslavia and
the Soviet Union or in the combination of evil and profligate exploitation of the
environment which has created starvation in Ethiopia and is still extending the
219
world’s deserts. Can we find hope in the rampaging destruction of the rain-forests,
the past decimation of bison and the present slaughtering of dolphins and whales,
the extinction of more animal and plant species than many of us have ever seen?
Suddenly the prospect of a future race of garbage dwellers becomes no less realistic
than the possibility of nuclear winter. We can already find parallels between the
garbage dwellers of Delhi and the conditions in which some people live in London
and New York. The more affluent in these cities can literally live above the mess
and enjoy a life-style which might have been envied by ancient kings and emperors.
At the same time, we have seen that affluence depends on energy and that energy
in the form of fossil fuels is not a renewable resource. Our renewable resources will
only remain renewable if we can somehow continue to avoid Man’s pillage of our
environment.
Why then do we choose to continue to procreate like the rabbits on the island?
Sex, of course, is only marginally less of a driving force than food. Prolonged
starvation of the sort experienced by the inmates of concentration camps or
castaways in lifeboats eventually eliminates strong sexual desire and may even
inhibit reproductive function as it does in anorexic women. On the other hand, whole
races of people who are either chronically under-nourished or who experience
intermittent starvation (or both) are often amongst the most prolific. Perhaps it is all
down to the “selfish gene” and there is some deep biological tendency in people, as
in plants, to flower when stressed or when facing elimination but, in many societies,
there is the simple but painful fact that children hold the only promise of survival
for parents; particularly ageing parents. In the West, life may be very difficult for
those who must rely entirely on what the State provides but in some Third World
countries only the charity of relations, friends or neighbours lies between the aged
(or incapacitated) and death by starvation. In primitive rural communities, what
wealth there is often resides in the number of hands available to work the land. None
of this accounts, of course, for the fact that when Victorian Britain was at the height
of its wealth and power it was not unknown for women to give birth to more than
twenty children and large families were as common amongst the affluent as amongst
the poor. Nor does it account for the prevalence of families of four children in
wealthy middle class families in the United States in the 1950’s. So perhaps we all
tend to seek our own immortality in our children or are moved by deep seated
emotions which are not met by sex without issue. Religion cannot be dismissed as
entirely irrelevant in this context. Where it sets its face entirely against contraception
or abortion and finds no favour in sex which is not intended to induce pregnancy,
it is not going to help to solve problems of over-population. This, no doubt, is why
the Archbishop of Canterbury recently said that the Roman Catholic Church should
reconsider its attitude to contraception. Some would argue that Catholic countries are
no more prolific than non-Catholic countries, that the forces that encourage large
families are many and varied and there are some rules that are more honoured in the
spirit than in the observance. Nevertheless, there is little doubt that, if the Catholic
Church were to set its stamp of approval on contraception, it would encourage
population control measures in those countries in which it has a major influence on
government.
That there is a need to limit population is self-evident. It is simplistic to

suppose that there will soon be standing-room only, or that Earth could not
accommodate many more than it does at present. The awful fact that the net gain
in population is currently running at about 250 per minute, (and rising), speaks for
itself. In the short term this will continue to happen without most of us being even
aware of it. This is not to say that the majority of these newcomers will have an easy
life but we are talking about net gains. When we talk about 250 per minute we are
not talking about births but the extent to which numbers of births exceeds numbers
220
of deaths. Despite the enormity of this problem we are not going to be overwhelmed
by it, this year or next. The world could, and will, find space for an extra New York
next year, the year after, and for many years to come. Moreover, given modern
technology, and despite dwindling oil reserves, it will be able to feed most of these
extra mouths well into the next century. That much seems certain but it is equally
certain that such a path cannot be followed indefinitely. The smallest constraint is
space in which to live. Not all of Earth’s surface is very hospitable, indeed much
of it is extremely hostile but there is still lots of it. Race and religion are much bigger
factors. Despite the demise of what was the Soviet Union there are many Russian
Jews who are prepared to exchange the vast expanses of their native country for the
tinyness and dangers of Israel. All over the world there are populations which would
apparently prefer to engage in mayhem than to exist in peaceful coexistence with
others. The motto “what we have, we hold” could be aptly applied to 99% of the
worlds population. Already, the European Community reacts fearfully to the prospect
of increased migration from the east and the south. Space for effective agriculture
is also not limitless. Arithmetic in Chapter 6 led to the conclusion that 300 to 400
square meters were needed to supply each person with a modest sufficiency of
potatoes. Meat eaters would need a great deal more. Multiply this space requirement
by 13 million per annum and it points, once again, to an eventual (and perhaps not
too distant) limitation. Pollution may seem trivial by comparison. It is not. True we
all produce some excrement and many of us a great deal of garbage. This can do
all manner of nasty things to our environment and is not to be lightly brushed aside
but it pales into insignificance by its potential threat to our atmosphere. The impact
of CFCs on the ozone layer (Sections 7.7 to 7.9) is no longer dismissed, even by the
chemical companies which produce them. Rising carbon dioxide is very real even
though there are immense uncertainties about consequences. At worst, this sort of
pollution, by affecting agriculture, climate and sea levels could drastically affect
living space and food supplies.
“In 1971, Georgescu-Roegen published a book entitled ‘The Entropy Law

and the Economic Process’ which puts forth the proposition that waste, which
may be considered to be degradation (or an increase in probability or entropy
in a thermodynamic sense) of the environment, is the inevitable consequence
of economic activity and that the production of “bigger and better” washing
machines, automobiles, and superjets must lead to “bigger and better”
pollution. On thermodynamic grounds therefore it is not possible to get rid
of pollution simply by using nonpolluting industrial techniques. Degradation
of the environment is a corollary to economic activity” ....Geoffrey P. Glasby
All of these possibilities must be taken seriously but, in the end, it is energy
which is the greatest constraint of all. Contemporary agriculture is a relatively
inefficient way of converting oil into potatoes. Whether or not the line is drawn at
the farm gate, or at the supermarket door, there is no way in which people can be
fed without the use of large amounts of fossil fuels (Table 6.2). Moreover intensive
agriculture brings related problems in its wake. A decade ago much of the
agricultural research in the Netherlands was focused on agricultural pollution rather
than production. The Dutch are clean and tidy people living in a small densely
populated country. Nevertheless they earn a lot of money from the tomatoes, cheeses
etc., that they sell to their neighbours. No self-respecting Dutchman likes to live
down-wind from a pig-farm. Spreading pig shit on fields may be economically and
even ecologically sound but, like so many other things, we would prefer it not to be
done in our back yard. There are arguments about how great is the impact of manure
and fertilisers on our drinking water but there is no doubt that the provision of clean
and acceptable drinking water is a major problem world wide and that all manner
of things, including pesticides, can find there way into areas where they are neither
221
desirable or welcome. There are innumerable lakes, once teeming with fish, now
green and stinking because of algal blooms made possible by phosphates and nitrates
draining into them as a result of human activities. Methane released by grazing
herbivores (page 169) is not entirely a laughing matter and even something as
seemingly innocuous as growing rice can do substantial harm once it is on a large
enough scale. The CFCs released from factories producing frozen foods are much
greater in volume than those released from domestic refrigeration although these can
also be justifiably regarded as part of the whole process that brings food to the table.
In the end, however, it is CO2 (by its effect on the atmosphere) which looms largest
in regard to agricultural pollution just as it does in regard to industrial pollution.
Geologically speaking we are actively engaged in putting CO2, fixed into plant
products by millennia of primeval photosynthesis, back into the atmosphere in a very
short time. Clearly we cannot continue to do this indefinitely. Sooner or later there
will be no more such CO2 to return. Nor, by implication, will there be any more coal
or oil; at least none that we can afford to burn.
[Hubbert has calculated that Man will utilise 80% of the entire fossil fuels
accumulated by 600 million years of photosynthesis in a mere 300 years.]
At this point, the agriculture, presumably needed to feed much larger populations
than at present, will need an alternative source of energy. True, we could go back
to horses and peasant labour. We could leave the combined harvesters rusting in the
fields and use animal manure rather than artificial fertilisers. We could abandon
selective herbicides and pesticides. Perhaps, in the end, the world would be a happier
place. It was once written that the English country gentleman of the eighteenth and
early nineteenth centuries led the best life ever so far experienced by mankind. The
poorer workers on his estates might not have thought themselves so well blessed but
a modern and more equitable rural society could still have much to recommend it,
particularly if it proved feasible to retain some aspects of contemporary technology
222
and medicine. What is quite certain, however, is that such a population would not
be large. Living in equilibrium with the environment is as feasible now as it was
before oil was thought of but only on the basis of the small population (an order of
magnitude smaller than present population) that contemporary photosynthesis
supported in the past. It is difficult, of course, to imagine a world in which oil is not
consumed in vast quantities in internal combustion engines but edifying to look at
how this has changed in a relatively short time. When oil was re-discovered in the
UK. in the early part of the last century it was actually exported to the United States
for use in cooking and lighting.
“About the year 1847 E. W. Binney of Manchester, England, called attention

to the petroleum discovered at Riddings, near Alfreton in Derbyshire, and a
few years later he, together with James Young and others, commenced the
manufacture of illuminating and other oils from it. The supply of crude
material from this source soon became inadequate, and they then commenced
distilling the Boghead mineral that had been found near Bathgate in Scotland.
The success attending this enterprise soon attracted attention in the United
States of America and a number of establishments were in operation in the
course of a few years, some of them being licensed under Young’s patents.”
The author of the above entry in the Encyclopaedia Britannica of 1885, not
knowing about the forthcoming impact of motor vehicles and aircraft on life in the
Twentieth century, struggled with prediction:-
“Looking towards the past, it may be said that petroleum has attained
universal diffusion as a lighting agent; it is fast displacing animal and
vegetable oils as a lubricator in all classes of bearings, from railroad-axles
to mule-spindles, and also where other oils are liable to spontaneous
combustion; it is very largely used as fuel for stoves, both for heating and
cooking; it is very successfully used for steam purposes when other fuel is
scarce and petroleum plentiful; it is likely to be used for production of pure
iron for special purposes; and it has become a necessity to the apothecary
as petroleum ointment. Looking towards the future, what assurance have we
that these varied wants, the creation of a quarter of a century, will be
satisfied? While it is not probable that the deposits of petroleum in the crust
of the earth are being practically increased at the present time, there is
reason to believe that the supply is ample for an indefinite period. Yet the fact
is worthy of serious consideration that the production of petroleum as at
present conducted is everywhere wasteful in the extreme.”
He was right about the wastefulness but if he had looked into a better crystal
ball he might not have wished to use the term “indefinite” except in its sense of
“uncertain”. Of course, prediction is a fools game. Who in the heyday of the English
country gentleman could have foreseen radio, television, telephones, cars, word-
processors, commonplace travel by air, let alone genetic engineering and all that is
implied by that? So there may be a future “technical fix”, quite unimaginable now,
which would not (like nuclear fission and nuclear fusion - Section 9.4) create more
problems than it would solve. All that can be said is that if there is to be such a
technical fix it is not on the horizon now and that all existing alternatives, however
desirable, would require some drastic downturn in the number of people that the
planet could support. At the end of the day we are back to the laws of
thermodynamics. These cannot be repealed or circumvented. There is a universal
tendency for entropy (i.e. disorder) to increase. Living creatures are the only things
which can reverse this tendency for a while. They can only reverse it, building order
out of chaos, by utilising energy. Putting aside a few specialised bacteria, the source
223
of that energy is (and always has been) nuclear fusion of protons in the sun. The
process of energy transduction has been photosynthetic. Life, as we know it, is based
as much on past photosynthesis as on present photosynthesis. The more of us there
are, the quicker we will exhaust the products of past photosynthesis and the more
strain we put on contemporary photosynthesis.
“Whats to do about it? Lets put out the lights and go to sleep”
In the circumstances this might not be the best remedy but restriction of
family by decree, in the manner tried by the Chinese, would not be widely welcomed
however well intentioned. Similarly, the Indian attempt to reward vasectomy with
transistor radios, while understandable, is hardly laudable. We can really only hope
for changes in society, such as provision in old age, which will make more than two
children per “family” seem socially, morally and financially less desirable than the
alternatives. In the West it ought not to be beyond the wit of politicians to arrive at
taxing policies which help those on low incomes but do not, at the same time, offer
financial rewards to those on high incomes who choose to have large families. Much
of this could be less painful and less intolerable to some religious convictions than
might be imagined. In the U.K. and Germany, populations are more or less stable,
certainly not expanding in the way they were thirty years ago. Easier contraception
and the availability of abortion on demand may have played some part in this but
the situation has not been materially different in Ireland where such steps are
frowned upon or even not permitted by the nation’s constitution. It is economic and
social considerations which have been more important. Western women now
frequently wish to work outside their homes as well as having children. Usually they
are encouraged to do so by their male partners. Many more, who do not work from
choice, do so because it is the only way in which they can afford the things that they
would like to buy for themselves and their families. For reasons such as these,
families are postponed and the biological constraints on the age of child-bearing
diminishes numbers. In countries like the U.K. large families are no longer regarded
as “normal” or desirable. In such societies, having only two children is not regarded
as a disaster. Some couples do not wish to have children or are not able to have two
or even one. This is a prescription for stable or declining populations. It seems
preferable to the converse in which an uncomfortably large population would
become limited by factors quite outside its control.
9.3 An Inversion of Ends and Means

Until relatively recently, nations and communities have tended to evaluate
their future energy needs almost entirely on the basis of existing per capita
consumption and predictions about future growth in population. Little or no thought
was given to the continuing availability of fossil fuels, to the impact of alternative
technologies, to effects on the environment or on social implications. To quote
Lovins:-
“this approach is unworthy of any organism with a central nervous system,

much less a cerebral cortex. For those of us who also have souls it is almost
incomprehensible in its inversion of ends and means”
However incomprehensible, this is precisely the sort of argument used by the

proponents of nuclear power who imply that there is no real alternative. Even those
who are concerned about their environment and yet regard themselves as realists, are
often genuinely puzzled about what might be done to pave the way to an acceptable
future. In this chapter some of the alternatives will be touched upon but the most
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AN INVERSION OF ENDS AND MEANS
important first step is implicit in the above quotation. If we are running into debt,
there are really only two things that we can do about it - acquire more money or
spend less. There is always the possibility that we can improve our financial
resources by earning more, by robbing a bank, by successful gambling or by
stumbling on hidden treasure. Mankind as a whole has often been well-served by
those who have produced great works of literature, or whatever, because they needed
the money. As a general rule, however, the course of action which most recommends
itself in the short term is to spend less on those things which offer no future return
or amelioration of our debts. There seems to be a natural law which ensures that if
you put your last pound, dollar, rouble or deutschemark on to a horse it will almost
inevitably fall at the first fence. Robbing banks or old ladies has little to recommend
it and chancing on nuggets of gold is a fairly infrequent occurrence. These facts are
self-evident but past energy policies have rarely been better based. The first response
to an energy shortage has been to seek more energy rather than to use less. The
acquisition of more has often had consequences much worse than languishing in jail
for theft. The concept that someone, somewhere, will come up with some totally new
technological fix in the future is like counting on winning a lottery; it happens but
don’t hold your breath.
Imagine an immense stone wall in the North East of England, an area not
noted for the clemency of its climate. Along the wall, having obviously once grown
in profusion, the remains of peach trees. How could that possibly have been
achieved? The answer lies on the other side of the wall which turns out to be hollow
and constructed out of fire brick. Every few metres along the wall, a blackened
aperture; running alongside the wall, the railway line that brought the coal wagons
to feed the fires. The owner of the wall was a very wealthy man, the owner of the
nearby coal mine. His answer to British winters was to heat his whole environment.
This is not a course of action which is open to us all and it would, of course, have
made its own minor contribution to the social deprivation of nineteenth century
miners, to increasing carbon dioxide and to the pollution which was already changing
the British landscape.
Today, of course, no one would contemplate anything so outrageously

expensive, or would they? Sadly little has changed. Putting aside the Chernobyls, the
pollution of the Irish Sea by the Sellafield nuclear reprocessing plant and the
devastation caused by burning “brown” coal in Eastern Europe and we can still arrive
at energy policies which are as indifferent to environmental considerations and as far
removed from rational thought as the hole-in-the-wall solution. Currently, for
example, an electricity generating company in the U.K. is trying hard to displace
relatively clean coal with an imported product so rich in “nasties” that it has
environmentalists apoplectic with outrage. British Gas offers a substantial discount
to those who use most of what it produces - a natural and logical extension of
discounting for bulk or wholesale purchasing which has been a common aspect of
business procedures the world over for many years. Inevitably, of course, this is a
real disincentive to energy conservation. A local education authority, bent on saving,
succeeded in using 20% less gas for heating. It was rewarded by a 20% higher bill
as a consequence of having dropped out of the discounted price range. It is reported
that the response of the gas-producing utility was to tell the education authority to
burn off the gas which would otherwise have been saved in order to get back into
the lower price bracket. All of this could be dismissed as sound commercial practice,
bringing benefits to industry but it has to be asked if it should be allowed. Burning
more gas is not always bad. It is better, for example, (in terms of carbon dioxide
released per Kjoule) than burning coal. It may make more sense, in the long term,
than burning oil but it is still, basically, something to be discouraged. Those who live
in the environment in which gas is burned have as much right to be protected from
225
the consequences of burning it as they have to be protected against passive smoking;

an expectation that their governments will not stand idly by and permit some to profit
by inflicting unreasonable penalties on others. Even the ethics of using vast quantities
of electricity to make artificial snow (for skiing) is questionable. For sure there is
general acceptance of the fact that everyone should be allowed maximal freedom to
spend their money as they wish but, equally, no one cares to have someone else’s
rubbish dumped in their backyard. If we accept the principle that “the polluter pays”
it ought surely to follow that using energy should be discouraged and that saving
energy should be rewarded.
The alternatives to present means of energy production are numerous. Some

will be considered below. There is no doubt, however, that the first, practical and
imperative alternative is to ask if we can manage with less. There was a time in
Man’s past when he lived in equilibrium with his environment. Some few in the
depths of fast vanishing rain-forests still do. No doubt, in many ways, they have a
hard life. Whether it is harder or more enviable than that of some “inner-city”
dwellers, in otherwise affluent societies, is debatable. However, it does not follow
that the only escape from the deprivations of “civilisation” is a return to an ancestral
life style. We cannot in any case go back to what prevailed before the Industrial
Revolution. The question that should be asked, however, is whether or not it is really
unthinkable to have the best of all worlds. Asked what he thought of American
civilisation, Gandhi apparently replied “I think that it would be a good idea”. He
had a point even if his own solutions were perhaps not eminently practical at that
time. Today, in many respects, the “need” for urbanisation has gone. We no longer
have to think of cottage industries only in terms of Harris Tweed. Human ingenuity
is such that we can probably continue to squander our resources and pollute our
planet for decades, or even centuries, to come but we cannot do these things
indefinitely. If Man (with anything like the attributes which we currently admire in
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GOING CRITICAL
ourselves, or envy in others) is to continue into the future he will have to cry a halt
to endless expansion, despoliation and pollution.
The twentieth century has seen all manner of political, religious and social
orthodoxies challenged. On the other hand there has been scarcely any erosion of the
very similar factors in these categories which divide people on the basis of culture,
colour, language and religion. These, in turn, are exacerbated by pressures of
population, opportunity and economics. Those members of the Muslim community
of the United Kingdom who currently call for the death of Salman Rushdie cannot
comprehend why a supposedly tolerant British population is so slow to understand
why the “Satanic Verses” causes devout Muslims so much offence, why the British
are seemingly so indifferent to blasphemy (in either a Muslim or a Christian context)
and, at the same time, so deeply dismayed by the Muslim reaction. Nor would better
understanding or education help. One person’s tastes in food, the climate which he
or she enjoys, or the values which he or she esteems, may be anathema to another.
Even within families there are aspects of behaviour which no amount of love,
tolerance, or understanding can accommodate. Such problems are mostly solved by
a degree of separation. Offence only follows when people of different tastes, cultures
or patterns of behaviour are thrown together, not from choice but because of
economics. What the Muslims of Pakistan do in Pakistan is of little concern to the
British in Britain, or vice versa. Aggravation only follows economically propelled
association. Energy, economics and population levels are clearly inter-related. The
world is large enough to support many hundreds of millions of people living in
equilibrium with their environment and almost any number of groups with widely
disparate beliefs and requirements. It is equally clear that its resources are not large
enough to maintain indefinitely the present rate at which energy is being used. It is
threatened by effects, on the environment, of energy use. In turn, the rate at which
energy is being used is directly related to global population and to the competition
between different populations for available energy and energy-related sources. To
propose much smaller communities, capable of freely using much larger amounts of
renewable energy and sufficiently isolated from one another to cause little real
offence might seem a naive, simplistic and hopelessly optimistic solution for existing
strife. The cynical and pessimistic alternative (continuing population growth,
feckless squandering of resources and ever increasing pollution) would seem to offer
little prospect of a world worth living in. Perhaps the real future will be somewhere
between these extremes. The following sections consider some of the options that
still remain open to us.
9.4 Going Critical
The present government of the U.K. is wedded to nuclear power just as it is

wedded to its “independent” nuclear deterrent - in part, a cause and effect
relationship.
“For the first decade of British nuclear activities, uranium was not a fuel and
reactors were not for generating electricity. That was all to come later. In the
1940s and early 1950s uranium was bomb-material, and reactors were a way
to turn uranium into a better bomb-material” ....Walter C Patterson.
Against a background of increasing public concern about the environment, the

fact that nuclear electricity generating plants, once built, would not add to the
Greenhouse Effect came as a godsend to politicians desperate to bolster a nuclear
image profoundly diminished by Chernobyl. Particularly if the enormity of
radioactive waste disposal could be conveniently disregarded, nuclear power could
227
be proclaimed as “green”. Beneath the evident sophistry there is a real point. Nuclear
electrical generation does not normally discharge carbon dioxide to the atmosphere
(although there have been some inadvertent releases of radioactive carbon dioxide).
It is, therefore, reasonable to ask how much carbon dioxide emission could be spared.
Fortunately, the arithmetic is simple. Nuclear plants currently provide about 7% of
the U.K.’s primary energy.
[Primary energy is the sum of all fuel inputs used in producing the energy
purchased by final users. It is normally based on a fossil fuel equivalent. Thus,
in 1991, U.K. primary energy was equivalent to 203 million tonnes of oil and
nuclear power is put at 7% of this on the basis that British nuclear electrical
output would have consumed about 14 million tonnes of oil if it had been
produced by conventional power stations.]
By the turn of the century, given the real probability of more of the older,
ageing, nuclear installations being closed, on grounds of safety and economy, it could
be as little as 3%. It is just conceivable that, despite public opposition, despite an
infirm economy and a diminished manufacturing capacity, the U.K. might find it
possible to increase its nuclear capacity again by the year 2010. At present, about
one third of U.K. carbon dioxide emission is directly attributable to generation of
electricity (as it is in the United States) so, at the most, nuclear generation could save
an output of carbon dioxide equivalent to about 6%. Doubling present nuclear
generation would, therefore, save further carbon dioxide release by the same order
of magnitude. A saving of 5 or 6% (say 25 million tons of carbon dioxide per annum
is not inconsiderable but neither is it a lot (global carbon dioxide emission is about
5000 million tons per annum) The same sort of arithmetic can be applied pro rata
to other countries, some like France and Taiwan with relatively large investment in
nuclear power, others like the United States where development is currently stagnant
or like Sweden where it is to be phased out. In total it seems unlikely that, in the
foreseeable future, switching from fossil fuels to nuclear power would have anything
other than a relatively modest impact on atmospheric carbon dioxide concentration.
It can also be argued that, since nuclear energy is so much more costly than energy
conservation, it would, for given expenditure, displace much less coal, gas, or oil-
fired electricity generation plant and thereby actually contribute to carbon dioxide
emissions and global warming rather than the converse.
At first sight, nuclear fusion would solve everything. There is absolutely no

doubt that it is an extremely effective source of energy. All of our metabolic energy
and all of our fossil fuels come, originally, from nuclear fusion of protons in the sun.
This conversion of hydrogen to helium involves a slight decrease in mass (4
hydrogen atoms weigh 0.7% more than the helium atom that is produced by fusion).
Remembering that energy and mass are interchangeable according to Einstein’s
famous equation:-
E = mc 2
(where E is the energy, m is the mass and c is the velocity of light) we can calculate
that although 0.7% of the mass of 4 protons is a very small number indeed it still
represents an awful lot of energy, relatively speaking. Thus, if we do our arithmetic
on the basis of one gram of hydrogen (i.e. Avogadro’s number of hydrogen atoms)
we get:-
E = (1 x 0. 07) x (2. 99 x 1010 )2 = 6.39 x 1018 ergs
= 6.39 x 1011 joules
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GOING CRITICAL
If, on the other hand, we wished to produce that amount of energy by oxidation we
would need to burn 4,580 Kg of hydrogen or 15,270 Kg of fuel oil. Such figures
suggest that we would be on to a good thing with fusion but the practical problems
are immense. First of all we have to learn how it is done. Despite occasional bouts
of optimism we have not yet discovered how to create conditions on Earth which
would allow this process to proceed and give rise to more energy than it consumes.
As a pure scientist, I applaud fundamental research of any sort. As a tax payer and
a biologist, seeking support for research, I must always question costs. It may be
parochial to suggest that the money spent on Concorde would have benefited the
travelling public more if it had been spent, instead, on the London underground
system but it could scarcely be denied that if the billions which have gone into the
research and development of nuclear (fission) electricity had been invested in
renewable energy technology the world would be a better place. We need to be as
financially circumspect in regard to fusion as we should have been about fission even
if we take the view that fission always had more to do with power politics than the
generation of electricity. Then there is the question of pollution. If there were no
other feasible alternatives we might have to regard fission as something worthy of
consideration despite all of its associated risks and the remorseless accumulation of
toxic products which cannot be made safe, or stored in a cheap and safe manner. It
is tempting to think that nuclear fusion would not bring comparable problems in its
train but fusion also produces radioactive materials because of the need to contain
neutrons (page 4). On a site 90 million miles from Earth, fusion is fine. Nearer home
it must, in the light of the fission story, be viewed with considerable suspicion.
229
It will have already become clear, from what I have written elsewhere in this
book, that I am not wildly enthusiastic about nuclear power. To be blunt, I regard
it as dangerous and expensive lunacy and I take some comfort in the fact that this
view is widely endorsed by many others in the scientific community, even though
there are those who still see no practical alternatives. Lest my view of the nuclear
industry immediately casts me in the role of a muddled thinker, with all of the
characteristics which that industry loves to attribute to its critics, may I restrict
myself to a mere two quotations in my support.
Sir Brian Flowers chairing a Royal Commission on “Nuclear Power and the
Environment” said:-
“We believe that nobody should rely for something as basic as energy on a
process that produces in quantity a product as dangerous as plutonium ... We
believe that security arrangements adequate for a fully-developed
international plutonium economy would have implications for our society
which have not so far been taken into account by the government in deciding
whether or not to adopt that form of economy” ....Sir Brian Flowers.
and in 1976, Gerald Ford then President of the United States said:-
“I have concluded that the reprocessing and recycling of plutonium should

not proceed unless there is sound reason to conclude that the world
community can effectively overcome the associated risks of proliferation ... I
have decided that the United States should no longer regard reprocessing of
used nuclear fuel to produce plutonium as a necessary and inevitable step in
the nuclear fuel cycle” ....Gerald Ford
But it was left to Tony Benn, himself extremely honest about his own basic
understanding of the underlying science, to put the politicians’ dilemma in a way
which carries a message for us all.
“There is another set of factors to which reference has been made in public
debate: I would describe them as domestic political factors arising out of two
considerations. One is the problem of security and the risk of terrorism and
the second arises from what happens when you have policies so complex that
the democratic process finds it hard to come to terms with the choices that
have to be made. Certainly as a Minister with these responsibilities...
...I have always found nuclear policy the most difficult because Ministers are
not experts, they are not scientists, they are not engineers, they are not
qualified to assess in any way the technical decisions that had to be made.,
And, yet whether you look at it in terms of the environment or safety or energy
policy, it is essential that nuclear policy be preserved within the democratic
framework of control and not subcontracted off to those whose only claim to
reaching decisions might rest upon their technical qualifications. I think it
would be very frightening indeed if we were to say that our fuel policy
required us to adopt a technique of production like nuclear power which in
its turn required the decisions to be taken from the process of government
answerable to Parliament and the public, and put into the hands of those
whose special qualifications for deciding them would rest upon their technical
knowledge”. ....Anthony Wedgewood Benn
An economic footnote might be added. Margaret Thatcher and her successor,

John Major, are great believers in “market forces”. This is why British Coal can only
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GOING CRITICAL
look to a future if it can produce coal at the same price as imported coal. Why, it
is asked, should the rest of British industry be asked to pay more for electricity, to
stop British Coal going into terminal decline? As a political philosophy based on
“market forces” this argument is hard to fault. Where market forces go out of the
window is the fact that all British consumers pay a higher price than they need for
their electricity because the distributors are obliged, by law, to buy electricity (from
nuclear generators) which is twice as expensive, per unit (5.5 to 7.5/pKWh), as
anything derived from coal. (3-4p/KWh for new coal-fired plant with flue gas
desulphurisation).
In another respect “market forces” have redeemed themselves. Certainly in

the U.K., Government consistently closed its ears to the cries of anguish from
“Greenpeace”, “Friends of the Earth”, and the greater part of the scientific
community all of which found no merit in nuclear power. Even Chernobyl, which
contaminated British uplands for years to come, was dismissed as “something that
couldn’t happen here” despite the appalling example of Windscale (now Sellafield).
But then Government sought to “privatise” the industry (i.e. to sell the plant owned
by the State to private investors). Wise investors declined to buy because of the high
running costs, the costs of decommissioning etc., and Government’s refusal to add
a further £2.5 billion (in the way of risk guarantees), over and above those already
included in the privatisation deal. In short, we are left with nuclear power, not
because it is simply too awful to contemplate but because no one in their right mind
was prepared to buy it. Sadly, British nuclear power has been comprehensively
protected since then by guarantees that its output will be bought irrespective of cost.
These guarantees expire in 1998. If not extended (and there is immense pressure from
the privatised electrical industry and consumer groups to deny extension) nuclear
power will be simply unable to sell its output. Thereupon we might all breathe a sigh
of relief if it were not for the legacy of the “Magnox” plants. Whatever happens it
is most unlikely that these will be allowed by safety considerations, to operate
beyond the year 2000 and then decommissioning will become a significant fraction
of national expenditure. As it is, “safe” long term storage of existing radioactive
materials has already been postponed by 50 years, a margin which might be
perceived by the uncharitable as long enough to ensure that all those currently
engaged in policy making will be safely buried themselves.
To authorities like Professor John Surrey (of the Science Policy Research Unit
of the University of Sussex) a nuclear revival seems remote, only to be contemplated
if circumstances altered such that nuclear power became much cheaper than the
alternatives.
“Given the public disquiet expressed over problems at the back end of the fuel
cycle, chiefly over reprocessing at Sellafield and the long-term storage of
radioactive wastes, there are certain other preconditions if nuclear ordering
is to be revived and accepted by the public. The first is clearly the absence
of a further major nuclear accident as at Three Mile Island and Chernobyl,
which might well lead to a moratorium on existing as well as new nuclear
plants.
The second precondition for re-launching nuclear power on a substantial

scale is the development of a reactor design with inherently safer features
(e.g. giving longer response times under fault conditions) so as virtually to
eliminate the chance of a catastrophic accident. This would need large scale
funding for R & D and prototype experience over about 20 years and it
scarcely seems a realistic option at a time when no ordering is taking place
in the UK and only a little overseas. Changing reactors’ systems would again
231
create upheaval and strain further the resources of the nuclear plant industry
which has no orders after Sizewell.
The third precondition is the emergence of a broad social consensus on the

issue of the long-term handling of radioactive wastes. This is essential as long
as the UK continues to reprocess spent fuel. Were reprocessing to be
abandoned, it would be necessary to devise publicly acceptable policies for
the long-term storage and ultimate disposal of spent fuel and to write-off the
new Thermal Oxide Reprocessing Plant at Sellafield, which has cost £2.7
billion to build, and forego its lucrative export earnings. Stopping
reprocessing would also in the longer term prevent the UK stockpile of
plutonium, which has no civilian use in the absence of fast reactors, from
getting even bigger.”
Only good fortune prevented Sellafield going the way of Three Mile Island
and Chernobyl. It persists as a major threat to the environment. Nuclear energy is
not the answer to our problems. There are , of course, still those who take a different
view. Dr. Robert Hawley is one. According to “The Observer” of May 17, 1992, he
states:-
“I think if the public were better informed people would be less misguided.
It is really a question of getting people to listen to the facts. The simple, plain
fact is that if you go back to the electricity side and took all the
environmentalists’ objections on board, we would be sitting here in the dark”
Who, might we ask is Dr. Robert Hawley? There are no prizes for correctly guessing
that, at least in May 1992, he was the newly appointed chief executive of “Nuclear
Electric”.
SATISFYING FUTURE ENERGY NEEDS
9.5 The Virtues of Thrift
If the draconian solution of switching to nuclear energy as a means of

delaying global warming is unlikely to work to advantage in the time available and
may even bring economic as well as other disadvantages in its train is it conceivable
that merely saving energy could do as well or even better? Perhaps surprisingly even
the most conservative estimates put the potential contribution of conservation (to
decreases in carbon dioxide emissions) much higher than the potential sparing effect
of nuclear power. Indeed its most optimistic proponents see it as the complete answer
to carbon dioxide increase in global warming. According to Lovins, for example,
energy-saving (in the period 1984-86) expanded U.S energy availability by nearly
thirteen times as much as did nuclear power despite the fact that nuclear energy was
80 times more heavily subsidised than efficiency improvements. Moreover, he
contends that:-
“full practical use, in existing buildings and equipment, of the best electricity-
saving technologies already on the market would save about three-fourths of
all electricity now used, at an average cost certainly below 1c/kW.h-1 and
probably around 0.6c/kW.h-1 much less than the cost of just running a coal
or nuclear power station, even if building it cost nothing; and ” -
“full practical use of the best demonstrated oil and gas saving
232
THE VITUES OF THRIFT
technologies (many already on the market and the rest ready for production
within 4-5 years) would save about three-fourths of all oil now used, at an
average cost well below $10/bbl and probably nearer $5-6/barrel less than
the typical cost of just finding new domestic oil.”
He also makes the point that (305)
“most of the best electricity saving technologies on the U.S. market today
were not available a year ago and the same was true a year ago” - i.e. that
the pace of technical innovation in energy conservation is manifestly rapid”.
In terms of what can be readily understood he cites the following example.
“An 18 watt compact fluorescence lamp, producing the same light as a 75-
watt incandescent lamp for ~ 13 times as long, will over its lifetime save about
one-ten-millionth as much electricity as a huge (1,000-megawatt) power
station generates in a year. A single such lamp will thus
avoid the emission from a typical U.S. coal plant of
a ton of CO2, which adds to global warming, and

~ 8 kg of SO2. which contributes to acid rain, plus NOx, heavy
metals, and other pollutants; or
avoid the production by a typical nuclear plant of
half a curie of strontium-90 and cesium-137 (two major

components of high-level waste) and
~25 milligrams of plutonium - about equivalent in explosive power

to 385 kg. of TNT, or in radiotoxicity, if uniformly distributed into
human lungs, to at least ~ 2,000 cancer-causing doses.
Yet far from costing extra, the lamp will save
the cost of a dozen ordinary lamps and their installation labor

(typically totalling ~$20), plus
the cost of generating 570 kW-h of electricity (typically ~ $20-30

worth of fuel),
and, during its lifetime, will defer
approximately $200-300 worth of generating capacity, reserve

capacity, grid and fuel-cycle equipment.
Since the lamp’s typical retail price is only $15-18, and its real resource cost
is about a half or third of that, its use generates for society, at least tens of
dollars of net wealth, not counting its avoided environmental costs.”
This message has already been taken to heart by a number of electricity utilities in
the United States. For example:-
“In a $215-million plant that is the first of its kind, Boston Edison, one of
New Englands largest utility companies, will at least temporarily forestall the
need for new power plants by paying instead for an array of energy
233
conservation measures. The conservation programme, negotiated by

representatives from the utility, state government and local environmental
groups, is hailed by all three groups as a “revolutionary shift” and “a model
of enormous importance for the rest of the nation”.
The plan is expected to reduce the demand for electricity in the Boston area
by a thousand million kilowatt hours over the next five years, roughly
equivalent to the amount of power generated by a small 120-MW power plant.
It is particularly notable for its timing, announced shortly after the Seabrook
nuclear power plant in neighbouring New Hampshire was cleared finally for
its full-power licence after a gruelling and costly decade-long ordeal (see
Nature 344, 96; 8 March 1990).
Boston Edison will invest immediately in measures such as making new

buildings more energy-efficient than present standards require, retrofitting
existing residential and commercial buildings and supplying energy-efficient
light bulbs free or at low cost.
During the next five years, the utility expects to save two dollars’ worth of
electricity for every dollar invested. In an innovative economic incentive
system, the utility will be allowed to retain a portion of this expected $400
million in energy savings as profit in addition to recouping its costs. The rest
of the savings will be passed on to customers. With such a market incentive,
conservation becomes equally if not more profitable for the utility as the
construction of new generating capacity.
Although conservation plans are not new, observers say that the Boston
Edison announcement marks a trend towards a distinctly new movement on
the part of electric utilities towards conservation. The intense opposition to
the Seabrook nuclear power plant may be an extreme case, but is indicative
of the difficulty of bringing any new power plants on line.”
....Seth Shulman (“Nature”, 282, 344, 1990).
Similar economic considerations apply to the more complex issues of abating

nuclear proliferation, and reducing dependence on Middle Eastern oil. “Achieving
these benefits by improved end-use efficiency lets one make money on the deal.” This
is, in a variant on Marv Goldberger’s memorable phrase, “spherically sensible”.
Energy efficiency makes sense no matter which way you look at it. It should be done
to save money, even if we’re not concerned about such issues as global warming.
9.6 Would Energy Conservation Help?
The implication of what is set out in the preceding section is that not only
is energy conservation a feasible and laudable strategy but that it might, unaided,
solve the greenhouse problem entirely. There are, of course, as many uncertainties
in this approach as in any other, not least the fact that
“people and nations are unlikely to behave wisely (until) they have exhausted
all other alternatives”.
Even so, it is both possible and informative to make educated guesses. These put
possible future increases in saving efficiency based on existing technology at
somewhere between 4 and 10 times those achieved in 1973. The more optimistic of
234
WOULD ENERGY CONSERVATION HELP?
these give considerable food for thought. One German study, for example, envisages
a world of 8 billion people in 2080 “uniformly industrialised to the level of the
Federal Republic of Germany in 1973” (at this time the FDR was one of the most
heavily industrialised and energy-efficient countries in the world). Such uniform
industrialisation would imply a 5-fold global increase in economic activity and a 10-
fold increase in under-developed countries (i.e. the scenario is not one which is
unrealistic about the natural aspirations of the third world). Nevertheless, if such a
world had fully embraced the use of energy saving technologies already available in
1980 it would, in 2080, need only about one third of the energy actually used by the
real world a century before, in 1980. Moreover, most areas of the world would be
virtually able to meet all of their energy requirements from renewable sources. In
Lovin’s words there would be “no energy problem - even on economic growth
assumption that most would consider implausibly high”. Such a world would use 4
or 5 times less energy (than conventional projectives would allow), cost much less,
stretch oil and gas for centuries, dispense with reliance on both the Middle East and
the atom and by 2030 have “attained” a carbon dioxide level barely above today’s
and rising by 5ppm every three decades or so, making this part (~40%) of future
global warming virtually vanish. Many other problems would also disappear such as
those associated with the million bombs worth of plutonium it is proposed to extract
annually and put into global commerce.
RENEWABLE RESOURCES
9.7 Looking at Alternatives

There are also other ways:-
Table 9.1
Renewable Resources
Solar Geothermal
Photovoltaics Hydrothermal
Active Solar Electricity
Passive Solar Direct Heat
Solar Thermal Binary Cycle
Hot Dry Rock
Biomass Geopressured
Direct Combustion Magma
Biogas
Ethanol Ocean
Gasification Tidal
Liquefaction Wave
OTEC (p. 237)

From Renewable Sources of Energy OECD
235
“The modern world demands energy that is concentrated and readily

available. The renewables, by contrast, are invariably the opposite. They are
diffuse - the waves off the Hebrides have an average power density of around
45 megawatts a kilometre but it would require a 300 kilometre stretch of wave
energy devices just to satisfy a fifth of Britain’s present electricity needs. They
are variable - the wind does not blow consistently over the face of the land.
And their supply does not always coincide with demand - solar radiation, for
example, is at its most intense in Britain in the summer months when the need
for heating is at its least. Moreover, while they are often thought of as being
totally benign, deploying the renewable energy technologies could exact an
environmental price. Wind farms, for example, may be considered visually
intrusive or too noisy; an over emphasis on energy forestry might upset the
ecology of the countryside; and tidal power schemes could have a detrimental
effect on the habitat of wildlife around river estuaries. The exploitation of any
form of energy always has its drawbacks” ...U.K Dept. of Energy
The Department of Energy, might have added that most of the above drawbacks
would pale into insignificance compared with the drawbacks of conventional sources
but it does make a valid point. Nevertheless, despite the very real disadvantages of
some renewable resources (Table 9.1) they are renewable and, collectively, offer real
hope for the future.
9.8 Ocean Energy
“Water, water everywhere nor any drop to drink”

....Samuel Taylor Coleridge (The Ancient Mariner)
At present the most important renewable resource is wood (Section 9.14) still
very widely used for cooking, heating and construction, and as newsprint. But, if we
are to look to the future, water has considerable potential. If, as a citizen of the U.K.,
you visit the capital of Australia it comes as a shock to discover how little the people
of Canberra pay for their electricity; that it is still possible to generate large amounts
of electricity by conventional methods (water running down-hill, or from the base
of dams, through turbines) in drought conditions in a country in which it might be
more realistic to talk of the number of acres per sheep rather than the number of
sheep per acre. In any country, with reasonable rainfall over hills, electricity can be
generated in this fashion. In addition many countries are blessed with waves and
tides. Let us take one very pertinent example. There are many sites in Great Britain
which would lend themselves, admirably, to the harnessing of tidal power.
Paramount amongst these is the Severn Estuary. Arguably this could displace nuclear
power entirely in the U.K. if this declined by the year 2000 to the 6.0 GW capacity
suggested by John Surrey. The Severn Barrage Development Project proposes 216
turbo generators each rated at 40 MV giving a total installed capacity of 8640 MW
(8.6 GW). The direct capital costs are approximately £1/Watt (i.e. about £8 billion
at 1988 prices - substantially less than the cost of the British “independent” nuclear
deterrent). This includes the initial cost of construction and the length of the
construction period before power is generated. Once up and running, the operating
costs would be low, no CO2 would be released into the atmosphere, there would be
no accumulation of radioactive or chemical waste. That is not to say that there would
be no environmental costs although present studies suggest that the estuary would
support more birds and fish, in total, than at present even though some species might
be adversely affected. Some 200,000 man-years of work would be involved in the
construction of the barrage and the turbines and, although the arithmetic is clearly
236
OCEAN ENERGY
simplistic, it is worth noting that the present cost to the U.K. taxpayer of 200,000
man years of “idleness” (i.e. unemployment benefit etc.) is approximately £1.8
billion. Thirteen additional sites in England have been identified as having potential
for tidal barrage schemes. It is not difficult, on this basis, to conclude that the
argument that there is no practical alternative to nuclear power cannot be sustained
or that renewable resources could not eventually displace fossil fuels. Sadly, the
decisions involved do not rest only on feasibility, cost and environmental
“friendliness”. Possibly the greatest obstacle in the U.K. is still the strength of the
nuclear lobby. For example, Britain is exceptionally well endowed with ocean waves.
There are sites off the Western Isles which compare favourably with any in the world
and the total potential has been put at about 40% (about 80 million tonnes of coal
equivalent a year) of the U.K.’s primary energy requirement. Despite this vast
potential of inexhaustible energy
“the Department of Energy concluded that large scale offshore wave energy
was unlikely to be economic in the U.K. for the foreseeable future”
and therefore suspended its research and development programme in this field after
spending less than £20 million (about six orders of magnitude less than that expended
on nuclear research). There have even been suggestions that some of those concerned
in decision making have been economical with the truth when weighing the relative
merits of wave and nuclear power. The “Salter Duck” ( a moored device with a row
of beaks which bobbed up and down and used internal hydraulic devices to capture
energy and generate electricity) was held to be a dead duck on the basis of cost but
newer, cheaper, versions still continue to offer real promise. In Britain, all that
remains is a number of tiny, individual devices for powering navigational aids (such
as tethered buoys) and a 180 KW prototype of a “Shoreline Rock Gully System” on
Islay (better known for its whisky). This involves a “Wells Turbine” in which the
rise and fall of waves drives air through a device which revolves in the same
direction regardless of the direction in which the air flows. A larger (2GW) off-shore
machine was deemed to have poorer economic prospects than other alternative
generating technologies. Evidently the engineering problems are formidable but,
given the success of oil companies in exploiting North Sea reserves it is difficult to
believe that a potentially larger, renewable, energy supply did not warrant further
development. In the United States there is continuing interest in a pneumatic wave
energy conversion (PWEC) system which works by alternately compressing and
expanding air and passing it through a unidirectional rotor. A possibility that 90%
of a wave’s energy could be extracted by judiciously placed sub-surface vertical flaps
is also being investigated.
Ocean Thermal Energy Conversion Technologies (OTEC) operate on the

principle that energy can be extracted from heat sources and sinks at different
temperatures. Warm surface water is pumped through an evaporator and thereby used
to vaporise ammonia or freon. The vapour drives a generator and cold water
condenses it for recycling. Alternatively, in an open system, the warm ocean water
itself is used as the working fluid. In the most advanced systems water is flash-
evaporated in an evacuated tube and the rising mist condensed by the cold water. The
condensate runs down a tube under gravitational pull and, in so-doing, drives a
conventional turbine. This system, if we forget the fact that all is ultimately driven
by a difference between hot and cold water (like conventional power plants in which
fossil fuels are used to heat the water), seems to come perilously close to getting
something for nothing. Nevertheless it does work and has much to offer to island
communities in the tropics. As a by-product it produces distilled water for drinking
and nutrient-rich cold sea water for fish farming etc.
237
9.9 Gone with the Wind
Go past Hollywood and away from Los Angeles towards Riverside and
beyond. In the deserts there are wind-farms, not very pretty but effective. By the end
of 1985 more than one gigawatt (GW) of wind capacity had been installed in the
United States, nearly 99% of it (some 13,000 machines) taking advantage of the
strong summer winds in California which represent 2.5% of installed capacity and
producing 1% of demand. In Denmark, second only to the United States but still way
Table 9.2
WIND ENERGY PRODUCED IN 1985 BY LOCATION
CALIFORNIA INVESTOR OWNED UTILITIES1
- Pacific Gas & Electric Co. 50.0%
- Southern Californian Edison Co. 38.0%
DENMARK 5.3%
CALIFORNIA DEPT. OF WATER RESOURCE 1.6%
OTHER EUROPEAN COUNTRIES 1.3%
OTHER UNITED STATES LOCATIONS 1.3%
REST OF THE WORLD 2.8%
1. Interconnected to, but not owned by three utilities.
Source: American Wind Energy Association
behind, wind farms provided up to 0.5% of electricity in 1985. Wind farms of 5

megawatt (MW) capacity are proposed for the Netherlands and Belgium. Denmark
has plans to install 100 MW and to provide 8% of Danish consumption by 2000. The
U.K. Department of Energy believes that:-
“if predicted costs can be achieved in principle it is possible that by the year
2025 on shore window power could be supplying 10% of the countries
electricity needs and perhaps as much as 20% in the longer term”
....U.K. Department of Energy.
The cost of electricity generated by wind turbines is similar to that from coal-
fired power stations (i.e. half that of nuclear power). While the impact of wind farms
on the environment shrinks into insignificance when compared with conventional or
nuclear powered plant and coal mines, there is no doubt that they are noisy (audible
up to 2000 metres downwind) and visually intrusive. There is radio and television
interference extending up to 3 km or more from the largest turbines.
238
GONE WITH THE WIND
9.10 Let the Sun Shine In
We have all heard of surfaces which become so hot in the sun that can be used
to fry eggs. Dudley Moore, on film, has graphically illustrated the problems of
applying tender feet to hot sand. Along these lines, solar energy is widely used in
“passive” applications (particularly in countries with ample insulation) such as
heating domestic hot water and swimming pools. The best commercial hot water
system operates with an annual solar conversion efficiency of 40%. Typical solar
water heaters in the United States comprise 5-6 m2 of collector area, and cost the
user from $3000-5000 (1987 prices) installed and meet up to 80% of annual energy
needs for this purpose. Solar cooling can be based on conventional closed cycle
refrigeration techniques in which the high temperature needed to drive the cycle,
more usually provided by electricity or gas, is replaced by solar energy. There are
also systems based on open cycle evaporative cooling (i.e. ones in which the latent
heat of evaporation causes cooling and solar energy is then used to dry or regenerate
the desiccant). Simple but very effective evaporative cooling for glasshouses is based
on water trickling over large porous surfaces (bales of straw, bark from trees,
plastics) through which air is drawn by extractor fans at the other side of the house.
9.11 Photovoltaics
Robert Hill may be regarded as the father of modern photosynthesis in that

the Z-scheme (Section 4.3) is the basis of our present understanding of the
photochemical events concerned in energy transduction. The Royal Society, in
recognition of his major contribution, to this field awarded him its prestigious Copley
Medal a distinction previously afforded to such familiar names as Joseph Priestly,
Charles Darwin and Francis Crick. In 1791 the Copley medal was also awarded to
Allessandro Volta (1745-1827) who is repeatedly remembered, like Ampere and
Watt, in electrical terminology - as in the terms “volt” and photovoltaics”. The
“photovoltaic effect” itself was discovered by Edmund Becquerel in 1839, some
twelve years after Volta’s death, when he noticed that when light shone on one side
of a simple battery cell the generated current could be increased. The first selenium
photovoltaic cell followed in 1883 but it was left to Albert Einstein to describe how
the interaction of photons with the electrons in orbit about an atomic nucleus (c.f.
Section 1.1) could generate a flow of electrons (an electric current). As figure 9.1
shows this is essentially the same, in principle, as electron transport in thylakoid
membranes initiated by light excitation of chlorophyll (Section 3.1).
In 1954, Bell Laboratory Scientists produced a solar (photovoltaic) cell from

pure silicon with an efficiency of 4%. Since then the efficiencies have risen and
production prices have fallen (from US $20/Wp to US $5-8/Wp in 1985 and a
prospect of US $1/Wp in 1992).
[“A peak watt (Wp) is the power generated on a clear day when the sun’s rays
strike perpendicular to the cell”.]
In practical applications, groups of cells are mounted on a rigid plate and

bonded together to form a module, typically about 1m2 in size with a generating
capacity of 50 - 100 Wp and an efficiency of 9-12% (90-120 W.m-2).
Present day photovoltaic cells were largely a by-product of space research and
large arrays of solar cells are used to power satellites. On Earth they are increasingly
used in circumstances in which there is a need (in the absence of mains electricity)
239
to power telecommunications, lighting, refrigeration, water-pumping, water-

treatment, navigational aids etc. but the rapidly advancing technology holds out real
hope that they could become major sources of renewable energy. There are vast areas
of desert in Africa, Australia and elsewhere which could accommodate massive
arrays of photovoltaic modules in areas of high insolation presently making no
contribution to Man’s energy requirements. At a more modest level the
“Forschungshaus Remscheid” in Germany, has the distinction of being the world’s
first residence with photovoltaic roof tiles, generating up to 7800 Kwh/year. If it ever
becomes technically and economically feasible to tile most houses in this way the
direct savings in fossil fuels would be amplified by the enormous savings inherent
in transmission losses through national grids and the erection and maintenance of
such systems. No doubt, there would be an increase in the tendency, already
apparent, of major industrial electrical consumers to generate power, on site, by more
conventional methods. This, in turn, would lead to the efficiencies associated with
the utilisation of waste heat for space heating.
Light
Electron flow
_
Load
Conventional
direction of
current
n -Silicon Metallic contact finger

(electron pick up)
Total Antireflection coating
thickness p -Silicon
250-350 µm Cell junction
Metal baseplate
Fig. 9.1 A photovoltaic cell. (After McNelis, Derrick & Starr). The principle is similar
to the generation of electron transport in photosynthesis (Section 2.8). Incident photons
liberate (negatively charged) electrons thereby creating positively charged holes which
constitute a sink. Thus an electric current is created, carrying electrons to fill the holes.
Despite its present usefulness and efficiency, photovoltaic generation of

electricity on a really significant scale does not yet exist. To some, the prospect that
it might seems fanciful. It would be difficult to argue, however, that the likelihood
of appreciable generation by this mechanism is either remote or less probable than
by fusion. Indeed it is a better bet, in almost every regard, than nuclear fusion.
“It is likely that a 15% efficiency for amorphous silicon (asi) thin-film
cells can be reached fairly soon which would assure the viability of
amorphous silicon for power applications in addition to its widespread use
in consumer speciality products.” ...OECD International Energy Agency.
240
HOT ROCKS
9.12 Hot Rocks
Seek to order a Bourbon or a Scotch in a bar in the United States and you
might well be asked if you want it “on the rocks” or “straight up” (i.e. with or without
ice). But there are hot rocks as well.
“Geothermal energy derives from the heat flowing outwards from the interior
of the earth, due to the cooling of the core and in some places the decay of
long-lived radioactive isotopes of uranium, thorium and potassium. It can be
tapped from aquifers - underground deposits of hot water in porous rocks -
and from hot dry rocks “ ....U.K. Dept of Energy.
The Romans were into this with avidity, possibly learning from the Greeks,
certainly combining (in Britain) their sybaritic pleasure in bathing with the
availability of the warm aquifers which have kept the spa at Bath busy ever since.
Go to Yellowstone National Park in California and admire the geysers like “old
faithful” which erupt periodically on time and throw jets of hot water many feet into
the air. Go to Rotorua in New Zealand and see the spot where an erratic geyser
terminally despatched a group of tourists some years ago. Marvel at jets of steam
emerging from Maori graves or from lawns or flower beds. There, as in Iceland and
elsewhere, this steam and hot water is put to use (Table 9.3) and indeed, in Rotorua,
its unrestricted use is no longer allowed by the local inhabitants because such tapping
has diminished and even threatened the continuing existence of the more lucrative
tourist industry which it has attracted. All of these, like volcanoes, remind us that
the centre of the earth is still extremely hot and that exploitation of such heat
constitutes a source of power.
Table 9.3
Hydrothermal Electric Power Plants
Country No. Units MW
United States 56 2022

Philippines 21 894
Mexico 16 645
Italy 43 219
Japan 9 215
New Zealand 10 167
El Salvador 3 95
Kenya 3 45
Iceland 5 39
Nicaragua 1 35
Indonesia 3 32
Turkey 2 20
China 12 14
Soviet Union 1 11
France (Guadeloupe) 1 4
Portugal (Azores) 1 3
Greece (Milos) 1 2
Totals 188 4.7 GW
[Data for 1985 after Ronald DiPippo, Geothermal Electric Power-Scale of the World,
International Symposium on Geothermal Energy.]
241
Future potential exploitation of geothermal energy may not be restricted to

those few areas where hot water emerges from the ground or where there is volcanic
activity. Nevertheless despite the long history of geothermal energy applications it
was not until 1904 that natural steam was first harnessed for electricity generation
by Prince Piero Ginori Conti at Larderello in Italy. Table 9.3 lists the number and
capacity of such plants in 1985. Hot Dry Rock (HDR) technology seeks to heat
surface water by pumping it into hot impermeable rocks through fissures enlarged
by hydraulic fracture. One such project has been undertaken at Rosemanowes, in
Cornwall, where the heat flow on the Carnmenellis granite batholith is twice the U.K.
average. A three stage programme was based on examining the feasibility of a viable
HDR reservoir. Bore holes were sunk to 300 metres and subsequently to 2500 metres
with a view to eventually going to six kilometres. This latter would tap the 200°C
heat required for efficient and economical electricity generation. Similar geothermal
research is being undertaken in France, Germany, Sweden and Japan and at the Los
Alamos National Laboratory (New Mexico) in the United States.
9.13 The Rain Forests

“Look guys, the cure for cancer could be out there in the forest and
you’re about to destroy it.’ And they would say ‘Dream on”
....Wendell Wood (Oregon National Resources Council)
The inclusion of a section on rain forests here, in a chapter which addresses

the question of how we might satisfy future energy needs, carries no implication that
they constitute a major energy resource. Rather it springs from the fact that the
following section (9.14) summarises some of the ways in which contemporary
biological materials, rather than fossilised biological materials can, and do,
contribute to Man’s energy requirements and that once we start to think about wood
these days our next thoughts, if we have any concern at all for the environment, ought
to turn to the rain-forests. It is clear that these are areas of immense beauty which
deserve all the protection which we can afford them and that any exploitation should
be carried out in the manner which would sustain them and guarantee their future
existence. If there were ever a need for Man to exist in real equilibrium with his
environment it is here. Nevertheless there are misconceptions. Thus it has sometimes
been said that the destruction of tropical rain forests is to be deplored because these
vast tracts of vegetation act as huge sinks for carbon dioxide. There are many
compelling reasons for not destroying the rain forests but this is not one of them (see
page 243). Trees temper the impact of heavy rain which otherwise denudes top-soil,
and forests may absorb 20 times as much rain as bare earth. Transpiration returns
much of this water to the atmosphere, so that it is effectively recycled, In these ways
forests have a major effect on climate. But perhaps the most compelling reason for
conserving the rain forests, even if we only view things from a totally selfish
standpoint, is that they are the repository of a huge wealth of plant products and
genetic information which, once lost, might never be recovered. Rubber is a perfect
example. Once it was of no consequence and now, although still extremely
important, is not something for which there are not satisfactory alternatives, at least
in some uses. However, throughout the early development of electrical devices and
road transport it was a key commodity in the development of Man’s world as we
know it. Manaus, formerly a place of no consequence on the Amazon, became as
wealthy as an oil sheikdom because of rubber and its opera house was even able to
pay Caruso to spend many weeks travelling between there and his native Italy.
Eventually the perfidious British stole rubber plants and established plantations in
what is now Malaysia, world wars promoted the search for alternatives and that
aspect of rain forest economy is no longer what it was. Nevertheless, it is entirely
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THE RAIN FORESTS
feasible that there are, in addition to all of the plant products (like rubber) which are
currently known to be of value to Man, others which could play a vital role in some
not yet imaginable future technology - provided that, at this future time, they still
exist.
Pacific yews, once felled and burned to near extinction simply to provide
logging companies access to Giant Redwoods have been found to contain a chemical
regarded as a most important agent in the treatment of breast and ovarian cancer.
Drugs from plants are currently worth $40 million a year. Moreover, Man does not
live by bread (or rubber) alone. Happily, there is now a large body of public opinion
which believes that it is at least as important to cherish our natural environment and
conserve it as it is to maintain artefacts of our own history and culture. Properly
“managed” rain forest could not only give those who live there a better economic
return than forest either totally untouched or totally destroyed but could make its own
contribution to the sparing of the greenhouse effect. Fully mature forest does not do
this. It is in near equilibrium with its environment, producing as much carbon dioxide
and methane by respiration and decay as it fixes or withdraws from the atmosphere,
in photosynthesis. Young, actively growing forest, on the other hand, consumes more
carbon dioxide than it releases and this is equally true of northern, temperate and
continental forests. Of course, if an existing forest is burnt, this releases carbon
dioxide to the atmosphere in the same way as the burning of fossil fuels but forests,
in themselves, are not the answer to the Greenhouse Effect. They fix enormous
quantities of carbon dioxide, so much that northern forests are largely responsible
for the annual “teeth” that are seen in the remorselessly rising carbon dioxide curve
(Fig. 7.4) - i.e. the difference in the rate of photosynthesis between summer and
winter, even in northern, evergreen, forests is sufficiently large to be detected in the
annual records of carbon dioxide accumulation. On the other hand, mature forests
produce equally large quantities of carbon dioxide.
It is clear then
(a) that burning forests adds to the carbon dioxide in the atmosphere
(b) that mature, stable forests are more or less in balance, consuming about as
much carbon dioxide as they release, and
(c) that only actively growing forests (i.e. newly established forests or forests in
which orderly felling of old wood permits active regeneration of new) act as
substantial sinks for carbon dioxide.
Japan makes one of the world’s largest contribution to the destruction of rain
forests and uses much of the hardwood that it imports to make plywood cases to
contain concrete poured into buildings during their construction. These plywood
boxes are then stripped away and burned. Wood is preferred for this purpose only
because it is cheap. Moreover, it is “cheaper” to destroy irreplaceable rain forests for
this purpose than it is to use freely replaceable softwood. In the United States, which
has a better record than most in some respects, President Bush calls upon scientists
to provide more and better facts on global warming before seeking to make a real
impact on his country’s contribution (about one fifth of world totals) to carbon
dioxide emissions. All of these and countless other arguments or evaluation of costs
miss the point. We have to do what is “spherically sensible” (Section 9.5) because
it is “globally sensible”. It is worth doing because it will bring benefit in its own
right. Burning rain forests is one of the largest contemporary contributions to global
catastrophe but, irrespective of this, the rainforests should be preserved because they
are home to an immense number of species including Man. As areas of great natural
243
beauty, they are as worthy of preservation as the Taj Mahal.
“worthy of preservation as the Taj Mahal”
Even at a purely material level they could, if properly managed, continue to provide
resources and a livelihood for their native human populations ad infinitum. Similarly,
a major acceleration of energy conservation in the United States would, at least in
the eyes of some economists (Section 9.5) make that nation even wealthier and more
competitive than it is at present. A diminution in smog would be as welcome to the
inhabitants of Los Angeles as would the prospect of relatively stable sea-levels to
the inhabitants of the Maldives. There is nothing wrong with the accountants’
approach, provided that we remember that accountants know the cost of everything
but the value of nothing. We must all pay our bills but it is perfectly proper to insist
that accountancy includes accountability. Saving money by energy conservation is
laudable because everyone is likely to benefit in the long term. Saving money by
fouling up our environment is unacceptable. Saving money in the short term, by
exporting our CO2, SO2, plutonium, dioxins, into someone else’s environment, is
criminal.
9.14 Biofuels
“at current energy prices, biofuels could make a potential economic

contribution to United Kingdom energy supplies of over four million tonnes
of coal equivalent a year (4Mtce/yr) And given modest increases in energy
prices, the size of the contribution could rise to fifteen Mtce/yr by 2025.”
....U.K. Department of Energy
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BIOFUELS
“Biofuels” are derived from “biomass”. “Biomass” is everything derived,

directly or indirectly, from photosynthesis carbon assimilation. Globally, this
comprises some 150-200 billion tons of dry mass annually whereas
consumption is nearer 1 billion tons.
[Half of the world’s population uses firewood, or recently produced organic

matter, such as dung, for cooking and heating. The average daily consumption
is about 1 Kg of dry biomass per person per day (i.e about 150 W on a
continuous basis which is equivalent to about 300 GW, worldwide). Thus the
poorest inhabitants of the Third World use half as much energy again, for
cooking and heating, as for metabolic purposes, largely because of the
inefficiency (5%) of open fires. It will be remembered that the corresponding
figure in the wealthy West (for all non-metabolic purposes) is 5-10 KW.]
As a small boy it was my task to procure the family firewood. I scoured local
shops for surplus wooden crates and chopped them into neat bundles of sticks. These
were used with newspaper to pass the flames to the coal which was burned on open
fires as the sole source of warmth and hot water. We all bathed once a week, not
because we were basically unclean but because our hot water was strictly limited by
rationing or hard economics. Had I known it, I was doing much the same task, at
that time, as many in the Third World (where firewood is still immensely important
for cooking and heating) continue to do on a daily basis.
Now, in partial retirement, the wheel has come full circle and, in a rural
retreat, my wife and I rely on wood-burning stoves for warmth and hot water. A
hectare of adjacent woodland will make us more or less self-sufficient in this regard.
In the northern hemisphere, at least, wood warms four times (i.e. in felling, leading,
chopping and burning) and happily it does nothing, whenever it is used, to adversely
influence the level of CO2 in the atmosphere, provided that any generation of people
burns only that which it grows or allows to grow. Only actively growing forests
remove more CO2 from the atmosphere than they return. Only burning vast areas of
forest increases atmospheric CO2 and, in this regard, there is a clear comparison with
burning fossil fuels. Both return, in short measure, CO2 removed from the
atmosphere over long periods. Burning the products of contemporary photosynthesis
is simply a part of a re-cycling process. As David Hall and his colleagues have
pointed out, a gigajoule of biomass substituted for coal would reduce CO2 emissions
by the carbon content of 1 GJ of coal (about 0.025 tonnes) and that, since biomass
with a heating value of 20 GJ per tonne is 50% carbon, growing 1 GJ of biomass
would sequester 0.025 tonnes of carbon. Moreover,
“biomass can play a larger role in global warming when used to displace
fossil fuel than when used for sequestration because land can be used
indefinitely in displacing fossil CO2 whereas removal ceases at forest
maturity in the “sequestration” strategy” ....D. O. Hall
[The “sequestration strategy” is the concept of growing trees, not to use, but
as living repositories for CO2. Actively growing trees abstract much more
CO2 from the atmosphere than they return. Mature trees do not. In the short
term, therefore, massive planting of trees would tend to offset rising CO2 to
some extent. In the longer term a new equilibrium would be established.
Using biomass, as suggested by Hall, is a better strategy.]
Even dung can play a role. The new visitor to India is surprised that sacred
cows do not bring clouds of flies in their wake. Rather climate and poverty combine
to ensure that cow “pats” are dried, often in neat and characteristic designs, on every
245
available wall and surface and then used to heat cooking-pots. The women and
children most exposed to the secondary products of this combustion in enclosed
spaces do not benefit from this experience but otherwise it is an ecologically sound
practice. Much research into more sophisticated systems is being undertaken
elsewhere. Sweden does not squander its forest wastes and has looked seriously at
the selection of fast growing willow varieties which could be coppiced for fuel and
building. Even the feasibility of burning sawdust in a vehicle’s engine has been
contemplated. Yields of 25 dry tonnes per hectare have been achieved without
nitrogen fertiliser, in Hawaii, by interplanting eucalyptes with nitrogen fixing Albizia
trees.
When bent on procuring firewood as a child I might well have chanted a little
doggerel which included the immortal condemnation “my mother doesn’t like her,
because she comes from Byker” but Byker is now one of the jewels in the crown
of the U.K. Department of Energy’s scheme for developing biofuel technologies. A
mile or two from the spot where a sad figure, contemplating execution, once wrote
altogether better words (about taking the high road or the low road to Scotland), the
Byker Reclamation Plant, produces densified RDF (refuse derived fuel) which can
have a gross calorific content equal to about 60% of that of British coal.
Straw is also something to be conjured with. It suffers from the fact that it
is very light compared with coal or even with wood, a drawback that it shares with
many other forms of biomass which might otherwise be used more widely as fuel.
The problem with lack of density has to do with difficulties in transport in the first
place and problems with burning in the second. Oil, by comparison, does not contain
water which must be transported willy nilly (thereby adding to costs) and feeding
oil from a container into a furnace involves little more than a pipe and a valve. On
the other hand straw contains a great deal less water than many forms of biomass
and lends itself to use on the farms on which it is produced, thereby solving the
additional problem of how else to dispose of it.
“Of the straw produced in the U.K. each year, some seven million tonnes,
with an energy content of 3.6 Mtce, finds no saleable outlet and is largely
burnt in the field. However straw could be put to cost-effective use as a fuel
on the farm , in local industry and in rural institutions. Already some 170,000
tonnes a year are used on farms and this could rise to around 800,000 tonnes
by the year 2000.” ...U.K. Department of Energy
We are all too aware of biogas (c.f. Section 7.6). Apart from the traces of
extremely poisonous hydrogen sulphide which, when present, can give it such an
unpleasant odour, biogas is usually a mixture of methane and CO2 so that burning
it is ecologically desirable in that methane, once burnt, becomes CO2 which is less
damaging than methane itself in terms of greenhouse effect. In the U.K. a great deal
of garbage goes into holes in the ground (“landfill”) where it generates methane by
bacterial action. Demonstrations have established the credibility of landfill gas as a
practical energy source equivalent to 120,000 tonnes of coal a year. This is expected
to rise quickly to about 400,000 tce/yr.
Elsewhere sewage, in pits, provides methane for lighting. Intelligent use of

biomass in the Third World includes, for example, burning sugar cane wastes
(bagasse) in distillation of alcohol (produced by fermentation) as a fuel for vehicles.
This is being increasingly imitated in the West. Sewage is a problem world-wide and
in places where temperature permits, as in Israel and California, algal ponds are often
used in sewage treatment. The algae photosynthesise and, at the same time, utilise
the organic nitrogen and minerals from the sewage. Although the algal end-product
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HYDROGEN POWER
has been used as animal feed and for other purposes (some too extraordinary to be
discussed in polite society) the principal by-product is clean water. This, of course
can be immensely valuable particularly in arid environments. So is the general
principle of yet again making a virtue out of a necessity.
Ethanol it would seem at first sight, has even more going for it than straw,
refuse or dung. Certainly Omar Khayam echoed a fairly common sentiment when
he wrote
“Come fill me with the old familiar juice,

methinks I might recover by and by”
and
“I often wonder what the vintner buys one half
so precious as the goods he sells”
Moreover, fermentation techniques are almost as old as Man and there is no

shortage of suitable biomass for this purpose. Brazil was producing around 8 billion
litres/year by the mid 1980s and, by now, total output will have been well in excess
of the equivalent of 300 million barrels of gasoline. Brazil uses sugar cane and some
Cassava as feedstock. The much smaller United States output (1.6 billion litres in
1984) is predominantly from corn (Zea mays).
The density and calorific content of ethanol (24 GJm-3) is less than that of
petroleum (39 GJm-3) because ethanol is more oxidised. It burns well and modified
engines running on ethanol can develop 20% more power and less polluting exhaust
gases. There, regrettably, the advantages stop because fermentation ceases at
relatively low alcohol concentration as the yeasts succumb to drunken stupor and
give up the ghost. Thereafter there is a need for distillation and this, involving (as
it does) a change from liquid to gas-phase requires very considerable energy inputs.
Certainly if arithmetic takes every aspect of the overall process into account it is clear
that ethanol production cannot constitute net energy gain. In the special
circumstances of places like Brazil this hardly matters. There are billions of acres
on which sugar cane will grow happily, like a weed, and the cane residues left after
sugar extraction make an excellent fuel which can be utilised in distillation plants.
Conversely in a country like Scotland (in which there are not too many arable acres
or warm days) barley, a C3 species, grows much less rapidly than does C4 sugar-
cane in subtropical climates. The products of distillation are then best stored for a
while in oak casks and finally savoured in front of a log fire.
9.15 Hydrogen Power
“I believe that water will one day be employed as fuel, that hydrogen and
oxygen which constitute it, used singly or together, will furnish an
inexhaustible source of heat and light, of an intensity of which coal is not
capable. I believe then that when the deposits of coal are exhausted, we shall
heat and warm ourselves with water. Water will be the coal of the future.”
....Jules Verne
The fact that it takes energy to split hydrogen-oxygen (H-O) bonds and that
energy is released when H-O bonds are re-formed, has also been a central theme of
this book. Most of Man’s energy is still derived (indirectly from nuclear fusion in
the sun) by re-joining hydrogens and oxygens separated during primordial
photosynthesis. In some regards gaseous hydrogen (H2) is an ideal fuel. Its
combustion:-
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2H 2 + O 2 → 2H 2 O Eqn. 9.1
releases much energy and the combustion product (H2O) is good enough to drink
(indeed it was drunk by cosmonauts). The trick, of course, is to produce hydrogen
in the first place. If we suppose that, by whatever future, unthought of, technical fix,
or by judicious use of renewable resources, we have succeeded in generating enough
electrical energy to maintain large populations in the manner to which they have
become accustomed, we would still have a need for a fuel as convenient as petrol
(gasoline). It is conceivable that improvement to batteries will soon make electrically
powered vehicles more of a practical proposition than they are at present but long
distance road haulage, tractors, combine-harvesters, ships and aircraft will seemingly
need some appropriate petroleum product, or equivalent, into the foreseeable future.
In many respects hydrogen would be better than hydrocarbon fuels. Apart from the
fact that it would not give rise to pollutants in the form of oxides of carbon, sulphur
and nitrogen, it produces 2.8 times as much energy per gm as hydrocarbons and the
propulsive efficiency of hydrogen-burning jet engine is significantly higher because
of the lower molecular weight of the exhaust products (18 g for water as against
44 g for the CO2 which is also produces by burning hydrocarbons). Against this there
is the fact that liquid hydrogen occupies ten times as much space as conventional
aviation fuels and, it is argued, can only be feasibly carried in refrigerated tanks.
[Hydrogen can also be stored as a metal hydride. In principle, this is highly

desirable because the reaction is freely reversible and therefore allows a
hydride store to be replenished by hydrogen gas. Moreover the hydride can
accommodate large quantities of hydrogen so that its energy content becomes
20 MJl-1 compared with 1.7 MJI-1 for hydrogen gas (at 150 atmospheres
pressure) and diesel oil at 30 MJl-1. The weight of the hydride, like the
weight of cylinders of refrigerated tanks, becomes, a problem when portable
hydride stores for use in vehicles is contemplated.]
Notwithstanding these very real drawbacks, feasibility studies have shown

that it is possible to use hydrogen to power both motor vehicles and aircraft and it
might be supposed that the relevant technology will improve as soon as the oil
companies’ predictions about petroleum prices suggest to them that they should
make a major investment in this area. (As oil reserves dwindle, and population
continues its inexorable rise, it is clear that, apart from short-term fluctuations, oil
prices will rise to a level at which it will be too expensive to use oil as a fuel rather
than as a source of petrochemicals). It is also conceivable that, if the worst aspects
of the rising carbon dioxide syndrome become reality, the gratuitous emission of CO2
will become as unwelcome as the use of CFCs or smoking in public places.
Companies like British Petroleum already have a solar division which produces
photovoltaic panels to power vaccine refrigerators etc., for use in areas without mains
electricity. It is possible, in principle, to use photovoltaics to drive electrolysis of
water and indeed a practical version of Fig. 1.2 has been used for ten years or more
as a demonstration in an Environmental Biology course in the University of
Sheffield. Producing hydrogen in this way, or by utilising other renewable sources
of electricity for this purpose (in order to provide a substitute for petroleum in
vehicles) may not be round the corner; neither is it unimaginable. It is much more
difficult to contemplate unchanging trends in petroleum usage well into the next
century as sources diminish (and become more difficult to process, e.g. petroleum
from coal and oil-bearing shales) and as pressures on the environment become less
and less acceptable. The writing is already on the wall and it is beginning to be
heeded.
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EPILOGUE
9.16 Epilogue
“When the Earth’s last picture is painted and the tubes are twisted and dried”
....Rudyard Kipling
In 1939 it was still true to say that “the sun never set on the British Empire”
and although, as a consequence of the first world war and its aftermath, Imperial
Britain was not even then the country of vast wealth and industrial innovation that
it had been in Queen Victoria’s day, it was still a major power. After the (1939-45)
war, Britain was devastated and impoverished but certainly not in worse state than
Germany and Japan. Today, despite the supposed advantage of North Sea Oil,
Britain’s economy is still a matter for major concern whereas that of Germany is
strong and that of Japan has come to dominate the world. Without detracting from
Germany’s famous flair for organisation and thoroughness, or the fabled Japanese
work ethic, it is evident that there must have been other factors which led these two
“vanquished” countries to prosper while Britain has merely muddled through to its
present economically vulnerable situation. The reasons are complex and hardly
capable of analysis (certainly not as an aside, in what is primarily a biological text)
but they cannot be ignored entirely because they illustrate, and are central to, the
contribution which politics might make to the environment in the next half century.
(It is worth noting immediately in this context that most of our present world leaders
will be dead in 50 years time and that, in Western democracies there are few
politicians who can look beyond the next election let alone the next 5 or 10 years).
So, although it would undoubtedly be challenged and contested by those of

some political persuasions, there is little doubt that the major factor which has
contributed to the economic miracles of Germany and Japan has been investment -
positive investment in new industrial plant and technology and negative investment
in armaments. Faced with the destruction of most of their industrial base and the need
to make reparation to the victorious allies, Germany and Japan had to start afresh
on what was bound to be a new and better basis. In so doing, they were bolstered
by massive aid programmes from the United States born of the perceived threat of
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world communism. Moreover, they were bound, by treaty, to strictly limit their
expenditure on conventional arms and totally forbidden to make or acquire their own
nuclear weapons. Conversely, Britain and France were encouraged, by reparations,
to persist with old technologies and anxious, because of their reluctance to lose
world-power status, and the widely accepted concept of Soviet Imperialism, to invest
heavily in “defence”. Most of all there was the concept of nuclear deterrence, still
claimed by those who favour it (but in the obvious absence of the “control”
experiment) to have kept the peace in Europe for the past 40 years. Whether nuclear
missiles have kept the peace or have been a threat to peace is a matter for argument
and future historians but there are few historians, even now, who can regard the
“independent” nuclear weapons of Britain and France as anything other than attempts
by these nations to maintain a major role in world affairs. The economic price of
these status symbols has been, and continues to be immense. Germany, so long a
symbol of economic stability and power, now struggles with the huge burden of
integration but the price, as a proportion of gross national product, is certainly much
less than that of the United Kingdom’s ill-advised marriage to nuclear fission and
fusion.
By now, the reason for this excursion into history, economics and politics will
have become self-evident. It is intended simply to illustrate the fact that, within
recent history, putting aside the influence of world figures like Hitler, it has been
possible for governments to have a profound impact on economics (itself an issue
central to energy and hence to the future of the environment). In addition, even
though governments and elected representatives would be expected to be primarily
driven by self-interest and material well-being, there is absolutely no guarantee that
their interests will not be subordinated to what might be most charitably described
as matters of great principle. It is such matters that led to the recent awful conflicts
in the Middle East, the intervention by the United States in Vietnam and any number
of relatively minor conflicts. It is against this background that we can not count upon
our elected representatives to do what is eminently logical in the face of the vast
consequence of carbon dioxide increase. It is one thing to sign the Montreal Protocol
on CFCs because the political kudos is considerable and the economic cost relatively
trivial. It is quite another to contemplate action which would involve the deflection
of substantial funds from an area of perceived orthodoxy (such as defence, or nuclear
power) into the maintenance of the environment. Those who support or advocate
such change are immediately classified as ill-informed or unworldly. For example
in the U.K. the whole tenor of advertisement by the pro-nuclear lobby has been to
dismiss alternative approaches as unrealistic, ill-conceived, ill-informed or eccentric.
Immensely expensive demonstrations have been mounted to show that trains
carrying containers of nuclear waste could crash at high speed without spillage, that
the excessive changes within reactors could be accommodated without the prospect
of a second Chernobyl, and so on.
So latter day Noahs must expect questioning and virulent attack not only by
those with vested interests but even by the innocent (who prefer not to think about
the future in the way that most of us prefer not to dwell upon the likely time and
manner of our departure from the land of the living). None of this means that so-
called “Green” politics are absurd or unworldly. None of us need to have sleepless
nights about the eventual failure of nuclear fusion in the sun. It is far too distant in
time to concern us but the decline in fossil fuel reserves and associated rise in
population and in atmospheric CO2 and methane is here and now. If what is written
here serves any useful purpose at all, it might convince some that these processes
cannot and will not continue indefinitely. In fact, no scientific argument should be
necessary. Expansion within a finite space is necessarily limited. Man cannot
continue to exist as Man except in equilibrium with the environment. At present we
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EPILOGUE
are very far from equilibrium and curving away from it rather than towards it.
Personally, I take the optimistic view that Man will survive. In view of what is
already possible in the realms of genetic engineering, the likelihood that Homo
sapiens will survive, as such, is quite another matter. When we considered the laws
of thermodynamics, back in Section 1.9, we learned that we can’t win. There is a
universal tendency towards disorder (increased entropy) which is only fleetingly
reserved by living organisms. As Glasby has also emphasised, both an increase in
world population and a corresponding increase in economic activity inevitably means
increased environmental degradation and pollution (i.e. increased disorder). However
smart we are we can’t get round the laws of thermodynamics. Not surprisingly this
is a bitter pill to swallow. We cling desperately to the view that we can have our
cake and eat it. Those who enjoy life in the relatively wealthy parts of the northern
hemisphere and have any feeling at all for those in the poorer parts of the southern
hemisphere are glad to accept the concept that the “under-developed” should
develop. Those in the Third World demand this as of right. No doubt they should.
No doubt the rich should help the poor if only out of self interest. The rich and the
poor make uncomfortable neighbours and it is facile to suppose that the juxtaposition
of wealth and poverty does not affect us all adversely. But it should be clearly
recognised that if some genial entity waved a magic wand and embarked us on a
master plan which would make us all as affluent as the average citizen of the United
States by the end of the next century, we would sink beneath the weight of our own
iniquities long before that happy day. Two to three hundred million people
consuming fossil fuels and producing CO2 at rates near to those that currently obtain
in North America have already created problems which will be solved only if there
is a major, rapid and concerted response by the international community. There is
simply no possibility that 10,000 million people (a figure fast being approached)
could use and pollute, at the same rate as these chosen few, without inviting
catastrophe. Mankind can only survive if the peoples of the Earth contrive to live
in equilibrium with their environment. At present the environment staggers under the
impact of a relatively small number of major exploiters and polluters. A better life
for all is not compatible with the sustained and universal growth which is central to
most political thought. The gulf between North and South will continue to widen.
The present trickle of economic migrants will become a flood. Starvation, pestilence,
pandemics and war will surely follow. Most of us have been acutely conscious,
during our lives, of the threat of nuclear holocaust. As that dark and dire possibility
apparently recedes we must become aware of an equally bleak future if we fail to
limit population growth. It is already too late to avoid calamity but we might still
spare ourselves total catastrophe. We all know that we will die. However, we also
like to think that, with the help of modern technology and a degree of good fortune,
we might manage a little more than the proverbial three score years and ten. While
we are here, most of us see some sense in making the best of what the world has
to offer and would take comfort in the thought that, in so doing, our children might
be assured of an environment that they could find joy in. If the worst is to be avoided,
now is the time to strive towards equilibrium rather than to accelerate our movement
away from it.
Finally, at the end of this tale, I wish to return, very briefly, to the question
of obesity and diet (page 127 et seq.) because our attitudes to these encapsulate many
of our responses to much greater problems. In the richer countries there are large
numbers of people who would like to weigh less. Avoiding excess weight is a
complicated matter. Volumes have been written about diet but we are no nearer
solving this problem than solving unemployment, destitution, crime or preventing
fearful acts of war. We still yearn for some technical fix and prefer not to believe
that body fat only accumulates when calorific input exceeds calorific output. But, in
the end, even though we may hate the thought we come up against the laws of
251
thermodynamics. Energy and mass are one, there is no escape. Our attitude to our
planet is similar to our attitude to our bodies. We abuse both, careless of the
consequences. We prefer not to think about what we are doing at all or to heap scorn
on those who have the temerity to urge moderation. The latter is as it should be.
Scepticism is to be applauded. No one can look into the future and the way ahead
is littered with the remains of discredited predictions. Nevertheless we must
recognise and accept the bottom line drawn by thermodynamics. My position in this
is simple yet I fear that a casual reader might conclude that my Malthusian stance
implies that I see over-population as the cause of all evil. I do not. I need to look
no further than my own country. During a relatively short period, biologically
speaking, the population of the British Isles has not merely doubled it has increased
thirty fold. Everyone knows that this increase was made possible by the Industrial
Revolution (i.e. by technology). Putting aside the (not unrelated) fact that more have
died in warfare during this period than the total original population it is self evident
that there have been immense benefits. We live longer, we are well fed, we are spared
a great deal of pain and suffering. We have leisure. While we have undoubtedly
changed our environment out of all recognition we still live in a green and pleasant
land. Moreover, for many years now, our population has been stable. So why do I
conclude that the rest of the world cannot do the same? Why should it not continue
to increase (as it most certainly will), stabilise sometime in the middle of the next
century (at somewhere between 8 and 12 billion), and then live happily ever after.
Perhaps it will. At this moment we could feed probably 20 billion if we put our minds
to it. We will not run out minerals in the foreseeable future. There will still be oil
in the ground when we have ceased to use it. But, there’s the rub. The oil will be
there because it has become too expensive to extract. There may well be vast reserves
of oil and coal still to be discovered but the future is infinite and reserves of fossil
fuels are finite. What is worse, as we return all of this fixed carbon to the atmosphere
in a perilously short time we clearly risk major adverse effects on our environment.
We must then ask “for what?” It can be successfully argued that there is no past
correlation between increasing population and decreasing human welfare. On the
contrary, better times have come with more people. That the two have gone hand
in hand in the past, however, does not mean for one moment that they will continue
to go hand in hand in the changed circumstances of the future. Nor can it be
reasonably argued that the present exponential increase in population and its
associated pollution will make it easier to solve the inevitable problems that are
following in its wake. If earth science is right and fossil fuels are fast diminishing,
despite the fact that we currently float in a pool of oil, it is the decline in fossil fuels
which will first threaten increasing starvation. As we have seen, we eat the products
of past photosynthesis as we eat the products of contemporary photosynthesis and,
if that is to reflect the pattern of future agriculture, the two will decline together.
O.K., so we may come up with alternatives to oil, coal and gas and everything will
be fine again. All that CO2 and methane that we have blown off in the meantime
may not be so bad anyway and who cares if we never get to see a whale or a rain
forest? Such questions scarcely deserve answers. Instead we might reasonably pose
others. Much has been made in these pages of renewable, alternative energy sources.
Given the inevitability of short term increases in population, can it be doubted that
new and alternative technologies would not benefit from a longer period of
development? As we go through the looking glass into the future will we not have
to run to keep in the same place? Come what may, what is left of our flora (and its
dependent fauna) will have to cope with high CO2, and the distinct possibility of
significant changes in climate. Can it be maintained that a longer period of adaptation
to these changed circumstances would not be desirable? And, in the end, (why beat
about the bush) would not life be altogether sweeter if we could once again walk
through relatively safe and pleasant city streets rather than perilously and nervously
riding the subway from one foul patch to another?
252
CHAPTER AND VERSE
CHAPTER AND VERSE
Rationale
In writing a scientific paper it is often necessary to give the authority for

almost every important statement that is made. This can be carried to extremes and
there is the story about the author who wrote “In the beginning...” and then cited
Genesis as his authority. Conversely there are lazy authors who are inclined to skip
a few references or cite reviews by someone other than the person who should be
credited with the original statement or observation. Ambitious and unscrupulous
scientists have also been known to deliberately neglect previous work in the hope,
surprisingly often realised, that they will reap the rewards for seeds sown by some
earlier research, thereby denying the original authors the modest enjoyment of being
credited with a new idea or observation. Others may simply, or understandably, be
unaware of publications that they should mention or, growing long in the tooth, quite
genuinely forget that they had read the seminal work on a particular topic many years
before. Everyone’s papers and books, these days, gets a mention in “Citation Index”
which lists those authors who have cited their work in previous years and decades
and all manner of judgements about a scientist’s worth are sometimes made on this
basis. Naturally this can be very misleading because individual scientists inevitably
tend to cite their own work on every conceivable occasion and someone who has
invented a useful technique may be cited by all and sundry for evermore even if they
might wish to be remembered, or acknowledged, for other things.
All of this is mentioned here for two reasons. One is the hope that this book
may be read by prospective researchers who have yet to put pen to paper and should
be warned of what fate awaits them if they do. The second is to explain to a reader,
who has no intention of engaging in such matters, what policy has been adopted in
this book. It will be immediately obvious that although many names are mentioned
in the text there are very few specific citations such as:-
Hill, R., Nature Lond., 139, 881-882 (1937).
Citations of this sort have not been made frequently because, if this is to be
done at all, it should be done properly and the work involved in checking every
reference is so immense that it would have added at least one more year to the writing
of the book and might even have tipped the author into an early grave. There is also
the still unsolved problem of how to insert lots of reference into a text without
making it unpleasant to read. Not every reader wants chapter and verse for every
statement and to have almost every sentence peppered with unasked for references
can be a pain. At the same time most readers might wish to read other related works
and some, out of interest or proper scepticism, might wish to know where the author
got his “facts”. What I have done is to offer some sort of compromise. Naturally,
like all compromises, what follows is far from perfect.
PHOTOSYNTHESIS
Since the book is much concerned with photosynthesis it aims to be self-

sufficient for the present purpose but:-
“Photosynthesis” by D.O. Hall and K.K. Rao. Published by Edward Arnold, London
(1987).
is an excellent, and comprehensive, introductory text and
254
CHAPTER AND VERSE
“Light and Living Matter” by R.C. Clayton, McGraw-Hill Book Company, New
York (1970)
illuminates the underlying physics in a very clear fashion.
Even if it is slightly dated and out of print (but still obtainable through any
good library), it will not be too hard to guess why
“C3, C4, Mechanisms, and Cellular and Environmental Regulation of

Photosynthesis” Edwards, G.E. and Walker, D.A., Blackwell Scientific Publications
Ltd, Oxford. (1983).
C 4 Photosynthesis: “An unlikely
is listed here. Much more recent, but rather more general, information can be found process full of surprises” by Hal Hatch,
in:- Plant & Cell Physiol 33, 333-342
(1992) and Biochim Biophys Acta 895,
“Molecular Activities of Plant Cells” by John W. Anderson and John Beardall, 81-106 (1987).
Blackwell Scientific, Oxford (1991).
This is authoritative and well presented. For every last thing you might wish
to know about photosynthesis, the key to the older literature is the monumental:-
“Photosynthesis and Related Processes” by Eugene Rabinowitch, Interscience

Publishers Inc. New York in three parts; Vol I (1945), Vol II 1 (1951) and Vol II
2 (1956).
Similarly comprehensive multi-author reviews and lists of references to the

more recent literature can be found in:-
“The Encyclopedia of Plant Physiology” (New Series), edited by A. Pirson and

M.H. Zimmerman by Springer Verlag, Berlin, Heidelberg New York.
Of the many volumes of this, 5 (1977), 6 (1979), 12A (1981), 12B (1982) and 19
(1986) are the most immediately relevant.
PLANTS IN RELATION TO THEIR ENVIRONMENT
For those who wish to learn more about this subject:-
“Plants” by Watson M. Laetsch, published by Little, Brown and Company, Boston,

(1979).
is a delight.
GLOBAL WARMING, ENERGY, ETC.
Such is contempory interest in matters “green”, fostered by splendid

organisations like “Greenpeace”, “Friends of the Earth”, and “The World Wide Fund
for Nature” that newspapers and magazines are currently overflowing with
information (not invariably accurate) about global warming, the demise of the rain
forests (fast following the dinosaurs) and the culpable follies of politicians intent on
re-election like George Bush. Here, in short, you are spoiled for choice at the popular
level but, if you do wish a relatively recent overview:-
255
CHAPTER AND VERSE
“Hothouse Earth -The Greenhouse Effect and Gaia”- by John Gribbin, Bantam
Press, London, New York, Toronto, Sydney, Auckland. (1990)
is gripping and very readable (even if you might not care to embrace the Gaia bit).
To get into the hard stuff, the most recent comprehensive source of information
undoubtedly lies in the three volumes of:-
“Energy Technologies For Reducing Emissions of Greenhouse Gasses”

Proceedings OECD “Experts Seminar”, Paris (1989)
Like any multi-author work, some chapters are better than others but that by
Lovins (“Energy, people and industrialisation” Vol 1, pp. 301-326), is one of the
most electrifying, significant and philosphically amusing articles that I have ever
read. For this compelling reason I have drawn from it extensively in Chapter 9.
If rising carbon dioxide happens to by your forte, then the font of all
knowledge is:-
“Trends ‘9O” A Compendium of Data on Global Change from the Carbon Dioxide
Information Analysis Centre of the Oak Ridge National Laboratory Tennessee Ed.
by T. A. Boden, Paul Kanciruk and M. P. Farell.
This invaluable work is sponsored by the United States Department of Energy but
be warned that it is what the title suggests and not light reading. Finally if we turn
to renewable resources, the U.K. Department of Energy publishes excellent and well
presented information (in colour) on this subject which is intended for the public at
large. These come from the:-
Renewable Energy Enquiries Bureau, ETSU, Building 156, Harwell Labotatory,

Oxfordshire OX11 ORA.
A wealth of more technical information can be found in:-
“Renewable Energy Resources” by J. Twidell and A.D. Weir, E & F. N. Spon

Limited, London & New York (1986).
and
“Renewable Sources of Energy” International Energy Agency, Paris (1987).
OTHER READING
I also gladly acknowledge the use that I have made of the following books
etc.:-
“History of the Earth’s Atmosphere” by Budyko M.I., Ronov A.B., Yanshin A L,

Springer Verlag - Berlin, Heidelberg, New York, London, Paris, Tokyo (1987).
“Options for Mitigating the Greenhouse Effect” by K. Currie, Seminar on Climate

Change, the Department of the Environment, London (1989).
“Saving the Tropical Forests” by J. Gradwohl and R. Greenberg, Earthscan

Publications Ltd, London (1988).
256
CHAPTER AND VERSE
“Vegetation History” by B. Huntley and T.W.Webb III, Kluwer Acad. Publishers

Dordrecht, Boston, London (1988).
“Energy and Food Production” by G. Leach, IPC Science and Technology Press
(1976).
“Planets and Their Atmospheres - Origin and Evolution” John S. Lewis and Ronald
G. Prinn. Academic Press, Inc., Orlando, San Diego, San Francisco, New York,
London, Toronto, Montreal, Sydney, Tokyo, San Paulo (1984).
“Solar-powered Electricity - A survey of photovoltaic power in developing

countries” by Bernard McNelis, Anthony Derrick & Michael Starr, Intermediate
Technology Publications, London (1988).
“Can Britain Feed Itself?” by K. Mellanby, Merlin Press, London (1975).
“IPCC (Intergovernmental panel on climate change)” Meteorological Office,

London Road, Bracknell, RG12 2SZ (1990).
”An Assessment of the Effects of Climatic Change on Agriculture” by M. L. Parry

and T. R. Carter, Climatic Change 15: 95-116, Kluwer Academic Publishers (1989).
“Going Critical” by W.C. Patterson, Paladin Grafton Books, London, Glasgow,

Toronto, Sydney, Auckland (1985).
“The Energy Fix” A. Porter, M. Spence and RR. Thompson, Pluto Press, London,
Sydney, Dover-New Hampshire (1986).
“Scales and Global Change” by T. Rosswall, R.G. Woodmansee and P.G.Risser,

John Wiley and Sons, Chichester, New York, Brisbane, Toronto, Singapore (1988).
“Nuclear Power: Phoenix or Dodo?” by J. Surrey, British Gas Key Environmental

Issues 10 (1991).
“Technological Responses to the Greenhouse Effect” edited by G. Thurlow. Twenty-

sixth Consultative Conference, The Watt Committee on Energy, Savoy Hill, London
(1990).
“Probing Plant Structure” by John Troughton and Leslie A. Donaldson, Chapman

& Hall, London (1972).
“Evolution of the Atmosphere” by James C. G. Walker, Macmillan Publishing Co.,

Inc., New York (1982).
“Scientific Assessment of Climate Change and its Impacts” by T.M.L. Wigley,

Seminar on Climate Change, the Department of the Environment, London (1989).
“Hydrogen power: An introduction to hydrogen energy and its applications” by L.O.

Williams Pergamon Press, Oxford, U.K. (1980).
257

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Energy, Plants & Man

David Alan Walker

Digital Edition, 2006

First published in 2002 by Oxygraphics

Text copyright 2000 David Alan Walker

This edition first published in 2004 by Oxygraphics

David Walker, Ph.D., D.Sc., FRS was

His filial collaborator, Richard Walker, M.A.,

Simply click HERE to order from Michael Packard. Or, if you

Alternatively, if like David Walker, you find virtue in PDF,

There you will find other digital offerings, from

“What is the use of a book”, thought Alice, “without pictures or conversations”.

Chapter 1 A FEW FUNDAMENTALS 9

MATTER AND ENERGY

THE SOURCE OF ORGANIC CARBON

ENERGY TRANSDUCTION IN PHOTOSYNTHESIS

THE PHILOSOPHER’S STONE

Chapter 2 WHERE IT ALL STARTS 25

Chapter 3 HARVESTING THE SUN 43

3.1 The Photoreceptors 44

3.10 Beyond PSI 52

Chapter 4 ASSIMILATORY POWER 65

4.1 Equations Old and New 66

Chapter 5 THE DARK BIOCHEMISTRY 85

CRASSULACEAN ACID METABOLISM

Chapter 6 OF PLANTS AND MEN 121

6.1 All Flesh is Grass 122

6.2 Eating Potatoes 124

Chapter 7 DOOM AND GLOOM 151

PREDICTION, SCEPTICISM, OPTIMISM AND PESSIMISM

THE GREENHOUSE EFFECT

THE GREENHOUSE GASES

Chapter 8 CONSEQUENCES AND UNCERTAINTIES 179

8.1 What Might Happen 180

Chapter 9 IS THERE ANOTHER WAY? 217

9.1 An Excursion into Dangerous Ground 218

Fig. 1.1 Relationship between photosynthesis and respiration 16

Fig. 2.1 Electromagnetic radiation 27

Fig. 3.1 Absorption spectra of chlorophylls in acetone 45

Fig. 3.10 Starch Pictures 58

Fig. 4.1 The Z-scheme by analogy 69

Fig. 5.1 Light and dark events in photosynthesis 89

Fig. 7.2 The atmospheric heat balance 154

Fig. 9.1 A photovoltaic cell 240

David Walker, June 1992

Helping, in various ways, to transcribe thoughts and illustrations into printed

I am most grateful to the University of Sheffield, to Arthur Willis, David

David Walker, June 1992

ENERGY AND THE FUTURE OF MAN

“Any man’s death diminishes me, because I am involved in Mankind;

Green plants undertake photosynthesis. As we shall see, this is a process

There are, of course, any number of possible alternative energy sources -

Recent demonstrations of cold fusion have created considerable interest but

as food, are in short supply in many places (although starvation is frequently a

The utilisation of energy, and of organic carbon is inextricably linked to

Linked to all of these considerations is the “Greenhouse Effect”. Carbon

A greenhouse would become even hotter if made of glass which transmitted

Carbon dioxide in the atmosphere was diminished to something below its

Extrapolation of current increases in carbon dioxide suggests that many of

What follows is an attempt to introduce some of the physical and biological