UNIT 3 J.

ATMOSPHERE
The Chemistry of the Environment:
The Earth's Atmospheric Cycle
 The atmosphere is a protective blanket which nurtures life on the Earth and protects it from
the hostile environment of outer space. It is generally believed that three billion or four
billion years ago, Earth’s atmosphere consisted mainly of ammonia, methane, and water.
 Ultraviolet (UV) radiation from the sun probably penetrated the atmosphere, rendering the
surface of Earth sterile.
 Primitive organisms use energy from the sun to break down carbon dioxide to obtain
carbon, which they incorporated in their own cells.
 The major by-product of this process, called photosynthesis, is oxygen.
 Another important source of oxygen is the photodecomposition of water vapor by UV light.
Nitrogen Cycle
 Molecular nitrogen, with its triple bond, is a very stable molecule. In the conversion of
molecular nitrogen into nitrogen compounds, atmospheric nitrogen gas is converted into
nitrates and other compounds suitable for assimilation by algae and plants.
 Lightning also produce nitrates from nitrogen gas.
 Nitric acid is converted to nitrate salts in the soil. These nutrients are taken up by plants,
which in turn are ingested by animals. Animals use the nutrients from plants to make proteins
and other essential biomolecules. Denitrification reverses nitrogen fixation to complete the
cycle.
Oxygen Cycle
 Atmospheric oxygen is removed through respiration and combustion to produce carbon
dioxide. Photosynthesis is the major mechanism by which molecular oxygen is regenerated
from carbon dioxide and water.
Layers of the Atmosphere
 The most active region is the troposphere, the layer of the atmosphere that contains about
80% of the total mass of air and all of the atmosphere's water vapor. The troposphere is
the thinnest layer of the atmosphere (10 km), but it is where rain, lightning, and hurricanes
occur.
 Above the troposphere is the stratosphere, which consists of nitrogen, oxygen, and ozone.
One of the products of this reaction sequence is ozone (03), serves to prevent harmful UV
rays from reaching Earth's surface.
 In the mesosphere, the concentration of ozone and other gases is low, and the temperature
decreases with increasing altitude. The Kármán line (or von Karman line) is an attempt to
define a boundary between Earth's atmosphere and outer space
 The main components of air in the thermosphere or ionosphere include helium, atomic
nitrogen, and atomic oxygen. The thermosphere absorbs a lot of the UV radiation and X-ray
given off by the sun.
 The exosphere is the uppermost region of Earth's atmosphere as it gradually fades into the
vacuum of space. The air in the exosphere is extremely thin - in many ways it is almost the
same as the airless void of outer space.

Air Pollutants and Treatment

 Environmental pollution can be divided among the categories of water, air, and land
pollution.
Air Pollution
 Pollutant is substance present in greater than natural concentration as a result of human
activity. This has detrimental effect in the environment.
 Contaminants are not classified as pollutants unless they have some detrimental effect and
cause deviations from the normal composition of an environment.
 The source is particularly important because it is generally the logical place to eliminate
pollution. After a pollutant is released from a source, it may act upon a receptor. The
receptor is anything that is affected by the pollutant.
Oxides of Carbon
Carbon dioxide, CO₂ is the most abundant pollutant. It is a natural atmospheric constituent, and
it is required for plant growth. However, the level of carbon dioxide in the atmosphere, now at
about 360 parts per million (ppm) by volume, is increasing by about 1 ppm per year.
This increase in atmospheric CO₂ may well cause general atmospheric warming or greenhouse
effect with potentially very serious consequences for the global atmosphere and for life on earth.
Though not a global threat, carbon monoxide, CO, can be a serious health threat because it
prevents blood from transporting oxygen to body tissues.
Oxides of Nitrogen
The two nitrogen oxide air pollutants are nitric oxide (NO) and nitrogen dioxide (NO₂),
collectively denoted as NOx. These tend to enter the atmosphere as NO, and photochemical
processes (first step in the formation of photochemical smog) in the atmosphere can convert NO
to NO₂.
Oxide of Sulfur
Sulfur dioxide (SO₂) is a reaction product of the combustion of sulfur-containing fuels such as
high-sulfur coal. Part of this SO₂ is converted in the atmosphere to sulfuric acid (H₂SO₄)
normally the predominant contributor to acid precipitation.
Methane
It is the most abundant hydrocarbon in the atmosphere, CH4, from sources as natural gas and
produced by the fermentation of organic matter. It is one of the least reactive atmospheric
hydrocarbons and is produced by diffuse sources.

Particulate Matter
Particles ranging from aggregates of a few molecules to pieces of dust readily visible to the
naked eye are commonly found in the atmosphere. Some atmospheric particles, such as sea salt
formed by the evaporation of water from droplets of sea spray, are natural and even beneficial
atmospheric constituents.
Very small particles called condensation nuclei serve as bodies for atmospheric water vapor to
condense upon and are essential for the formation of rain drops.
Colloidal-sized particles in the atmosphere are called aerosols. Those formed by grinding up
bulk are known as dispersion aerosols, whereas particles formed from chemical reactions of
gases are condensation aerosols; the latter tend to be smaller.
Smaller particles of fly ash enter furnace flues and are efficiently collected in a properly
equipped stack system.
UNIT 3 K.THE CHEMISTRY OF WATER
 Water plays a role in nearly everything that takes place on our planet. We humans are in fact
60% water, and 71% of Earth is covered with water.
 But according to Rachel Carson (1907–1964) noted in Silent Spring, “By far the greater part
of the Earth’s surface is covered by its enveloping seas, yet in the midst of this plenty we are
in want.”
 Ice floats on water, ecosystems in lakes and streams can survive beneath the ice during frigid
winter days.
 Water also absorbs more heat per gram than most other substances, allowing bodies of water
on Earth to serve as heat reservoirs.
 Your body can go weeks without food, but only days without water and one of the greatest
solvent today.
UNIQUE PROPERTIES OF WATER
 Water is a liquid under standard temperature and pressure (STP); that is, a temperature of
25 °C and pressure of 1 atm. This is surprising because almost all other compounds with a
similar molar mass to water are gases under these conditions.
 Further, when water freezes, it exhibits another somewhat bizarre property—it expands. Most
liquids contract when they solidify.
 Water also has an anomalously high boiling point of 100 °C (212 °F); in contrast, liquids
with similar molecular structures—such as hydrogen sulfide, H2S—have much lower boiling
points.
 The electrons in an O–H bond are pulled closer to the more electronegative oxygen atom.
 This unequal sharing results in a partial negative charge (δ– ) on the O atom, and a partial
positive charge (δ+ ) on the H atom
 Experimental evidence indicates that the O atom attracts the shared electron pair more
strongly than does the H atom.
 Electronegativity is a measure of the attraction of an atom for an electron in a chemical
bond.
 Consider what happens when two water molecules approach each other. Because opposite
charges attract, a H atom (δ+ ) on one of the water molecules is attracted to the O atom (δ– )
on the neighboring water molecule. This is an example of an intermolecular force; that is, a
force that occurs between molecules.
 A hydrogen bond is an electrostatic attraction between a H atom, which is bonded to a
highly electronegative atom (O, N, or F), and a neighboring O, N, or F atom—either in
another molecule, or in a different part of the same molecule.
 Because of hydrogen bonding, water is a liquid at room temperature, as well as at body
temperature (about 37 °C). In fact, life’s very existence on our planet depends on this fact!
 Hydrogen bonding can also help you understand why ice cubes and icebergs float. Ice is
composed of a regular array of water molecules in which every H2O molecule is hydrogen
bonded to four others Note the empty space in the form of hexagonal channels.
 Specific heat is the quantity of heat energy that must be absorbed to increase the temperature
of 1 gram of a substance by 1 °C.
 The specific heat of water is 4.184 J/g·°C. This means that 4.184 J of energy is needed to
raise the temperature of 1 g of liquid water by 1 °C.
UNIT 3 L. THE CHEMISTRY OF SOIL
NATURE AND POLLUTION
Chemistry of Soil
 Soil is a mixture of weathered rocks and minerals, decayed plants and animal material
(humus and detritus), and small living organisms which includes plants, animals and
bacteria. Soil also consists of water and air.
 A typical productive soil is 5% organic matter and 95% inorganic matter.
Importance of Soil
 production of food
 maintaining the balance of carbon, nitrogen, and phosphorus;
 for the construction of building materials.
Distinguished Layers of Soil
 A layer of typical soil is called a horizon. It is the product of complex interactions between
processes that develop during weathering.
 A horizon or topsoil is the top layer of soil and several inches in thickness. Maximum
biological activity in the soil happens in this layer. This layer also contains most of the soil
organic matter and is important in the productivity of plant. In defining the composition of
soils, the parent rocks where soils are formed play an important role.

Water and Air in Soil

The other characteristics of soil includes:
o Strength
o Workability
o Soil particle size
o Permeability
o Extent of maturity.
 Water is important because it is the basic transport medium for carrying essential plant
nutrients from solid soil particles into plant roots and to the farthest reaches of the plant’s leaf
structure.
 Transpiration happens when the water in a plant evaporates into the atmosphere from the
plant’s leaves.
 Soil carries the nutrients to the plant extremities by this process wherein plants remove
carbon dioxide from the atmosphere and add oxygen by photosynthesis. The reverse of this
process occurs during plant respiration.

 If soil becomes saturated with water, the oxygen will immediately be consumed by the
respiration of microorganisms and will cause degradation of organic matter in soil.
 Excess water in soils is harmful to plant growth, and the soil does not contain the air required
by most plant roots. Most important crops (exception of rice) cannot grow on soil soaked
with water.
Inorganic matter in soil
 Inorganic colloids are produced from the weathering of parent rocks and minerals.
These colloids:
o are repositories of water and plant nutrients which can be made available to plants as
needed
o plays a role in the detoxification of substances that could harm plants
o often absorb toxic substances in soils
 Minerals composed of Silicon and Oxygen constitute most of the mineral fraction of the
soil.
Common soil mineral constituents are:
 Finely divided quartz (SiO2)
 Orthoclase (KAlSi3O8)
 Albite (NaAlSi3O8)
 Goethite (FeO(OH)) Magnetite (Fe3O4)
 calcium carbonate (CaCO3) Magnesium carbonate (MgCO3)
 Oxides of manganese and titanium.
Organic matter in soil
 Organic matter determines soil productivity even though it typically constitutes only <5%
of a productive soil.

These organic matter:

o becomes source of food for microorganisms
o undergoes ion exchange chemical reaction
o contribute to the weathering of mineral matter (process by which soil is formed)
 The build-up of organic matter in soil is greatly influenced by temperature and by the
availability of oxygen. Since the rate of biodegradation decreases with decreasing
temperature, organic matter does not degrade rapidly in colder climates and tends to build up
in soil.
 The organic content may reach 90% in areas where plants grow and decay in soil saturated
with water.

Components of Soil
Organic Soil- Composed mostly of decayed plant and animal matter
Inorganic Soil- Composed mostly of minerals

Soil Humus
 Humus is composed of a base-soluble fraction called humic and fulvic acids (organic
material that remains in the acidified solution), and an insoluble fraction called humin (the
residue left when bacteria and fungi biodegrade plant material).
 Humic substances have an influence in properties of soil even though it has a small
percentage in soil composition.
o They have an acid-base character which serve as buffers in soil and they significantly
increase the water-holding capacity of soil.
 o Humic substances also strongly bind metals and serve to hold micronutrient metal ions in
soil.
o The aggregates of soil particles can also be stabilize by these substances and
additionally, can increase the sorption of organic compounds by soil.
Soil Solution
 The soil solution is the aqueous portion of soil that contains dissolved matter from
the chemical and biochemical processes in soil and from the exchange with the
hydrosphere and biosphere.
 This medium transports chemical species to and from soil particles and provides contact
between the solutes and the soil particles.
 It is also an important pathway for the exchange of plant nutrients between roots and
solid soil aside from water which is vital for plant growth.

Adjustment of Soil Acidity

 One important process that occurs in soils is sorption. Sorption is essentially the
attachment of a chemical to either the mineral or organic portions of soil particles and
includes both adsorption and absorption.

Macronutrients
 Elements that occur in substantial levels in plant biomass and fluids are called
macronutrients.
 The elements that are usually recognized as essential macronutrients includes: C, H, O, N, P,
K, Ca, Mg, and S.
 C and H can be absorbed from the atmosphere while others can be obtained from soil. But
N, P and K are commonly added to soil as fertilizers.
Micronutrients
 There are 7 essential plant nutrient elements defined as micronutrients.
 These include boron (B), zinc (Zn), manganese (Mn), iron (Fe), copper (Cu),
molybdenum (Mo), chlorine (Cl).
 They constitute in total less than 1% of the dry weight of most plants.
 They play important roles in redox reactions and in photosynthesis.

Fertilizers
 Major components of crop fertilizers are magnesium, sulfate and micronutrients may also
be added.
 Fertilizers are designated by number, such as 6 for nitrogen (equivalent to 6%) expressed as
N, 12 for phosphorus (equivalent to 12%) expressed as P2O5, and 8 for potassium
(equivalent to 8%).
 Farm manure corresponds to an approximately 0.5-0.24-0.5 fertilizer. The organic fertilizers
such as manure must undergo biodegradation to release the simple inorganic species
(NO3-, H𝑥(PO4-3)𝑥, K+) absorbed by plants.
 Ammonium nitrate, NH4NO3, is a common solid nitrogen fertilizer which has 33.5%N.
 Although convenient for its application to soil, it requires considerable care during
manufacture and storage because it is explosive.
 One of the common problem that is produced from the use of fertilizer is water pollution
resulted by agricultural runoff
 Eutrophication can occur. It is the excessive growth of algae in water body which is caused
by the nutrients in fertilizers.
 Due to this, there would be algal biomass decay that will consume oxygen, and bodies of
water are seriously damaged because of oxygen depletion.
SOIL POLLUTANTS
Pollutants from Livestock Production
 Livestock manure has a very high BOD (biochemical oxygen demand) and can rapidly
deplete oxygen when it gets into waterways.
 Decomposition of animal waste products produces inorganic nitrogen that can
contaminate water with potentially toxic nitrate
 Methane generated in the anaerobic degradation of livestock wastes is a potent greenhouse
gas.

Pesticides and their Residues In Soil

There are four major concerns regarding pesticides in soil:
o carryover of pesticides and biologically active degradation products to crops grown in
later seasons
o biological effects on organisms in terrestrial and aquatic ecosystems including
bioaccumulation and transfer through food chains
o groundwater contamination
o effects on soil fertility
 Herbicides are considered the most common chemicals that affect soil and organisms. It
is well studied that these pesticides and other foreign compounds that remain in soil for a
long period of time have its effects. Some are listed below:
o The substances become increasingly resistant to extraction and desorption process
o they become significantly less bioavailable to organisms
o overall toxicity is decreased
Wastes in Soil
 Large quantities of waste products are received by soil. Sulfur dioxide emitted in the
burning of sulfur-containing fuels ends up as sulfate in soil. Nitrogen oxides from the
atmosphere that are converted to nitrates are eventually deposited in soil.
 Soil is the receptor of many hazardous wastes from landfill leachate, lagoons, and other
sources. In some cases, land farming (land treatment) of degradable hazardous organic
wastes is practiced as a means of disposal and degradation. Volatile organic compounds
 (VOCs) such as benzene (C6H6) and toluene (C7H8),may contaminate soil in industrialized
and commercialized areas. Some of the sources of these VOCs are: leaking underground
storage tanks and landfills built before current strict regulations which improperly
discarded solvents.
 Soil receives enormous quantities of pesticides as an inevitable result of their
application to crops. The degradation of these pesticides on soil largely determines
their ultimate environmental effects. Among the factors to be considered are the sorption
of the pesticide by soil; leakage of the pesticide into water, as related to its potential
for water pollution; effects of the pesticide on microorganisms and animal life in the
soil; and possible production of relatively more toxic degradation products.

Soil Loss and Degradation

 Soil is a fragile resource that can be lost by erosion or become so degraded that it is no longer
useful to support crops.
 The physical properties of soil and its susceptibility to erosion, are strongly affected by
the cultivation practices to which the soil is subjected.
 Desertification refers to the process associated with drought and loss of fertility by which
soil becomes unable to grow significant amounts of plant life. Desertification involves
erosion, climate variations, water availability, loss of fertility, loss of soil humus, and
deterioration of soil chemical properties.
 Soil erosion is the loss of soil by the action of both water and wind; water is the primary
source of erosion.
 A related problem is deforestation or loss of forests. The problem is particularly acute in
tropical regions, where the forests contain most of the existing plant and animal species. In
addition to extinction of these species, deforestation can cause devastating deterioration of
soil through erosion and loss of nutrients.
Soil Preservation
 Preservation of soil and its ability to support plant life is the most basic part of food
sustainability.
 Soil erosion is one of the problem that could affect the soil. The preservation of soil from
erosion is commonly termed soil conservation.
 There are numerous traditional solutions to the soil problem as agricultural practices
which include terracing, contour plowing, and periodically planting fields with cover
crops.
 For some crops, conservation tillage (no-till agriculture) surely decreases erosion. This
practice consists of planting a crop among the residue of the previous year’s crop without
plowing. In the newly planted crop row, weeds are killed by application of a herbicide
prior to planting. The surface residue of plant material left on top of the soil prevents soil
erosion.
Agroforestry
 Agroforestry is a promising alternative in sustainable agriculture in which crops are
grown in strips between rows of trees. The trees help to preserve or balance the soil
particularly on sloping terrain. For example, choosing trees with the capability to fix nitrogen
then the system can be efficient in this essential nutrient.
Soil Restoration
 Soil can be impaired by loss of fertility, erosion, buildup of salinity, and contamination by
phytotoxins (such as zinc from sewage sludge).
 However, in many cases, more active measures called soil restoration are required to restore
soil productivity, through the application of restoration ecology. Measures taken in soil
restoration may include physical alteration of the soil to provide terraces and relatively
flat areas not subject to erosion.
 Organic matter can be restored by planting crops. Residues of which are cultivated into the
soil for partially decayed biomass. Nutrients may be added and contaminants are neutralized.
Green Chemistry and Sustainable Agriculture
 The practice of green chemistry may significantly enhance agricultural productivity and
sustainability.
 The application of green chemistry to agriculture holds promise for preventing or
alleviating problems such as the following:
a) Pesticides, herbicides, and fertilizers and their products have accumulated on agricultural
lands and waters leading to adverse effects on wildlife, the environment, and potentially
humans as well.
b) Nontarget organisms have suffered and insect and weed pests have built up resistance
to agents used in their eradication.
c) Poorly trained and inadequately protected personnel in less developed countries have
suffered adverse effects from modern agricultural products.
d) Disposal problems have arisen with respect to obsolete pesticides.

 Agriculture is a science of living organisms applied to human needs for food and fiber
production. So in attempting to find more sustainable and environment-friendly approaches
to agriculture, use an approach like biomimetics. It is when humans attempt to mimic natural
life systems.
 Pesticides that come from natural sources such as plants or bacteria are called
biopesticides. These substances are usually more environmentally friendly than
synthetic pesticides, although the blanket assumption that anything from a natural source
is automatically safer than synthetic materials should not be made.
Biopesticides has its advantages which include:
o a generally lower toxicity than conventional pesticides
o has high specificity for target pests
o effective even in very small quantities
o rapid decomposition