UNIT 1 ENVIRONMENTAL

CHEMISTRY AND POLLUTION

Structure
1.0 Objectives
1.1 Introduction
1.2 EnvironmentalPollution
1.2.1 Sources of Pollution
1.2.2 Types of Pollution

1.3 Atmospheric Effects and the Reactions inAtmosphere

1.3.1 Atmospheric Effects
1.3.2 Reactions in Atmosphere
1.3.3 Photochemical Reactions
1.3.4 Redox Reactions
1.3.5 Acid-Base Reactions

1.4 Greenhouse Gases and Global Warming

1.4.1 Global Warming Potential
1.4.2 Sources of Greenhouse Gases
1.4.3 Ozone Layer
1.4.4 Ozone Layer Depletion

1.5 Let Us Sum Up

1.6 Key Words
1.7 References and Suggested Further Readings
1.8 Answers to Check Your Progresss

1.0 INTRODUCTION
The life on earth cannot exist without its environment or without collaborating with
other species or ecosystems, which are the significant units of life on earth. The life
cycle of living things involves assembling and de-assembling of various atoms from
the environment and returning back to the environment. This cyclic process occurs
in three open systems- the biosphere, the lithosphere and the hydrosphere that you
have studied in Course -1. These spheres are separated from earth to outer space
bya thin layer of gases known as the atmosphere. Matter is continuouslyinterchanging
within and amongst all these spheres in the environment. The industrial revolution
has played a major role in the change of the atmospheric gases and the presence of
particulate matterand their effects on natural environment leading to environmental
pollution
In this unit, we begin with defining environmental pollution and classifying it into
various types. We would discuss the importance of natural chemical processes and
how anthropogenic activities disturb these processes and affect the life adverselyon
the earth. 5
Air, Water and Soil Pollution
1.1 OBJECTIVES
After studying this unit you should be able to:

 define and classify the types of environmental pollution and pollutants;

 describe the different atmospheric effects;

 analyse the concepts of chemical processes of the environment;

 explain various atmospheric reactions;

 define greenhouse gases and explain their effects; and

 describe the process of ozone layer depletion and its impact.

1.2 ENVIRONMENTAL POLLUTION

The term pollution is derived from the Latin word pollutioneum which means
to defile or make dirty. There are many definitions for pollution worldwide.

According to U.S. President’s Science Advisory Committee (1966):

“Environmental pollution may be defined as the unfavorable alterations of our

surroundings largely as a byproduct of man’s action through direct or indirect
effects of change in energy pattern, radiation levels, chemical and physi-cal
constitution and abundance of the organisms”.

According to National Academy of Science, USA (1966), pollution may be

de-fined as, “an undesirable change in physical, chemical and bio-logical
characteristics of water, air and soil that may harmfully affect human, animal and
plant life, industrial progress, living con-ditions and cultural assets.”

According to National Environmental Research Council (1976), “Pollution

is viewed as the release of substances and energy as waste prod-ucts of human
activities which result in harmful changes within the natural environment”.

According to Environmental Protection Agency (EPA) - “Pollution is the

presence of substance in the environment that, because of its chemical
composition or quantity, prevents the functioning of natural processes and
produces undesirable environmental and health effects”

Dear learner after going through these definitions we can come to a consensus
that pollution is a contamination of air, soil and water with undesirable amounts
of material or heat which have adverse effects on natural environment as well as
human health.

A pollutant may be defined as a physical, chemical or biological substance

unintentionallyreleased into the environment, which is directlyor indirectlyharmful
to humans and other living organisms.

1.2.1 Sources of Pollution

Pollution can be classified broadly two types on the basis of their sources. These
6 are given below:
Point Source Pollution (PSP):According to US. Environmental ProtectionAgency Environmental
Chemistry and Pollution
(EPA);itisanysingle identifiable source of pollutionfromwhichpollutants are emitted.
Emission of contaminants in to the environment from a particular location is called
PSP. For example:
 Emissions from waste water treatment plants
 Toxic effluents from industries
 Sewage effluents
Non-Point Source Pollution: It is the emission of contaminants into the environment
from more than one location over a large wide spread area. There is no specific area
of source; instead it comes from many unidentifiable areas. For example:
 Toxic chemicals which have not been properly disposed off
 Harmful bacteria and microorganisms from cattle wastes
 Pesticides, fungicides and nutrients from agricultural fields, residential areas.
 Oil, grease, metals and cleaning agents washed from roads, workshops
 Sediments from construction sites, forests and agricultural fields
 Leaching from garbage dumps etc.
Besides these sources of pollution another source of pollution is fugitive emissions.
In this the pollutants are released into the atmosphere from leaks in equipment,
pipelines, seals, valves etc., but not from the usual source.

Do You Know?
Terminology used in the pollution
Sources: The place from where the pollutants originate is called
‘Source’.Example: Cooking and heating (combustion) are the sources of
CO, NOx, and VOCs.
Sink: The place where the pollutants are transferred/moved/transported
from another place or source.
Example: The major sink for atmospheric N2O is stratosphere wherethe
majority undergoes photolysis to give N2 + O.
Receptor: Anything that is negatively affected by the pollutants.
Example: Human beings and plants
Transport: It is the process by whichthe pollution travels from a source to
a receptor.
Example: Air and water are the transport medium.
Dispersion: Changes that occur in spreading of the pollution through the
environment in the process of transport.
Example: Pollutants from various sources like vehicles, factory emissions
dispersed into the atmosphere and removed from the transport medium
(air) through deposition due to rain.
7
Air, Water and Soil Pollution 1.2.2 Types of Pollution
Pollution may be of the following types:
 Air Pollution:Due totheindustrial revolutionandcertainanthropogenic activities
the gaseous mixture and particulate matter in our atmosphere began to change
and lead to air pollution.Air pollution may be defined as any substance (gases,
aerosols) including radioactive radiation present in such concentrations that
mayhaveharmfuleffectsonthelivingthingsanddisturbsthe naturalenvironmental
processes. The factors which determine the level of air pollution and their effects
will be discussed in detail in the following units of this course.
 Water Pollution: Presence of undesirable substance in water bodies, which
have adverse health effects is called water pollution. The diversity and breadth
of impact of pollution caused by the introduction of pathogens, organic wastes,
chemical pollutants, sediments and nutrients and their effects will be discussed
in detail in the following units of this course.
 Soil Pollution:Addition of undesirable substance, which is non-biodegradable
that adverselyaffects the soil qualityand fertility, is known as soil pollution. The
range of soil pollutants mayvary from polluted water to solid waste to acid rain
and dry deposition.The details of these types of pollution will be studied in the
followingunits.
 Noise Pollution: In general noise is a sound without value. It is a shadowy
human health hazard that can damage hearing and evoke other gynecological
and pathological reactions besides disturbing rest, sleep and communication
that in turn disrupt the balance of human or animal life.
 Thermal Pollution: Industries like chemical, thermal andnuclear power plants,
utilize water from natural water bodies for cooling the conversion losses. The
resultant waste heat energy in the form of hot water gets transferred to the
natural waterways and increase its temperature by 10-150 C known as thermal
pollution which have deleterious effects on aquatic ecosystem.
 RadiationPollution: The emission of energyas electromagnetic waves, which
have high energy,addition of radiation to the natural environment by using
radioactive elements is known as radiation pollution. All of us are exposed to
natural radiation, which comes from radioactive material in the earth like
Uranium-238, inhalation of radon gas and radionucleide in food.
The details of these types of pollution will be studied in the following units. In the
next section you will study about the atmospheric effects and the reactions taking
place in the atmosphere but after answering the following questions.
Check Your Progress 1
Note : a) Write your answer in about 50 words.
b) Check your progress with possible answer given at the end of the
unit.
1. Define pollutant and pollution.
..............................................................................................................
..............................................................................................................
..............................................................................................................
8
2. List out the types of pollution. Environmental
Chemistry and Pollution
..............................................................................................................

..............................................................................................................

..............................................................................................................

..............................................................................................................

1.3 ATMOSPHERIC EFFECTS AND THE

REACTIONS IN ATMOSPHERE
Dear learners, to understand the pollution and its impacts you have to learn what we
mean by the atmospheric effects and the factors responsible for the changes in the
components of atmosphere. The study forms the basis of understanding of the
concepts involved and the interactions within systems related to biosphere which
directly influences the environment as well as the human health by controlling the
global and regional environmental conditions. We begin with the atmospheric effects
in the following subsection.

1.3.1 Atmospheric Effects

The atmosphere is considered as the smallest geological reservoir of the earth. As
mentioned before natural atmosphere has three open systems viz., biosphere,
lithosphere and hydrosphere. The lowest layer of atmosphere is known as
troposphere, above the troposphere is the stratosphere and beyond the stratosphere
are two more layers- mesosphere and thermosphere. All the layers are separated
byboundaries called tropopause, stratopause, etc.The composition of the atmosphere
is approximatelysame all over the earth because of the high level of mixing inside the
atmosphere. However, some of the meteorological factors keep changing due to
changing conditions.The dailyalterations in temperature, air, pressure, wind, humidity
and precipitation together are known as atmospheric effects. By having an
understanding of these effects we can easily predict the human induced changes,
therefore, these are very significant.
Convection:- The movement of air due to the atmospheric heating and cooling.
For example,thunderstorms are the most apparent of the driving forces.
The molecules in the atmosphere absorb light energy and undergo certain reactions
which do not occur at normal temperature or in the absence of light. The reactions
determine the effect of chemical species responsible for air pollution. The following
subsection deals with some of the important reactions that occur in atmosphere.

1.3.2 Reactions in Atmosphere

Most of the chemical reactions in atmosphere take place in the troposphere region.
The chemical composition of the atmosphere is balanced due to the chemical reactions
which lead to redistribution of chemical species thereby moderate the atmospheric
temperatures. This is explained as follows.
The troposphere in atmosphere contains a mixture of important gases – O2,
N2,CO2,etc. along with water vapour. It is responsible for moderating and the driving
energy flow to the earth, which in turn maintains the biogeochemical cycle of the
gases and water vapours, etc.The troposphere is also known as “turning sphere” 9
Air, Water and Soil Pollution because it is well mixed by convection process. The gases are generally stable but
due to some changes react to form new compounds. The chemical reactions in this
part of atmosphere are initiated bythe solar radiations. The sun emits radiations with
wide range of energies and we are concerned here with visible light that can be
recognized by human eye and UV light which cannot be recognized by human eye
and is of higher energythan visible light.
The earth gets heated up due to solar energy, which in turn heats up the overlying air
causing the convective mixing. This is due to the hot air, which has a tendency to
rise. The rising air generates high pressure up in the atmosphere, leaving low pressure
area near to earth. The rising air at high pressure is cooled by radiating heat and
thereby generates precipitation. Then the air flows horizontally. This pressure
difference in air leads to winds.
All the gases are released into the atmosphere by some process. This could be
either by natural sources or by anthropogenic sources that occur on the surface of
the earth. Along with these gases some electrically charged species also exist. Most
of these species found in the troposphere region have oxidising capabilities. The
important species which participate in most of the atmospheric reactions are given
below.
1. Hydroxyl radical (OH.): It is a short lived free radical and effective scavenger
for trace gases in this region. Therefore, the hydroxyl radical is known as the
detergent of the atmosphere. It is formed during day time by the photochemical
reaction series by the photon of light.
O3(g) + hõ O2(g) + O(g) ——————— equation (i)

O(g) + H2O(g) 2OH (g) ————————— equation (ii)

Thehydroxy radical is ubiquitous hence it reacts with various compounds in the

atmosphere.
For example:
The reaction between nitrogen dioxide (NO2) and the OH radical in series of
reactions that leads to the formation of nitric acid (HNO3), one of the contributors
to acid rain.

NO2 (g) + OH (g) HNO3 (g)

Kinetic measurements show that some gases (Table 1.1) have slow rates of
reactions with the OH radical and have long residence time in the atmosphere.
These gases accumulate in the atmosphere and escape across the hydropauseinto
the stratosphere.
Table 1.1: Naturally occurring trace gases of the atmosphere with their
residence time and concentration (from Brimble Comb1986)
Gas Residence Time Concentration
(ppb)
Carbon dioxide (CO2) 4 years 360000

10 Carbon monoxide (CO) 0.1 year 100

 Environmental
CH4 3.6 years 1600 Chemistry and Pollution
HCO2H 10 days 1
N2O 20-30 years 300
NO 4 days 0.1
NO 2 4 days 0.3
NH3 2 days 1
SO2 3-7 days 0.01-0.1
H2S 1 day 0.05
CS2 40 days 0.02
OCS 1 year 0.5
CH3-S-CH3 1 day 0.0001
CH3Cl 30 days 0.7
CH3I 5 days 0.002
HCl 4 days 0.01
2. Nitrate radical (.NO3) - It does not sustain in sunlight hence it is a
dominant oxidant during night. It is formed during night time byas low
oxidation reaction of NO2 with ozone. Nitrate free radical again reacts with
NO2 to form N2O5 to establish a chemical equilibrium.
NO2 + O3 NO3 + O2

NO3 + NO2 N2O5 (dinitrogen pentoxide)

3. Peroxy radical (RO2.)and Hydroperoxy radical( HO2.):

Formation of hydroperoxy radical is as per the following reaction:
OH + CO + (O2) HO2 + CO2

OH + RH + O2 RO2 + H2O

RO2 further reacts with another molecule of RO2 either in self-reaction or cross
reaction to form HO2 radical.
For Example:
Methyl Peroxyradical

CH3O2 + CH3O2 2CH3O.

2CH3O. + O2 HO2. + HCHO

4. Dismutation: Simultaneous oxidation and reduction reaction in a biological

process
Hydrogen peroxide (H2O2): The main source of gaseous peroxide is the
dismutationof the hydroperoxy radical.
2HO2. H2 O2 + O 2 11
Air, Water and Soil Pollution The source of aqueous H2O2 is the dissolution of gaseous H2O2 into atmospheric
hydrometeors. The other sources are reduction of superoxide byorganic compounds,
hydrogen carbonate, photolysis of aqueous ozone and water vapour photonucleation.
The photonucleation involves mainly the oxidation reaction of S (IV) to S (VI) in
aqueous phase. This is the important source of sulphate particles that act as cloud
condensation nuclei, which play a key role in the formation of acidic aerosols and
acid rain.
Aqueous H2O2 is also involved in Fenton and Photofenton process. The Fenton
reagent (Fe (II) + H2O2) oxidises organic and inorganic compounds present in water
droplets in the atmosphere. In the photolysis process, Fe (III) complexes are
converted into Fe (II) in the atmospheric hydrometeors.
Dear learners, having learnt about the species present in the atmosphere we can
summarise the synergistic effect of these species in the atmosphere.
In the troposphere, there are three important end-removal processes taking place.
1. Atmospheric pollutants get converted into nonpolluting constituents like water
and oxygen.
2. Gaseous pollutants are absorbed by plants, water and soil by the phenomenon
of dry deposition.
3. The soluble species are eliminated by the process of precipitation.
H2O2 reacts with nitrous acid to form peroxynitrous acid, HOONO. It is highly
unstable species and transformed into.OH + .NO2and.NO3. It also increases the
rate of corrosion of silver when exposed to atmosphere.
In the stratosphere region, the oxygen molecule (O2) in the presence of UV radiation
forms atomic oxygen. Atomic oxygen further reacts with molecule of oxygen to
produce ozone (O3). For this reason, ozone concentration is higher in the
stratospheric region, which forms ozone layer. Stratosphere protects the earth
surface from the harmful effects of the sun radiation by absorbing UV light.
Chlorofluorocarbons (CFCs) are a group of volatile organic compounds (VOCs)
capable of reaching stratosphere. These react with UV light to generate chlorine
atoms. Chlorine molecules present in atmosphere convert ozone to oxygen molecule
hence the concentration of ozone would be decreased.
The chemical reactions which take place in the atmosphere by absorbing solar
radiations are:
1. Photochemical reactions
2. Redox reactions
3. Acid base reactions
These are explained in the following subsections.
1.3.3 Photochemical Reactions
Photochemical reactions are the reactions in the atmosphere that are catalysed by
the electromagnetic solar radiations. These reactions are controlled by two basic
principles given below.
a. Grotthus-Draper Law: It is also known as the principle of photochemical
activation. It states that the solar radiation (light) must be absorbed by a
12
 compound in order for a photochemical reaction to take place. For example, Environmental
Chemistry and Pollution
only the light which is absorbed by a molecule can be effective in producing
photochemical changes in the molecules.
Some of the photochemical reactions are given below.
1. Photosynthesis: Plants use solar energy to convert carbon dioxide and water
into glucose and dispose of oxygen as a by-product. Both carbohydrates and
oxygen are required to sustain life on earth.
CO2 + H2O C6H12O6 + O2 (g)
2. Formation of Vitamin D:It is a vital vitamin for bone and teeth development
and kidney function. It is formed by the reaction of 7-dehydrocholesterol with
sunlight.
3. Ozone Formation: When oxygen is exposed to sunlight it gets converted into
ozone which will be discussed in Sec 1.4.
b. Stark- Einstein’s Law of Photochemical Equivalence: It states that for
each photon of light absorbed by a chemical system only one molecule is
activated for subsequent reaction. The energy absorbed by one molecule of
the reacting molecules is given by E= h
Where E= Energy of each quanta
h= Plank’s constant (6.6 x 10-27 erg. Sec)
= frequency of the radiation
Therefore, the number of molecules absorbing radiation is equal to the number of
photons absorbed. This means that one molecule is activated by each quantum of
radiation.
a. Primary Photochemical Reactions
In aprimary photochemical reaction molecules absorbs solar radiation, move to the
excited state, and are relatively energized and reactive as well. These molecules
either transfer the energy to other molecules/atoms or lose their energy by emitting
light to reach the normal state.
Example: Photo dissociations
h
1. NO2 NO2.

NO 2 NO + O
h
2. NOCl NOCl.

2NOCl 2NO + Cl2

b. Secondary Photochemical Reactions

In a secondary photochemical reaction, it is not necessary that the absorbed
radiation by a molecule in the form of photon undergoes further reaction. The
absorption of one photon by a molecule in the first step results in the formation
of an activated molecule. This may lead to the reaction of more molecules through
13
a chain mechanism.
Air, Water and Soil Pollution Example: Formation of Free Radicals
In a chain reaction light energy stimulate a series of reactions by generating free
radicals, which are reaction intermediates.
For example: h
SO2 SO2

SO2 + O2 SO4
This reaction can be terminated byreacting with other free radical or suitable species
and terminates the reaction.
Example: SO4. + O2 SO3 + O2
.CH3 + .CH3 CH3 – CH3
The other important reaction is the formation of photochemicalsmog, where the
photooxidation reaction between NO2 and SO2 leads to the formation of
photochemical smog. The formation of photochemical smog is a significant
phenomenon and also an important environmental issue.
Check Your Progress 2
Note : a) Write your answer in about 50 words.
b) Check your progress with possible answer given at the end of the
unit.
3. What is a photochemical reaction and explain chain reaction.
..............................................................................................................
..............................................................................................................
..............................................................................................................
............................................................................................................. \

1.3.4 Redox Reactions

Redox reactions are the reactions in which oxidation and reduction reactions occur
at the same time with transfer of electrons. These redox reactions in the atmosphere
decide the abundance and the effects of manyorganic and inorganic pollutant species.
Kinetics of these reactions indicates that these reactions in the atmosphere are very
slow. This significant propertyis useful in controlling the air pollution.
The abundance of oxygen is very high in the atmosphere.Since it contains21% of
oxygen,oxidation reactions in the atmosphere are thermodynamically favourable.
The available oxygen in the atmosphere either reduces or oxidises the compounds
containing carbon, nitrogen and sulphur.
You know that in oxidation and reduction reactions two components are always
present in which one component is oxidised and the other one is reduced. When an
organic compound is oxidised by a catalyst, the catalyst itself must be reduced.
Likewise, when an organic compound is reduced by a catalyst, the catalyst
getsoxidised. This phenomenon can also be understood bysome general statements
as given in Fig.1.1.
14
 Increase in the number of C-O bonds or decrease in the number of C-H bonds Environmental
Chemistry and Pollution
is termed as oxidation.
 Increase in the number of C-H bonds or decrease in the number of C-O bonds
is termed as reduction.
For example: Formation of CO2 from methane
Increase in the number of C-O bond
Increase in the number of C-H bonds

Fig. 1.1: Formation of CO2 from methane indicating oxidation and reduction reaction

Some of the oxidation-reduction reactions are given below.

1. Corrosion: Rusting of Iron
When iron is exposed to moist air, it converts iron into rust and disintegrates it
slowly. Rusting is acommon term used for corrosion of iron. Rust consists of
hydrated iron (III) oxides, Fe2O3. nH2O, iron (III) oxide-hydroxide (FeO (OH),
Fe (OH)3.
2. Acid Rain: Nitric oxide is oxidized to nitrogendioxide then reacts with
atmospheric moisture to form nitric acid,whereas sulphur dioxide is oxidised to
sulphate radical,then gets converted to sulphuric acid. These compounds
precipitate as snow or rain which is known as acid rain which we will discuss
in detail in Unit-2.

1. 4NO + 3O2 4NO2

4NO2 + 2H2O 4HNO3

2. SO2 + O2 2SO4-2

2SO4-2 + 2H2O 2H2SO4

The products from these reactions show adverse effects on the atmosphere like the
photochemical smog that will be discussed in Unit-2.
1.3.5 Acid- Base Reactions
All the species existing in the atmosphere can be classified either as acids, bases or
salts. Acid-base reactions occur between acidic and basic species. In simpler
terms, proton [H] donor is an acid whereas proton acceptor is a base. 15
Air, Water and Soil Pollution Example: Inorganic Acids
HCl, H2SO4, HSO4, H2O, H3O+
Example: Inorganic Bases
H2O, NH3, OH,  NH2
Compounds like H2O that contain both hydrogen atoms and lone pair act as
both acid and base depending on the reaction. Our atmosphere is slightly acidic
in nature because of the presence of CO2 that dissolves in atmospheric water
droplets and dissociates in the following way.
H 2O H+ + OH

CO2 (g) + H2O H+ + HCO3

SO2 (g) + H2O H+ + HSO3

Strong acids like HNO3 and H2SO4 are produced by the atmospheric oxidation
reactions of NO, SO2 and H2S.
The abundance of basic species in the atmosphere is relatively small when
compared to the acidic species. The most important basic species in the
atmosphere is ammonia (NH3). It enters the atmosphere from biodegradation
of nitrogen containing biological matter and from bacterial reduction of nitrate
ion. It neutralizes acidic species in the atmosphere like HNO3, H2CO3, H2SO4
because it is soluble in H2O.
Example:
NH3 + H2O NH4+ + OH 

NH3 +HNO3 NH4NO3

NH3 + H2SO4 NH4HSO4

After studying the important reactions taking place in the atmosphere, in the
next section we take up an important global phenomenon which is a consequence
of many factors including those discussed in the above subsections. The
phenomenon is called the global warming and the related factors include the
greenhouse gases.

1.4 GREEN HOUSE GASES AND GLOBAL

WARNING
As mentioned in the previous section, there are gases present in the atmosphere
that absorb IR radiations and radiate heat because of which these are responsible
for increased temperature across the globe. The gases are called the greenhouse
gases due to their behaviour like that of a greenhouse. On a global scale, six
main gases are referred to as greenhouse gases. These are: carbon dioxide (CO2),
methane (CH 4) nitrous oxide (N 2O), fluorinated industrial gases like
hydrofluorocarbons (HFCs), perfluorocarbons (PFCs) sulphur hexafluoride (SF6)
and chlorofluorocarbons (CFC). Water vapour is also considered a greenhouse
16 gas. The greenhouse gases are responsible for the well known global warming.
CO2 average life time cannot be measured with a value since it is not destroyed Environmental
Chemistry and Pollution
over a period of time. It travels from ocean to atmosphere to land system.
Since the absorption in the sink is very slow process it will remain in the
atmosphere for thousands of years. Its 100 years global warming potential is
one ton.
An example is given here to make you to understand the greenhouse gases and
the phenomenon of global warming. The interior of a closed car heats up when
the car is parked in the sun. This is due to the radiation from the sun entering
through windows and getting absorbed by the inner objects of the car, then
converting light energy into heat energy, which releases in the form of IR radiation.
Unlike, sunlight this IR radiation is blocked inside the car and cannot leave the
car. The trapped heat energy causes the rise in temperature inside the car. In
the same way, gases that trap the heat in the atmosphere similar to that of glass
in a greenhouse hence they are called greenhouse gases. Greenhouse gas effect
increases the average temperature of the earth’s climate system that is, known
as global warming. The increase in the greenhouse gas concentration is the
major cause of global warming. Let us try to understand global warming potential,
a term related to global warming.
1.4.1 Global Warming Potential
All greenhouse gases (GHGs) may vary in atmospheric lifetime and heat-trapping
potential.
Global Warming Potential (GWP) unit has been developed to compare the ability
of each greenhouse gas to trap heat in the atmosphere relative to carbon dioxide
(CO2) over a specified time. In general, greenhouse gas emissions are calculated
in terms of how much CO2 would be required to produce an equivalent warming
effect in the given time. This is called the carbon dioxide equivalent (CO2e)
value and is calculated by multiplying the amount of gas by its global warming
potential (GWP).
GWP value provides policy makers to compare the impacts of emissions and
reductions of different greenhouse gases. For example, methane is a notable
contributor of the greenhouse effect and has a GWP of 21. This means that
methane has approximately 21 times more absorption capacity of heat radiation
than carbon dioxide per unit of weight. Methane emissions in permafrost areas
could be higher than CO2.

DO YOU KNOW?
The Greenhouse effect was first indentified by French scientist Jean- Baptise
Fourier in 1927. The Greenhouse gases are like heat blankets, insulating
Earth and slowing down the process of IR energy into the space. Without
this insulation average surface temperatures on earth would be about -
19OC instead of +14OC and it would be impossible to sustain life. Therefore,
our global climate depends on the concentrations of greenhouse gases in
Earth.

After understanding the Greenhouse gas phenomenon we should learn about

the sources and effects of greenhouse gases in the following subsection. 17
Air, Water and Soil Pollution 1.4.2 Sources of Green House Gases
The greenhouse gases are generated by different sources as detailed below
for all of these.
1. Carbon dioxide: The increasing source of carbon dioxide in the atmosphere
is by burning fossil fuels (coal, natural gas and oil) solid waste, trees and
wooden products and manufacturing process of cement.
Sink: The terrestrial sink is the absorption of CO2 in the process of
photosynthesis. The oceanic sink is by uptake of CO2 by phytoplankton
as well as dissolution acid-base reactions and reactions of carbonates. The
atmospheric life-time (ALT) of CO2 is 12.4 years and 100 years GWP is
28-36 tons.
2. Nitrousoxide: The main source of nitrous oxide in the atmosphere
isoxidation of ammonia (NH3) in the atmosphere and also from tropical
soils. Anthropogenic sources are agricultural burning of biomass and
anaerobic denitrification process.
Sink: Most of the nitrous oxide (N2O) participate in the photolytic process
and convert it into N2 + O. in stratosphere. The rest of the N2O reacts
with oxygen to generate nitric oxide (NO) that can participate in the ozone
depletion reaction.
3. Methane: It is a third most important greenhouse gas and is a product of
fermentation reactions catalyzed by microbes. The natural source of
methane (CH4) is wet lands. Bacteria emit methane in the process of
decomposing organic materials in the absence of oxygen (anaerobic decay).
Anthropogenic sources are from livestock (methane is generated in the
ruminants stomach as a part of digestive process), natural gas production
and transmission, rice cultivation landfills, coal mines and manure storage
systems.
Sink: The sink for methane is the atmospheric oxidation by hydroxyl radical.

Do You Know?
Human activities that produce CH4 include energy production from natural
gas, coal and petroleum, decomposition in landfills, raising ruminant animals
and rice farming. Wetlands are the main natural source of CH4 (marsh gas
produced by the anaerobic decay of vegetation). A similar induced effect
is caused by the warming planet that has recently caused permafrost
melting in the Arctic with accompanying decay of vegetation that had been
frozen.

CH4 now bubbles from shallow newly-formed lakes caused by permafrost

subsidence and collects under the ice when these lakes freeze over in the winter.
Poking a hole in the ice and igniting the resulting rush of gas produces a striking
effect, Fig. 1.2.
4. Chlorofluorocarbons and Halocarbons: The source of chlorofluoro-
18 carbons and halocarbons are only anthropogenic in nature. This contains
 hydrofluorocarbons, perfluorocarbons, sulphur hexafluoride, chlorofluoro- Environmental
Chemistry and Pollution
carbons and nitrogen trifluoride. These gases are emitted from various
industrial processes, commercial and household uses like refrigerants and fire
retardants.
Sink: Removal process is very slow and they will persist from GWP-1000
yrs/10,000 years and are permanent residents.
5. Water Vapour: It is one of the most abundant greenhouse gas. It absorbs IR
radiation and obtained through evaporation and precipitation. It undergoes
rapid turnover in the lower atmosphere controlled by local temperatures. Due
to the ‘positive feedback’ phenomenon it increases the climate sensitivitythereby
increases the anthropogenic greenhouse gases.
The effects of these gases on global warming and therefore climate change
depend upon the following:
1. How much is too much?It means that the adverse effects will be measured
in concentrations (concentrations are measured in ppm/ppb/ppt).
2. How long is too long? Which means average times it remains in the
atmosphere.
3. How strong is too strong?How strongly it absorbs energy.

1ppm- is equal to one drop of H2O into 13 gallons of liquid.

Dear learner, we will quickly go through the consequences of global warming.

Global warming results in to the following effects:
1. Rapid changes in global temperature
2. Extreme weather patterns resultin more hurricanes and drought to
occur. Longer duration of heat waves and intense rain is generally
experienced.
3. Ecosystem impactslikespecies habitats decrease and the chances for
various ecosystems to adapt naturally would diminish.
4. Rising sea levels due to water expand when heated resulting into melting
of polar caps.A large mass of human lives in the coastal line suffers.
5. Ocean acidification caused by dissolving more atmospheric CO2 into
the oceandisrupts the ability of oceanic life to make shells and skeleton
of calcium carbonate.
6. Increase in pests and diseases of the agricultural crops

1.4.3 Ozone Layer

The Earth’s atmosphere consists of various layers. The troposphere is the lowest
layer extending to 15 kms in altitude. Next layer is stratosphere that extends upwards
to an altitude of 50 kms. The terrestrial life cannot sustain in stratosphere since its
density is too low but it is the house of the ozone layer, which has the ability for life
to survive on earth. About 90% of ozone present in stratosphere and remaining
ozone is located in troposphere. Dear learners, you have learnt in school about 19
Air, Water and Soil Pollution
ozone layer that filters the UV radiation from the sun before reaching the earth
and is known as protecting layer.
The molecular oxygen (O2) and the ozone (O3) interconvert in stratosphere in
the presence of UV radiation of the sun.
Interconversion reaction in the stratosphere can be written as follows:
h
1. O2 2O (i)

O2 + O O3 (ii)

h
O3 O2 + O (iii)

The high energy solar radiation splits O2into oxygen atoms, which combine with
other molecules of O2 to produce O3 as in the first and second reactions. Ozone
is a bluish gas with pungent odor. Ozone may be generated by many ways by
the atmospheric reactions. Sometimes, ozone may be produced near high-voltage
equipment by the action of electrical discharges. In the troposphere, ozone is
produced by NO2. NO2 splits in the presence of sunlight, releases oxygen atoms
and in the lower atmosphere it produces ozone. Ozone can also produced by
carbon monoxide (CO)(Fig. 1.3). Oxidation of CO produces hydrogen atom
that reacts with oxygen in the following way.

CO+OH CO2+H

H+O2  HO2
The HO2 radical undergo self-reaction to produce hydrogen peroxide.

HO2 + HO2 H2O2+O2

This hydrogen peroxide acts in three different ways in the atmosphere.
1. Due to its soluble nature it is removed from the atmosphere and deposited
by rain water.
2. It produces hydroxy radical on photolysis.
h
H 2O 2 2OH

3. It reacts with hydroxy radical to produce HO2 radical.

H2O2 +OH HO2+H2O
The regenerated HO2 reacts with atmospheric NO produce ozone in the following
manner.
HO2 +NO OH+NO2
h
NO2+ O2 NO+O3

The sequences of repeated chain reactions that occur in the atmosphere are as
20
follows:
 O2 Environment Pollution and
Chemistry
CO+OH CO2+ HO2

HO2+NO OH+NO2
h
NO2+ O2 NO+O3

The over all reaction is

CO+2O2 CO2+O3

hv

O3 Stratosphere

Troposphere
hv
NO2 NO
O3 hv
H2O OH HO2 H2O2
co

Deposition

Fig. 1.3: Mechanism for O3HOXNOX  CO chemistry

Ozone acts as a natural atmospheric filter for biologically damaging UV-B light
by absorbing it in the range of 200-310 nm frequency where interconversion of
ozone and molecular oxygen occurs as shown in the above reaction. The role of
stratospheric ozone is by undergoing photo dissociation reaction where it
intercepts the damaging UV radiations from reaching the Earth’s surface. This
absorption of UV radiation by stratosphere prevents 99% of UV radiation from
reaching the Earth’s surface. The radiation energy in this range is enough to
cause skin cancer in human beings and damages our environment. For that reason
stratospheric ozone is termed ozone shield and the ‘good ozone’. The ozone
in the troposphere is highly reactive with living tissue causing adverse effects on
humans, forest damage and reduced crop production and finally alters the
ecological welfare. Hence the ozone in the troposphere is known as destructive
ozone or ‘bad ozone’.
Let us read in the next section how the ozone layer depletion is affecting the
whole ecosystem.

1.4.4 Ozone Layer Depletion

The depletion of ozone layer is not good for the living beings as has earlier been
mentioned.A number of factors play role in this for example; chlorofluorocarbons
play a major role in the depletion of ozone. Specific examples like CFCl3 (CFC-
11), CF2 Cl2 (CFC-12) compounds are non-flammable, volatile but readily
liquefiable, non-toxic and relatively inert in nature. Because of these beneficial
properties they are useful in refrigerators as coolants, in foam plastic
manufacturing, aerosol propellants and industrial solvents. These properties
are useful for human comforts but adversely affect the stratospheric ozone. Once, 21
Air, Water and Soil Pollution these gases release into the atmosphere, these persist for very long time because
of relative inertness in the troposphere and enter into the stratosphere through
atmosphere mixing. The high energy solar radiation in the stratosphere
decomposes chlorofluorocarbons and is involved in reactions which curtail the
concentration of ozone.
Series of chemical reactions that deplete the ozone layer in the stratosphere are
cleavage of C-Cl bond that results in chlorine free radical as shown in the
following steps:n the stratosphere are cleavage of C-Cl bond results in chlorine
free radical
Step (i)

h
CFCl3 (g) CF 2Cl. (g) + Cl. (g)
Step (ii)
The chlorine free radical reacts with ozone molecule by chain reaction mechanism
producing chlorine monoxide free radical and an oxygen molecule.Chlorine
monoxide free radical reacts further in the following way.
Cl. (g) + O3 (g) ClO. (g) + O2(g)
Step (iii)Chlorine monoxide reacts with oxygen atoms to form oxygen molecule
and chlorine free radical.
ClO. (g) + O Cl.+ O2
The net reaction for conversion of two ozone molecules into three oxygen
molecules
2O3 (g) 3O2
The chain reaction increases the rate at which stratospheric ozone is destroyed
but it does not alter the rate of ozone formation. The reports says that, one
chlorine atom will destroy as many as 1, 00,000 molecules of O3 before it is
suspended to the troposphere as HCl.
The cycle of ozone destroying reactions disturbs the abundance of ozone since
ozone is depleted quickly than it is being produced.
The evidence of stratospheric ozone depletion is the formation of Antarctic
ozone hole. According to the British atmospheric report in 1985, thinning of
ozone layer in the stratosphere over the south pole in September and October.
Scientists found reasons that during summer, NO2 and CH4 react with chlorine
monoxide to trap the chlorine forming chlorine reservoirs. During winters in the
extreme cold weather a vortex of extremely cold air forms clouds containing ice
crystals provides surface for various chemical reactions which produce hydrogen
chloride and chlorine nitrate (ClONO2). They react with each other to form
chlorine molecules.
HCl (g) + ClONO2 (g) Cl2 (g) + HNO3 (g)
During spring, the chlorine molecule photodissociate into chlorine free radicals
that can further involve in the ozone destruction reaction.
22
 Environment Pollution and
Do You Know? Chemistry

Newer alternatives to CFCs are hydrochlorofluorocarbons (HCFCs) and

hydrofluorocarbons (HFCs).These compounds have similar properties as
CFCs, but decomposed by OH radical before reaching the stratosphere,
hence these will not participate in the radical reactions resulting in
O3destruction. Propane and butane are now used as propellants in spray
cans in place of CFCs.
The 1995 Nobel Prize in chemistry was awarded to Mario Molina, Paul
Crutzen and F.Sherwood Rowland for their work in elucidating the
interaction of Ozone with CFCs.

Check Your Progress 3

Note : a) Write your answer in about 50 words.
b) Check your progress with possible answer given at the end of the
unit.
4. Enlist the gaseous pollutants in the atmosphere?
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
5. What are the anthropogenic sources of methane?
.............................................................................................................
.............................................................................................................
.............................................................................................................
6. Write a brief note of global warming potential.
.............................................................................................................
.............................................................................................................
.............................................................................................................

1.5 LET US SUM UP

This unit dealt with environmental pollution and different reactions that occur in the
atmosphere, since the source of pollution is occurred by anthropogenic activities.
Every substance or chemical or material produced by humans or nature can pollute
the environment. Based on the chemical composition, and properties atmosphere is
divided into various regions. There are different physical and chemical reactions
occur in the atmosphere because of chemical interactions between its components.
Tropospheric ozone, methane and nitrous oxide are considered as green house gases.
These have both natural and anthropogenic sources and contribute to the global
warming. The stratospheric ozone is useful for life on earth by protecting them from 23
Air, Water and Soil Pollution UV radiation. Where as tropospheric ozone harmful to the humans and other living
beings.

1.6 KEYWORDS
Acid deposition : Any form of acid precipitation and also fallout of
dry acid particles.
Acid precipitation : Includes acid rain, acid fog, acid snow, and any
other form of precipitation that is more acidic than
normal (i.e., less than PH 5.6). Excess acidity is
derived from certain air pollutants; namely, sulfur
dioxide and oxides of nitrogen.
Aerosols : Microscopic liquid and solid particles originating
from land and water surfaces and carried up into
the atmosphere.
Anthropogenic : Referring to pollutants and other forms of impacts
on natural environments that can be traced to human
activities.
Base : Any compound that releases hydroxyl (OH-) ions
when dissolved in water. Asolution that contains a
surplus of hydroxyl ions.
Biosphere : The overall ecosystem of Earth. The sum total of
all the biomes and smaller ecosystems, which
ultimatelyare all interconnected and interdependent
through global processes such as the water cycle
and the atmospheric cycle.
Biotaliving : Thesumtotalofalllivingorganisms. Thetermusually
is applied to the setting of natural ecosystems.
Buffer : A substance that will maintain the pH of a solution
by reacting with the excess acid in the solution.
Limestone is a natural buffer that helps to maintain
water and soil at a near-neutral pH.
CFCs : Nuclear reaction wherein each atom that fissions
(splits) causes one or more additional atoms to
fission.
Chlorinated hydrocarbons: Synthetic organic molecules in which one or more
hydrogen atoms have been replaced by chlorine
atoms. Chlorinated hydrocarbons are hazardous
compounds because they tend to be non-
biodegradable and therefore to bio-accumulate and
many have been shown to be carcinogenic. They
are also called organochlorides.
Chlorine cycle : In the stratosphere, a cyclical chemical process in
which chlorine monoxide breaks down ozone.
Chlorofluorocarbons : Synthetic organic molecules that contain one or
(CFCs) more of both chlorine and fluorine atoms and that
24 are known to cause ozone destruction.
Convection : The vertical movement of air due to atmospheric Environmental
Chemistry and Pollution
heating and cooling.
Environmental impact : Effect on the natural environment caused by human
actions. Includes indirect effects, for example,
through pollution, as well as direct effects such as
cutting down trees.
Photosynthesis : The chemical process carried on by green plants
through which light energy is used to produce
glucose from carbon dioxide and water. Oxygen is
released as a by-product.
Precipitation : Any form of moisture condensing in the air and
depositing on the ground.
Primary pollutants : Pollutantsreleased directlyintothe atmosphere mainly
as a result of burning fuels and wastes, as opposed
to secondary pollutants.
Troposphere : The layer of Earth’s atmosphere from the surface to
about 10 miles in altitude. The tropopause is the
boundary between the troposphere and the
stratosphere above. The troposphere is well mixed
and is the site and source of our weather, as well as
the primary recipient of air pollutants.

1.7 REFERENCES AND SUGGESTED FURTHER

READINGS
1. Fundamentals of Environmental Chemistry byA.K.De
2. Environmental Chemistryby StanleyManahan
3. Environmental Science textbook by Richard T. Wright

1.8 ANSWERS TO CHECK YOUR PROGRESS

1. A pollutant may be defined as a physical, chemical or biological substance
unintentionally released into the environment which is directly or indirectly
harmful to humans and other living organisms. Whereas pollution is the
presence of substance in the environment that, because of its chemical
composition or quantity, prevents the functioning of natural processes and
produces undesirable environmental and health effects.
2. Air pollution, water pollution, soil pollution, Noise pollution,Thermal and
Radiation pollution.
3. Reactions that occur by absorbing sunlight are known as photochemical
reactions with the formation of various types of free radicals as intermediate
species. A chain reaction is a sequence of reactions where a reactive product
or by-product causes additional reactions to take place. In a chain
reaction, positive feedback leads to a self-amplifying chain of events. Due
to the abundance of oxygen molecules in the atmosphere oxidation and
reduction reactions will occur. Some chemical reactions in the atmosphere 25
Air, Water and Soil Pollution can occur as gas phase collisions between molecules, on the surfaces of
solid particles (particulate matter) or in aqueous solution (in water droplets).
The reactions that take place in water droplets are mainly acid-base reactions.
4. CO2, CO, CH4, CFCl3, NOX, SOX.
5. Anthropogenic sources are from livestock (Methane is generated in the
ruminants stomach as a part of digestive process) natural gas production
and transmission, rice cultivation landfills, coal mines and manure storage
systems.
6. The Global Warming Potential (GWP) is a measure to allow comparisons
of the global warming impacts of different gases. It provides how much
energy the emissions of 1 ton of a gas will absorb over a given period of
time, relative to the emissions of 1 ton of carbon dioxide (CO2). The higher
the GWP the more that a given gas warms the earth compared to CO2 over
that time period. The time period usually used for GWPs is 100 years.
GWPs provide a common unit of measure, which allows adding up emissions
estimates of different gases and allows policymakers to compare emissions
reduction opportunities across sectors and gases for making decisions.

26