UNIT 1 AIR POLLUTION

Structure
1.1 Introduction
1.2 Objectives
1.3 Definition of Air Pollution
1.4 Types of Air Pollutants and their Sources
1.4.1 Primary Air Pollutants
1.4.2 Secondary Air Pollutants
1.5 Tropospheric Ozone
1.5.1 Tropospheric Ozone Formation
1.5.2 Tropospheric Ozone Concentration
1.5.3 Health Impacts
1.6 Volatile Organic Compounds
1.6.1 Sources
1.6.2 Impacts
1.6.3 Management and Policy
1.7 Atmospheric Deposition of Air Pollutants
1.7.1 Photochemical Smog
1.7.2 Industrial Smog
1.7.3 Acid Precipitation
1.8 Let Us Sum Up
1.9 Key Words
1.10 Suggested Further Reading/References
1.11 Answers to Check Your Progress
1.0 INTRODUCTION

Our present climatic conditions are relatively different from the pre-industrial
period’s atmosphere concerning pollution. We cannot find clean air nowadays due
to atmospheric pollution. Although, developing nations like India especially with
an upcoming economy, face infinite challenges with its increase in population and
ubiquitous scarcity and deprivation, in meeting consequential loyalty connected
with Sustainable Development Goals such as “poverty and hunger eradication”. In
the last 30 years, India has been growing steadily towards industrialization which
leads to environmental pollution specifically air pollution. We can realize that air
pollution started only after anthropogenic activities such as the burning of fossil
fuels. Continuous addition of air pollutants to the atmosphere from diversified
sources are accumulated in the atmosphere and changes its natural composition and
show adverse effects on the environment. In the environment, the duration of stay
of these pollutants will depend on the quantity of pollutants that accumulate from
different sources and the ability of the cleaning mechanism of the atmosphere either
to absorb or to disintegrate into harmless substances and disperse them. If it is so
we need to understand some of the facts about pollution that damages the health of
our beautiful natural environment including us. This unit makes you understand the
basic concepts of air pollution-related facts.
Atmospheric
Issues 1.2 OBJECTIVES
After studying this unit, you should be able to
•• define air pollution and describe its constituents;
•• explain various types of air pollutants and their sources;
•• describe sources of volatile organic compounds and their impacts;
•• explain tropospheric ozone and describe its effects and
•• describe air pollution management techniques and policies.

1.3 DEFINITION OF AIR POLLUTION

According to the United States Environmental Protection Agency (2007), air
pollution is defined as “the presence of contaminants or pollutant substances
in the air that interfere with human health or welfare, or produce other harmful
environmental effects”.
“Air pollution can also be defined as the presence of impurities in the air like toxic
gases, particulate matter of solid and liquid material at elevated concentrations,
aerosols that interfere with human health or welfare, or produce other harmful
environmental effects by changing the chemical composition of the natural
environment. In other words, a substance which is potentially harmful to the
natural environment and humans as well is known as air pollutant”. Now we
have to understand exactly what do you mean by harmful? Harmful means
any negative effect that can damage and destroy all living things and the
natural environment. Let us first discuss the air pollutants and their sources.
Air pollutants are the substances such as any gaseous substance or aerosols or
complex chemical mixtures in the atmosphere which have negative effects on
living things and the environment. Air pollution is considered an alphabetical
soup of gaseous and particulate pollutants mixed with the normal unpolluted
constituents of air. The level of air pollution is depending on the following.
i. Quantity of pollutants released into the atmosphere
ii. Dispersion area of pollutants
iii. Removal mechanism of air pollutants.

1.4 TYPES OF AIR POLLUTANTS AND THEIR

SOURCES
Pollutants are categorized into two groups. They are primary and secondary
pollutants.
1.4.1 PRIMARY AIR POLLUTANTS
Primary air Pollutants: Primary pollutants are the pollutants that are the direct
products of combustion and evaporation of fossil fuels. Most of the combustion
processes are incomplete and involve complex compounds. The evaporation
of volatile organic compounds combined with dust and smoke enters the
atmosphere.
Particulate matter (PM) / Suspended Particulate Matter (SPM): They exist
in liquid and gaseous form and their size is measured in terms of aerodynamic
8 diameter (Table1.1).
 Table 1.1 Size of air pollutants and their description Air Pollution
Particle size Description
‘Inhalable’ particles, enter the nose & mouth
Less than 100 microns
easily
‘Fine’ particles known as 'thoracic' enter the
Less than 10 microns (PM10)
respiratory system easily

‘Respirable’ particles enter the blood

Less than 4 microns
through the respiratory system

Less than 2.5 microns (PM2.5) ‘Fine’ particles

Less than 0.1 microns (PM0.1) ‘Ultrafine’

The particulate matter is in the form of smoke, soot, metal powder, and dust
released by wind and by atmospheric reactions. This suspended particulate
matter is generated from the condensation of gases and the pattern of the wind.
These particles scatter in space and absorb visible light and diminish visibility.
Fine particles are composed of precursor gas such as sulphuric acid that is
generated in the atmosphere by Sulphur dioxide oxidation. SO2 is released by
the combustion of fossil fuels, volcanic eruptions and various other sources.
Because of the low vapour pressure of H2SO4, they condense into aqueous
sulphate particles under any atmospheric conditions. It is produced by the various
combustion process. These sulphate particles further react with gases that have
low vapour pressure such as ammonia, nitric acid and organic compounds. The
other key component in the SPM is organic carbon, which is a major fraction
formed by the condensation of hydrocarbons released from anthropogenic and
biogenic sources. Earth’s surface releases soil dust, sea salt and detritus of
vegetation by the mechanical action of wind. These SPM consists of particles
with 1-10 micrometre diameter. Another type of SPM which is produced by
gaseous condensation during the combustion process is soot mainly consists
of elemental carbon and accumulated black carbon. In the atmosphere, these
particles scatter the radiation beam in its path without absorption. The scattering
of light radiation takes place by the process of reflection, refraction or diffraction
of the beam of radiation. These particles affect the lungs, trigger cardiovascular
disease, and impair the growth of lungs in children with increased mortality.
Volatile Organic Compounds (VOC), Carbon monoxide (CO), Carbon dioxide
(CO2), Oxides of Nitrogen (NOX), Oxides of Sulphur (SOX) and Radon (Rn) are
examples of primary pollutants.
Source: Combustion of fossil fuels, and waste liberates soot or smoke which
contains carbon particles. Incomplete combustion of fossil fuels releases Volatile
Organic Compounds (VOC). In the presence of air and at high temperatures
combustion of fuels generates nitric oxide (NO), nitrogen dioxide (NO2) and
nitrogen tetroxide (N2O4). Sulphur present in the coal oxidized during combustion
releases SO2. These oxides of sulfur are the reason to cause Sulphur Smog’ due
to the light absorption witnessed in the year 1952, as the London Smog episode.
Chemical toxins like benzene are produced from the combustion of fuels used in
transportation. Lead was added to gasoline as an anti-knocking agent and other
heavy metals were also primary pollutants released from automobile exhaust.
Some primary pollutants, their sources and their effects are discussed here.
9
Atmospheric Carbon monoxide: It is formed by the incomplete combustion of fossil fuels. It
Issues binds to haemoglobin in the blood and blocks the oxygen delivery to the tissues
which leads to dizziness, headache, unconsciousness and finally, death occurs.
Volatile organic compounds (VOC): They are produced from incomplete
combustion of fossil fuels, emissions from various industries, and evaporation
of gasoline and solvents. VOCs are carcinogenic. VOCs are described in detail
in the latter part of this unit.
Oxides of Sulfur (SOx): Burning of sulfur-containing fossil fuels such as coal,
volcanic emissions, sea spray and microbial processes release oxides of sulphur.
It reacts with nitric acid droplets to form acid rain and impairs breathing.
Exposure for a longer duration to SO2 can cause bronchitis.
Oxides of Nitrogen (NOx): Oxides of nitrogen are generated and released
into the atmosphere by burning nitrogen-containing fuels, biomass at high
temperatures, lightening and microbial processes. It reacts with sulphuric acid
droplets in the atmosphere to contribute to acid rain. Chronic exposure may
impair lung function and affect the immune system.
Radon (Rn): Radon breakdown of radium and uranium-containing rocks.
Exposure to radon for a longer duration causes lung cancer.
Lead (Pb): Previously lead was used to prevent engine knockout by adding it
to gasoline. It is also emitted by the burning of lead-containing fuels and solid
waste and remained airborne. Lead shows toxic effects at low concentrations
also. Once it is accumulated in the body that can lead to death by damaging the
brain.
Chlorofluorocarbons (CFC): CFCs are released into the atmosphere from
leakages from refrigerants and aerosols. CFCs are one main cause of
depleting the ozone layer and cause skin cancer.
According to Clean Air Act (1970) established National Ambient Air Quality
Standards, Particulate matter, ozone, carbon monoxide, Sulphur dioxide,
nitrogen dioxide and lead are considered ‘criteria air pollutants’ because US-EPA
controlled them by primary and secondary pollution criteria standards. Primary
standards protect public health and secondary standards prevent environmental
damage.
CHECK YOUR PROGRESS 1
Note: i) Use the space given below for your answers.
ii) Check your answers with those given at the end of the unit.
1. Define air pollution.
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1.4.2 SECONDARY AIR POLLUTANTS

Secondary air Pollutants: Primary pollutants undergo some chemical reactions
and produce additional unwanted compounds known as secondary pollutants.
Ex: Ozone, peroxyacetyl nitrates (PAN), H2SO4 and HNO3.
10 Sources: In the presence of sunlight VOC and NOX both undergo reactions in the
atmosphere to form ozone and these are collectively known as photochemical Air Pollution
oxidants. NO2 splits into atomic oxygen and NO in the presence of UV radiation
and forms ozone by further oxidation. In the presence of VOCs, nitric oxide
form highly reactive peroxyacetyl nitrates (PAN), Aldehydes and ketones by the
process of oxidation. These repeated reactions increase the ozone concentrations
in rural and urban areas. Sulfuric acid and Nitric acid produced from SOX and
NOX are the main components of acid rain.
Ozone O3: Tropospheric ozone is a secondary pollutant and is emitted into
the atmosphere by photochemical reactions of VOCs & NOx. The ozone
concentrations are likely to increase by afternoon and damage the rubber
material by oxidation, damage the lungs and show adverse effects on animals
and plants.

1.5 TROPOSPHERIC OZONE

Tropospheric ozone is considered a Secondary Pollutant because it is generated
by a series of reactions in the Troposphere mainly by the reaction between
primary pollutants such as NO2 and oxygen-containing organic compounds. It
can be easily identified even at the 0.02 ppm concentrations. Tropospheric ozone
is also known as ground-level ozone, which cannot be emitted directly into
the environment but is generated in the atmosphere by the chemical reactions
between NOx and VOC. Since it is formed in the lower atmosphere and present
in the ambient air and exposed daily to humans and the ecosystem.
These chemical reactions occur when these pollutants emitted from point
sources and non-point sources react with each other in the presence of UV
radiation. This reaction is also known as the photodissociation reaction of NOx.
The concentration of ozone increases in the summer season in urban areas but in
some countries, it can reach even higher levels in the winter season. Ozone will
travel for longer distances by wind, hence rural areas can also experience the
effects of ozone. In contrast to stratospheric ozone, tropospheric ozone present
in the air we breathe is a harmful secondary air pollutant that has adverse health
effects on the environment hence it is known as bad ozone.
The tropospheric ozone is a secondary air pollutant and not easily controlled
because it is continuously created with the continuous emissions from
automobile exhaust and the presence of sunlight. Ozone is continuously formed
by the reaction of VOCs, NOx and atmospheric oxygen at low levels. In the
winter season due to low temperatures, low intensity of light and high wind
speeds the ozone concentrations are low. Whereas in the summer season at high
temperatures, high intensity of light and stagnation of wind the concentrations
of ozone are high relatively.
1.5.1 Tropospheric Ozone Formation
The tropospheric ozone formation is dependent on many precursors. Dear
learner here we would like to give a simple way to understand the formation of
tropospheric ozone.
1. Some portion of the ozone is transported from stratosphere to troposphere
through tropopause which is a precursor for tropospheric hydroxyl ion
(OH). The transportation rate of ozone is in the range of 1-2 X 1013 moles/
year. Each ozone molecule that enters the troposphere can produce two
hydroxy molecules. A portion of the transferred ozone is consumed by some 11
Atmospheric reactions in the troposphere and the remaining portion is deposited on the
Issues surface of the earth. Apart from this, in the troposphere, the ozone is formed
by the following reactions.
2. The tropospheric ozone is formed by the reaction between oxides of nitrogen,
carbon monoxide and VOC in the presence of sunlight, hence these are also
called ozone precursors. The major source of these ozone precursors are
emissions from vehicles, industries and solvents. The reactions involved in
the formation of ozone are as follows.
Oxidation of CO by hydroxyl ion generates peroxyl radical (R1), which
undergoes self-reaction that gives rise to hydrogen peroxide (H2O2) (R2). Some
of the hydrogen peroxides undergo photolysis to produce hydroxyl radicals and
because of their high soluble nature in water, they can be removed from the
atmosphere by rain (R3). Hydrogen peroxide reacts with additional hydroxyl
radical to produce peroxyl radical again (R4). The peroxyl radical in the
presence of nitric oxide regenerates hydroxyl radical and nitrogen dioxide (R5)
that immediately photolyze to produce ozone (R6). Hence, the net reaction is
the generation of ozone (R7) in a chain reaction initiated by peroxyl radical and
terminated by the loss of peroxyl radical in reaction (R2) through propagation
reactions in the presence of abundant NOx. The coupling reaction between
ozone, oxides of nitrogen and peroxyl radical is shown in Figure 1.1.
O2
CO+ OH CO2+HO2 (R1)
HO2+HO2 H2O2+O2 (R2)
H 2O 2 hυ 2OH (R3)
H2O2+OH HO2+H20 (R4)
HO2+NO NO2+OH (R5)
NO2+O2 hυ NO+O3 (R6)
CO+2O2 CO2+O3 (R7)

12 Fig. 1.1 Mechanism of O3 generation in a chain reaction cycle

1.5.2 Tropospheric Ozone Concentration Air Pollution

The concentrations of tropospheric ozone depend on the influence of various

concomitant processes such as precursors gas-phase surface emission,
transportation, meteorological parameters like temperature and wind, hydrologic
cycle, solar radiation and exchanges between stratosphere-troposphere (STEs).
Monitoring of ozone can be done both horizontally and vertically in space. If
we will consider the vertical dimension, the space is divided into lower, middle
troposphere and stratosphere. The lower troposphere is termed the boundary
layer where ambient air is present. In the horizontal dimension, often the space
is divided into socio-economic zones like urban, rural and remote regions. The
tropospheric ozone concentrations at the ground level are due to the following
reasons.
• Local photochemical reactions between NOx and VOCs are emitted from
both natural and anthropogenic sources. Once ozone is formed it travels for
long distances. This dispersion is also known as the Urban O3 plume.
• Mixing of O3 rich air at the lower tropospheric boundary layer with ambient
air results in an increase in the O3 concentrations during the morning and
this increase in ozone levels is independent of local region production of
photochemical reactions.
• Due to the mesoscale transport of ozone from long distances and present in
an area where the production of ozone is nil.
• Invasion of stratospheric ozone into the troposphere due to the tropopause
folding events that occurred on the backside of a frontal system that results
in a hole in the tropopause, through which the stratospheric ozone enters into
the troposphere. And this exchange is minimum from July-October in a year.
• Mid tropospheric ozone formed from photochemical reactions transported
to the lower troposphere.
• Removal of tropospheric ozone by chemical scavenging by most potential
chemical scavengers such as nitric oxide.
• Removal of tropospheric ozone is also done by physical scavengings
such as rain washout and chemical decomposition mechanisms which are
temperature-dependent.
Tropospheric ozone is a secondary pollutant and a greenhouse gas. The source
of earth’s heat is solar energy, which is transferred from the Sun to the Earth
by radiation energy and is transformed to heat energy on the surface of Earth.
The earth has to balance this input of absorbed solar radiation with an output
of terrestrial radiation. Some of the reflected solar radiation from the earth is
captured by greenhouse gases in the atmosphere and radiated back to the Earth,
resulting in the surface warming known as the greenhouse effect. Dear learner
as you have learnt, in the previous courses trapping terrestrial radiation by
natural greenhouse gases is one of the key factors for maintaining the Earth’s
surface temperature above the freezing point. The ozone concentrations in the
troposphere are influenced by other greenhouse gases in different regions.
For example, the NOx and CO concentrations are high at midlatitudes of the
northern region in the lower troposphere showing that there is more fossil fuel
combustion. In the upper troposphere, the concentration of NOx is more due to 13
Atmospheric lightning. The NOx concentrations will be balanced in the range of 10-50 parts per
Issues trillion by volume in the entire troposphere. The concentrations of tropospheric
ozone increase with altitude due to the absence of upper troposphere chemical
loss. In the northern hemisphere, the concentrations of ozone are higher than
southern hemisphere because of abundant NOx.
In the tropics, the concentrations of OH are highest, where the concentrations of
water vapour and UV radiation are high, and maximum in the mid-troposphere
due to the opposite vertical trends of water vapour that will decrease with altitude
and UV radiation that will increase with altitude. Concentrations of hydroxyl
radical tend to be higher in the northern than in the southern hemisphere due to
the higher O3 and NOx concentrations and will be compensated for the swift
loss of OH in the northern hemisphere due to elevated concentrations of carbon
monoxide. Increasing the concentrations of NOx and O3 will increase OH,
whereas the increase in CO and hydrocarbons deplete the concentration of OH
since CO and CH4 have longer lifetimes than NOx and O3, their anthropogenic
accumulations are evenly spread in the troposphere.

1.5.3 Health Impacts

Ozone is a powerful oxidizing agent and can irritate the muscle in the passage of
air and trap the air in the alveoli in humans leading to the breathing problems such
as wheezing, breath shortness, cough, sore throat, inflammation of the airways.
In higher concentrations, it worsens the lung ailments like asthma, bronchitis
and emphysema. It weakens lung functioning there by humans experience
recurrent asthma attacks, susceptible to infection and finally cause Chronic
Obstructive Pulmonary Disease (COPD). Long term exposure aggravates
asthma, permanent lung damage and finally leads to death and irregular lung
development in children.
Impact on Ecosystem
The adverse effects of ozone extend to plant ecosystems in sensitive species
of vegetation in forests, and parks and destroy them, particularly during the
growing season. If the ozone concentrations are high in the atmosphere, it
reduces the process of photosynthesis thereby reducing the plant’s growth. In
sensitive plants like tulip poplar, white pine etc., it increases the risk of disease,
copes up with harsh weather, and insects and shows certainly visible evidence
on the plants. In some species, it has adverse effects individually and negative
effects on the whole species diversity, behaviour towards other plant species in
the forest and alters the water and nutrient cycle.
CHECK YOUR PROGRESS 2
Note: i) Use the space given below for your answers.
ii) Check your answers with those given at the end of the unit.
1. Describe the formation of tropospheric ozone.
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2. Which factors influence the concentrations of tropospheric ozone? Air Pollution
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1.6 VOLATILE ORGANIC COMPOUNDS

•• Volatile organic compounds are one of the significant categories of air
pollutants present at the ground level in urban regions and industrial areas.
There are many organic compounds listed under VOC with different
definitions. If we see by term volatile organic compounds suggests that these
compounds exist as liquids and solids at normal temperature and pressure
but in the atmosphere, they exist as gases. As per definition any organic
compound whose vapour pressure is less than 760torr and more than 1, at
200C, and the boiling points range from 500-1000C to 2400-2600C.
•• According to 40 CFR Part 51.100. “Volatile Organic Compounds (VOC)
are any compounds of carbon, excluding carbon monoxide, carbon dioxide,
carbonic acid, metallic carbides or carbonates, and ammonium carbonate,
which participates in atmospheric photochemical reactions”. VOCs have
various levels of reactivity and have varying levels of formation of ozone.
Some VOCs undergo reactions slowly and some produce less ozone. Hence,
local regions experience different levels of adverse effects on exposure to
ozone.
•• 1.6.1 Sources: VOCs are released into the atmosphere as a consequence of
anthropogenic activities, such as evaporation of petrol from vehicles, storage
& distribution of petrol, numerous industrial processes (oil refining, chemical
manufacture, oil and gas production etc.), photocopying, cosmetics, tobacco
smoke, solvents, landfills, food processing units and agricultural activities.
Natural biogenic processes like discharges from plants, animals, forest fires
and anaerobic processes in wetlands are also responsible for VOC emissions.
•• Biogenic Sources: Volatile Organic Compounds are ozone precursors and
most of them are released from the terrestrial ecosystem. Biogenic Volatile
Organic Compounds (BVOCs) are released from a functional group of plants
and are strictly regulated by meteorological actions. Isoprene (C5H8) and
monoterpene (C10H16) are the some of the most abundant biogenic species in
terrestrial vegetation. These emissions are temperature-dependent because
of the rate of photosynthesis. BVOCs are one of the important constituents
of the atmosphere and influence tropospheric chemical reactions.
•• According to EPA standard method TO 15/17, the list of 62 VOCs is
presented in Table 1.1
Table1.1 List of 62 VOCs as per EPA Standard TO 15/17
Ethyl dibromide
Acetone Ethanol
(1,1-Dibromoethane)
Benzene 4-Ethyltoluene Ethyl acetate 15
Atmospheric
Trichlorofluoromethane (Freon
Issues Benzyl chloride Ethyl benzene
11)
Dichlorodifluoromethane
Bromoform 1,4-Dioxane
(Freon 12)
Bromomethane 1,1,2-trichloro-1,2,2-
Propylene
trifluoroethane (Freon 113)
Bromodichloromethane 1,2-Dichlorotetrafluoroethane
Styrene
(Freon 114)
1,3-Butadiene Hexachloro-1,3-butadiene Carbon disulfide
Carbon
2-Butanone (MEK) 2-Hexanone (MBK)
tetrachloride
Dibromochloromethane 4-Methyl-2-pentanone (MIBK) Chlorobenzene

1,2-Dichlorobenzene Methylene chloride Chlorethane

1,3-Dichlorobenzene Methyl-tert-butylether (MTBE) Chloroform

1,4-Dichlorobenzene 2-Propanol Cyclohexane

1,1-Dichloroethane 1,1,2,2-Tetrachloroethane Chloromethane

1,2-Dichloroethane Tetrachloroethene Heptane

1,1-Dichloroethene Tetrahydrofuran Toluene

cis-1,2-Dichloroethene 1,1,1-Trichloroethane o-Xylene
trans-1,2-
1,1,2-Trichloroethane m-Xylene
Dichloroethene
1,2-Dichloropropane Trichloroethene p-Xylene
cis-1,3-
1,2,4-Trichlorobenzene Vinyl acetate
Dichloropropene
trans-1,3-
1,2,4-Trimethylbenzene Vinyl chloride
Dichloropropene
Hexane 1,3,5-Trimethylbenzene
1.6.2 Impacts
•• Ozone depletion in the stratosphere
•• Ozone formation at ground level
•• Chronic health effects
Most of these impacts are already discussed in the previous sections. The known
chemicals in general use under VOCs are Benzene, Toluene and Xylene (BTX).
The BTX compounds are toxic in nature and harmful pollutants.
Health Effects
Acute Effects: On exposure to these chemicals’ humans experience dizziness,
Headache, Nausea/Vomiting, Eye irritation/watering, Nose irritation, Throat
16
irritation, Asthma exacerbation. Air Pollution
Chronic Effects – Cancer, damage of Central Nervous System, Liver & Kidney
damage.
Ground-level ozone formation
Ozone is an important photochemical oxidant. Ozone in the troposphere
is formed by the reaction of VOC and oxides of nitrogen in the presence of
UV radiation. Ozone is formed in the stratosphere in the same way as in the
troposphere but the source of oxygen atoms is different. In the stratosphere,
the oxygen atom is available from the photodissociation reaction of the oxygen
molecule in the presence of UV radiation at < 240nm whereas in the troposphere
oxygen atom is from the photodissociation reaction of nitrogen oxides under
UV radiation at > 290nm.
The overall reaction is as follows

NO + VOC NO2

NO2 >hν NO(g)+ O(g)

>290nm
O(g)+ O2 (g) O3(g)

1.6.3 Management and Policy

a. The Air (Prevention and Control of Pollution) Act, 1981 in India is
an Act of the Parliament of India to control and prevent air pollution and
was amended in 1987. This is the first act of India established to prevent,
control and abate air pollution.
b. The Ozone-Depleting Substance (Regulation and Control) Rules,
2000, states that under Article 5, 1st paragraph of the Montreal Protocol
Regulation production and consumption of ozone-depleting substances.
This act also deals with monitoring and reporting requirements. In India,
MoEFCC has established an Ozone Cell that carries out the tasks of the
phaseout of the ozone-depleting substance.
c. National level strategy for pan India implementation to handle the
problem of increasing air pollution across the country in a comprehensive
manner in the form of the National Clean Air Programme (NCAP) was
launched under the Minister of Environment, Forest and Climate Change.
“The main objective of the NCAP is comprehensive mitigation actions for
prevention, control and abatement of air pollution besides augmenting the
air quality monitoring network across the country and strengthening the
awareness and capacity building activities.” The NCAP function with an
aim of collaborative, multi-scale and cross-sectoral coordination between
the relevant central ministries, state governments and local bodies.
There is no specific legislation of VOC specifically in India besides National
Ambient Air Quality Standard for Benzene by the Central Pollution Control
Board of India. Worldwide, the United States Occupational Safety and
Health Administration (OSHA) and World Health Organization (WHO)
have suggested a few regulations and guidance for VOCs and made them
not compulsory for individual governments to follow. 17
Atmospheric International Conventions
Issues The 1991 Geneva Protocol
The ‘Geneva Protocol on the Control of Emissions of Volatile Organic
Compounds or their Transboundary Fluxes’ was signed in Geneva (Switzerland)
on 18 November 1991. The main objective of this protocol is the reduction
of Volatile Organic Compounds (VOCs), which is a key air pollutant that is
responsible for the formation of ground-level ozone. The options are given by
this Protocol for the reduction in emission targets that have to be chosen upon
signature or upon ratification. The first option is by the year 1999 a thirty per
cent reduction in emissions of volatile organic compounds. The second option
is a 30% reduction within a Tropospheric Ozone Management Area (TOMA)
mentioned in annexe I to the Protocol and by ensuring the total 1999 national
emissions should not exceed the levels of 1988. Thirdly, if the 1988 emissions
did not exceed specified levels then Parties may choose for stabilization at that
emission level of 1999.
The 1999 Gothenburg Protocol
Gothenburg protocol is to Abate Acidification, Eutrophication and Ground-level
Ozone and signed on 30th November 1999 in Gothenburg, Sweden. The main
objectives of this protocol are to control and reduce emissions, establish national
emission ceilings for 2010-2020 for four pollutants (SO2, NOx, NH3) including
VOC and provide negotiation facilities based on “Scientific Assessments of
Pollution Effects and Abatement Options”. The protocol also emphasizes
stringent limit values for emission sources such as combustion, electricity
production, dry cleaning, paints and aerosols have to be controlled. The protocol
was amended in 2012, to include national emission reduction commitments to
be achieved by 2020 and beyond.

1.7 ATMOSPHERIC DEPOSITION OF AIR

POLLUTANTS
The adverse effects of these pollutants may be additive, synergistic or antagonistic
but more often synergistic. One of the important effects of air pollution is the
smog that reduces visibility and is comprised of tropospheric ozone (O3). In this
unit, we will discuss different types of smog.

1.7.1 Photochemical Smog

The primary pollutants trapped in the lower atmosphere on exposure to UV
radiation from the sun form a thick blanket of smog known as photochemical
smog. The pollutants like ozone (O3), hydrogen peroxide (H2O2), organic
peroxides (ROOR’), organic hydroperoxides (ROOH), and peroxyacetyl
nitrates (RCO3NO2) PAN are the main pollutants of photochemical smog. The
latter is formed by the irradiation of mixtures of alkanals, ozone and nitrogen
dioxide. The oxides of nitrogen emitted from the combustion process are
released into the atmosphere and initiate the process of ozone formation and
photochemical smog. The reactions involved in the formation of photochemical
smog are explained here. Small amounts of atmospheric oxides of nitrogen are
sufficient to initiate atmospheric chemical reactions for ozone formation and
photochemical smog formation.
18
 Air Pollution
hν
NO2 NO+O (R8)
M
O+O O3 (R9)
O3+NO NO2 (R10)
O3 O + O2 (R11)
hν
O+ H2O 2OH (R12)
HCHO H.+ HCO. (R13)
HCHO+OH. HCO.+H2O (R14)
M
H.+O2 HO2. (R15)
HCO.+O2 HO2.+ CO (R16)
HO2.+NO NO2.+ OH. (R17)
OH.+NO2 HNO3 (R18)
Note: The M in R9 is any 3rd molecule that is inert that is required to stabilize
the intermediate by absorbing vibrational energy in its excited state.
The reaction initiates with the photolysis of nitrogen dioxide (R8), to produce
nitric oxide and an oxygen atom. This dissociated oxygen atom quickly reacts
with an oxygen molecule in (R9) to produce ozone. Once ozone is formed it
reacts with nitric oxide (R10) to reproduce nitrogen dioxide. The steady-state
ozone concentration is predicted and measured based on initial concentrations
of nitrogen dioxide. At λ, 315 nm, ozone dissociates into an oxygen atom in
the excited state and oxygen molecule (R11). Sometimes excited oxygen atom
strikes water molecules and generates hydroxyl radicals (R12). The hydroxyl
radical unlike other radicals formed from organic molecules does not react with
abundant oxygen, but it reacts with other compounds such as CO, R-CHO,
hydrocarbons etc. The next reaction in the series starts from formaldehyde,
which undergoes photolysis and reacts with hydroxyl radicals resulting in
hydrogen radical and formyl radical (R13 & R14). The hydrogen radical reacts
with oxygen molecule swiftly to form hydroperoxyl radical ( R15) and the
formyl radical reacts with oxygen molecule resulting in both hydroperoxyl
radicals and carbon monoxide (R16). These hydroperoxyl radicals react further
with nitric oxide to reproduce nitrogen dioxide and hydroxyl radicals (R17). In
the end, hydroxyl radical reacts with nitrogen dioxide to form nitric acid (R18).
Next in the reaction series that contributes to the photochemical smog, we will
see the next higher aldehyde that is acetaldehyde, which undergoes a series
of reactions in two pathways like formaldehyde, photolysis and reaction
with hydroxyl radical to produce peroxyacetyl nitrate (PAN), which is a key
component in the photochemical smog. The reactions involved in the formation
of PAN are as follows.
CH3CHO CH3+HCO (R19)
CH3CHO+OH CH3CO+H20 (R20)
CH3+O2 CH3O2(R21)
CH3CO+O2 CH3COO2 (R22)
CH3O2+NO NO2+CH3O (R23)
CH3O+O2 HCHO+HO2 (R 24) 19
Atmospheric CH3COO2+NO NO2+CH3COO (R25)
Issues CH3COO+O2 CH3O2+C02 (R26)
CH3COO2+NO2 CH3COO2NO2 (PAN) (R27)
The photolysis reaction (R19) of acetaldehyde results in methyl radical and
formyl radical. In the reaction with hydroxyl radical, it produces acetyl radical
with the liberation of H2O (R20). The methyl radical generates methyl peroxy
radical in reaction with O2(R21), while acetyl radical reacts with oxygen and
produces acetyl peroxy radical (R22). The methyl peroxy radical rapidly reacts
with nitric oxide to yield nitrogen dioxide and methoxy radical (R23). Likewise,
in reactions (R24 - R27) resulting in peroxyacetyl nitrate. The general reactions
representing the photochemical smog are as follows.
The general reactions of Photochemical Smog are given below:
1) NO + VOC → NO (nitrogen dioxide)
2) NO2 + UV → NO +2 O (nitric oxide and molecular O)
3) O + O2→ O3 (ozone)
4) NO2+ VOC → PAN (peroxyacetyl nitrate)
Overall reaction:
NO + VOC + O2+ UV → O3 + PAN + other particulates
1.7.2 Industrial Smog
Industrial smog is well known as grey or black smog that is formed in cold
and humid temperatures, particularly in urban areas where industrial pollution
is more with the emission of sulfur. The sulphur reacts with water vapour in
the atmosphere to produce sulphur dioxide. SO2 is oxidized to form sulphuric
acid and sulphate particles as soon as it was produced. On catalytic oxidation
of industrial dust particles in the presence of water vapour in the atmosphere
makes the droplets more acidic. All these particulates form a thick layer of haze
known as acid smog or industrial smog. The general reactions to industrial
smog are given below.
1) C + O2→ CO (Carbon dioxide)
2
2) S + O2 → SO (Sulfur dioxide)
2
3) SO + O2→ SO + O (Sulfur trioxide)
4) SO2 + H2 O → H 3
2
SO (Sulfuric acid)
5) H2 SO4 + NH → (NH 4) SO4 (Solid ammonium sulfate)
3

3 4 2
1.7.3 Acid Precipitation
Acid precipitation is the type of deposition such as rain, fog, mist or snow
that is relatively acidic than normal. The pH of rainwater without pollutants
is approximately 5.6. Acid deposition is the deposition of rain and dry acidic
particle with a pH of less than 5.5. It consists of sulfuric acid (H2SO4) and
nitric acid (HNO3) mixture. Sulfur and nitrogen oxides are released into the
troposphere either by the burning of fossil fuels or by natural sources. They are
oxidized by hydroxyl radicals to sulfuric acid and nitric acids which dissolve in
rainwater and reach the ground as acid deposition. Wet acid deposition is known
as acid rain. Dry deposition is called acid fog.
CHECK YOUR PROGRESS 3

20 Note: i) Use the space given below for your answers.

 ii) Check your answers with those given at the end of the unit. Air Pollution
1. What impact does VOCs pollution have on human health?
……………………………………………………………………………
….…………………………………………………………………………
……………….……………………………………………………………
…………………………….………………………………………………
………………………………………….…………………………………

1.8 LET US SUM UP

Several forms of air pollutants exist in the form of gases, fumes, clouds,
smoke, mist, fog, smog, haze, dust, aerosols, etc. They are classified as natural/
anthropogenic, primary/secondary, particulates/gases, ambient air/indoor air/
global, stationary/mobile etc. Air pollutant concentrations are measured in the
form of their threshold values which are different for different pollutants. In
this unit, the emphasis has been made on the chemistry of tropospheric ozone
formation and volatile organic compounds. Atmospheric depositions of air
pollution such as industrial, photochemical and acid rain have been discussed.
Above these values, the pollutants show adverse effects on human beings. The
common problem is respiratory tract infection, bronchitis and other diseases
that can occur due to inhalation of toxic pollutants. Pollutants such as arsenic,
lead, fluoride, insecticides and pesticides affect human beings adversely. The
unit is concluded with some international protocols on VOC.

1.9 KEY WORDS

Acid Deposition: Any form of acid precipitation and also the 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, sulphur dioxide and oxides
of nitrogen.
Aerosols: Microscopic liquid and solid particles originating from land and
water surfaces carried up into the atmosphere.
Convection: The vertical movement of air due to atmospheric heating and
cooling.
Ecosystem: A group of plants, animals and other organisms interacting with each
other and with their environment in such a way as to perpetuate the grouping
more or less indefinitely.
Greenhouse Effect: An increase in the atmospheric temperature caused by
increasing amounts of carbon dioxide and certain other gases that absorb and
trap heat, which normally radiates away from Earth.
Photochemical Smog: The brownish haze that frequently forms on otherwise
clear, sunny days over large cities with significant amounts of automobile traffic.
Photochemical smog results largely from sunlight-driven chemical reactions
among nitrogen oxides and hydrocarbons, both of which come primarily from
auto exhausts. 21
Atmospheric Primary Pollutants: Pollutants are released directly into the atmosphere mainly
Issues as a result of burning fuels and wastes, as opposed to secondary pollutants.
Secondary Air Pollutants: Air pollutants resulting from reactions of primary
air pollutants resident in the atmosphere. Secondary air pollutants include
ozone, other reactive organic compounds, and sulphuric and nitric acids.
Volatile Organic Compounds: A category of major air pollutants presents in
the air in the vapour state. The category includes fragments of hydrocarbon fuels
from incomplete combustion and evaporated organic compounds such as paints,
gasoline, and cleaning solutions. VOCs are major factors in the formation of
photochemical smog.

1.10 SUGGESTED FURTHER READING/

REFERENCES
1. http://cpcbenvis.nic.in/air_pollution_main.html#
2. Manahan, Stanley E. “Frontmatter” Fundamentals of Environmental
Chemistry Boca Raton: CRC Press LLC,2001
3. Sources and Control of Volatile Organic Air Pollutants-United States
Air Pollution Training Institute (APTI) November 2002 Environmental
Protection Environmental Research Center, MD 17 (Revision 2) Agency
Research Triangle Park, NC 27711
4. Fundamentals of Environmental Chemistry by A.K. De
5. Environmental Chemistry by Stanley Manahan
6. Textbook of Environmental Science by Pearson.
7. https://www.atmos-chem-phys.net › acp-15-8889-2015

1.11 ANSWERS TO CHECK YOUR PROGRESS

Check Your Progress 1
1. Please refer to section 1.3
Check Your Progress 2
1. Please refer to section 1.5.1
2. Please refer to section 1.5.2
Check Your Progress 3
1. Please refer to section 1.6.2

22