ENVIRONMENTAL SEGMENTS

Broadly speaking, the environment consists of the following four

segments :
Atmosphere
Hydrosphere
Lithosphere
Biosphere
These segments are discussed below:
(i) Atmosphere: Atmosphere extends up to about 500 kms above the
earth's surface. The atmosphere comprises of a mixture of gases like
nitrogen and oxygen (major components), and argon, carbon dioxide
(minor components) etc.
Oxygen is essential for life on earth, Carbon-dioxide is essential for
photosynthesis. Nitrogen is used by nitrogen fixing bacteria and
ammonia- manufacturing plants to yield chemically bound nitrogen
essential for life.
The temperature, pressure and density of the atmosphere vary with
altitude. Depending upon the altitude the temperature of the atmosphere
varies from - 100° C to + 1200° C. The atmospheric pressure is 3 x 107
atmosphere at 100 Km above the sea level and it rises to 1 atmosphere at
sea level.
It also helps to maintains the heat balance of earth through absorption of
radiations emitted by Sun and reemitted from the earth. It also protects
the earth from dangerous cosmic radiations from outer space and helps in
sustaining life on earth through a phenomenon known as "Green-house
effect". Atmosphere is also a vital carrier of water from oceans to land (as
part of hydrologic cycle).
(ii) Hydrosphere: Hydrosphere constitutes About 80% of the surface of the
earth which is covered by water and because of this earth is also known
as blue planet. This includes all types of water resources-surface as well
as ground like lakes, streams, rivers, seas oceans etc. and ground water,
water locked in rock-crevices and minerals lying deep below the earth's
crust.
It is important to note that not even one percent of the total world's water
resources is available for exploitation by man for industrial, agricultural
and domestic purposes. This is due to the fact that water from 'oceans and
seas is too saline to drink and for the direct agricultural and industrial
uses. Without water life on earth would have been impossible.

(iii) Lithosphere: it is the rigid, rocky outer layer of the earth consisting of the
crust and the solid outermost layer of the upper mantle. It extends to a depth of
about 100 km.
The most important part of lithosphere is soil. This essentially consists
of complex mixture of inorganic and organic matter and water. The
mixture of silicates (of sodium, potassium, calcium, aluminium and iron);
oxides (of iron, manganese and titanium) and carbonates (of calcium and
magnesium) constitute inorganic matter.
The organic matter is present up to about 5 percent and it mainly
determines the productivity of the soil. Polysaccharides nucleotides,
organo-phosphorous and organo-sulphur compounds, sugar and humus
constitute organic matter content of the soil. In fact, lithosphere is the
outer surface of the earth and it consists of earth's crusts and soil.

(iv) Biosphere: Biosphere covers the entire realm of living organisms and
their interactions with the other segments of the environment. In fact,
biosphere is thin life supporting stratum of the earth surface, extending
from a few miles into the atmosphere to the deep sea layers of the oceans.
It is the region of the earth where life exists and is a self regulating
system. Broadly, biosphere is divided into two parts abiotic and biotic.

COMPOSITION OF ATMOSPHERE

The atmosphere is a blanket of air around the earth. Air is a mixture of

gases. In homosphere (Lower 80 km zone of atmosphere) the proportion
of various gases is fairly constant, except for varying amounts of water
vapour (which is restricted to troposphere). In heterosphere, the gases are
present in insufficient quantity failing to form a mixture similar to air.
The maximum concentration of atmospheric gases lie in the lower
atmosphere due to the forces of gravity.
The concentrations of the components of the atmosphere are given in
table 1.
Table 1: Composition of Dry Unpolluted Air by Volume

Gas Concentration
Nitrogen 78.084%
Oxygen 20.946%
Argon 0.934%
Carbon 340 ppm
Neon 18.18 ppm
Helium 5.24ppm
Methane 1.3-1.6 ppm
. Krypton 1.14 ppm
Hydrogen 0.5 ppm
Nitrous oxide - 0.25-0.35 ppm
Xenon 0.087oom -
LAYERS OF ATMOSPHERE

The atmosphere can be broadly divided into four major regions viz.
Troposphere, stratosphere, Mesosphere and Thermosphere. The important
characteristics of these regions are summarized in table 2. and Fig. 1.

Major
Name of theHeight above the Temperature
chemical
region earth's surface,range (OC) Species present
Troposphere 0-11
(km.) 15 to'- 56 02, N2, C02-
Stratosphere 11-50 -56 to-2 03
Mesosphere 50-85 -2to-92 02+,NO+
Thermospher 85-500 -92 to'12OD 02+,O+NO+

# Scaned figure is given in the last.

(a)Troposphere:
Essentially all the atmosphere's water vapour is in the troposphere,
which, therefore, encloses essentially all the storms and precipitation
of the earth. In the absence of any significant air pollution, the
composition of air in troposphere remains uniform due to convection
currents arising from differential heating and cooling rates between
the equator and the poles.
In the troposphere, the temperature of the air decreases with
increasing altitude up to 'tropopause' where the temperature starts
increasing with increasing altitude in the stratosphere. The change of
temperature with height is called the lapse rate. Positive lapse rate is the
decrease of temperature with increasing altitude (in the troposphere).
Temperature inversion occurs at the tropopause where the transition from
positive lapse rate to negative lapse rate takes place.

(B) Stratosphere:
Stratosphere is the region above the tropopause. In this region, the
temperature-altitude curve exhibits a negative lapse rate. the
temperature in this region continues to increase with height due to the
absorption of ultraviolet radiation from sun by ozone. At the top of the
stratosphere there is a narrow zone known as stratospause where the
temperature begins to fall again with increasing height as the
mesosphere is entered:

(C) Mesosphere:
Mesosphere is the region above the stratopause. In this region, the
temperature-altitude curve exhibits a positive lapse rate. The
temperature in this region continues to decrease with height due to the
absence of species like ozone which can absorb u. v. radiations from
the sun. The temperature attains a minimum at the mesopause, a thin
zone of coldest temperature where the temperature stabilizes and soon
start to rise again as the thermosphere is ascended.

(d) Thermosphere:
Thermospher is the region above the mesopause. In this region, the
temperature-altitude curve exhibits a negative lapse rate. The
temperature in this region increases very rapidly with increasing
altitude. This region is characterised by low pressure, low densities
and high temperatures (about 12000 C).
Oxygen and nitric oxide absorb the solar radiations in the far UV
resign and undergo ionisation.
It is important to note that apart from changes of temperature with
height, changes in chemical composition or activity also occurs.
For instance, in chemosphere (a region which includes whole of
stratosphere, mesosphere and lower part of the thermosphere) major
chemical changes occur. Mainly photochemical reactions take place in
this region. The most common is the photodissociation of oxygen
resulting in the formation of ozone

Green house effect/ global warming

The earth is heated by sunlight. Earth radiates some of this heat back into
space. However, some gases like carbon dioxide, water vapours, methane
and chloro fIuoro carbons in the lower atmosphere (acting like glass in a
greenhouse) allow solar radiation to come in but these gases strongly
absorb the infrared radiations which the earth sends back as heat. A part
of the heat so trapped in these gases is re-emitted to the earth surface. The
effect of radiation of thermal energy back to the earth by the atmosphere
is called Green House effect. In fact, this green house keep our planet house
effect keeps our planet and thus helps in sustaining life on earth because
in the absence of this effect, all the heat radiated by the earth would be
lost to the space and the earth would become very cold .
In recent time the condensation of green house gases increased at a very
fast rate due to industrialisation ,deforestation, and increased burning of
fossil fuels. The increased concentration of GHG , especially carbon
dioxide enhance green house effect leading to increase surface
temperature. The increase earth temperature is responsible for the global
warming.
Fig. Relative contributions of active gases to temperature rise.

consequences of Green house effect:

 The surface water would evaporate faster than normal on slight
increase in the surface temperature, creating drought.
 Global warming or Green house effect can adversely affect
world’s food production. This is due to the alterations in the pattern
of weather leading to crop damage and/ or crop failure.
 As a result of green house effect there would be a rise in sea level.
An increase in the average surface temperature of the earth could
melt most of the polar ice caps of Green land and Antarctica
resulting in the flooding of many of the low level coastal areas.
 Due to the warming of surface layer, biological productivity of the
ocean would also be decreased which in turn reduce transport of
nutrient from the deeper layer to surface by vertical circulation.

DEPLETION OF OZONE LAYER

A layer of ozone is constantly formed in the stratosphere from oxygen gas
by the absorption of ultraviolet light. The ozone layer acts as a protective
shield for the existence of life on earth. It absorbs most of the harmful
ultra-violet radiations coming from the sun in the region (220 - 330 nm)
and thereby protects the life from several radiation damages.
Importance of O3 layer

It is found that during past decades due to increased air pollution there is
an overall thinning of ozone layer everywhere especially above Antartica
and arctic,this thinning of ozone layer is called ozone depletion.
Chloroflouro carbon compounds are found to be main reason of ozone
depletion.
CFC are chemically stable ,odourless, noninflammable ,non-toxic and
noncorrosive compounds seems to be dream chemicals .Being cost
effective they become popular as coolant in air conditioners,
refridgerators,propellent in the aerosol spray cans, cleaners for electronic
parts such as computer chip, sterilants for hospital instruments, fumigant
for granaries and ship cargo holds etc.
How these CFCs are responsible for the depletion of ozone layer can be
understood as follows:
CFCs remain in the troposphere as they are insoluble in water and
chemically inactive Over 11-12 years they rise in to stratosphere mostly
through convection ,random drift, and turbulent mixing of air in the
troposphere. Once they reach the stratosphere CFC molecules break down
under the influence of high energy UV radiation. This releases highly
reactive chlorine atoms, which speeds up the breakdown of reactive
ozone into O2 and O in a cyclic chain of chemical reactions. This causes
ozone in various parts of the stratosphere to be destroyed faster than it is
formed. Finally each molecule can last in the stratosphere for 65-
385years depending on his types. During that time each chlorine atom
released from these molecules can convert upto 100,000 molucules of O3
to O2.

Ozone can also be destroyed by its reaction with nitric oxide, hydroxyl
radical etc. present in atmosphere due to
(i) chemical and photochemical reactions in the atmosphere, nuclear
explosions, supersonic jets, etc. generate Nitric Oxide (NO) ;
(ii) chlorine is released in atmosphere due to volcanic activity.
(iii) bio-mass burning leads to OH' generation
In the absence of ozone layer, these ultraviolet radiations would cause
 diseases like skin cancer ill men and animals, swelling of skins,
burning sensation,
 skin aging, leukaemia, breast cancer,. cataracts of eyes,
haemorrhage, lungs injury,
 premature aging, visual impairment, dizziness, inhibition and
alteration of DNA's
 replication and formation of DNA adduct, and may even lead to
Death.
 DNA mutation,
 damage the plants, and
 faster deterioration of paints, fabrics, plastics etc.
 AIR POLLUTION
Air pollution may be defined as the presence of one or more pollutants
(or combination thereof) in the outdoor atmosphere in such quantities
and of such durations, which might be injurious to human, plant or
animal life or property. These pollutants may unreasonably interfere
with the comfortable life or the conduct of business.

AIR POLLUTANTS
Air is never found clean in nature, due to natural and manmade pollution.
Gases such as CO, SO2 and H2S are continually released into the
atmosphere through natural activities, e.g. volcanic activity, vegetation
decay and forest fires. Besides, tiny particles of solids or liquids are
distributed throughout the air by winds, volcanic explosions and other
similar natural disturbances. In addition to these 'natural pollutants', there
are manmade pollutants-gases, mists and particulates, aerosols resulting
from the chemical and biological processes used by man The latter are
present in relatively high concentrations compared to the background
values in air. These pollutants hardly exist beyond 2000 feet above
ground level. Air pollutants are present in the atmosphere in
concentrations that disturb the dynamic equilibrium in the atmosphere
and thereby affect man and his environment.
Causes of air pollution;
 Population explosion
 Industrialisation
 Urbanisation
 Automobiles
  Natural phenomena like volcanic eruption, radioactivity, forest
fires etc.
Depending of their origin pollutants are divided into two categaries
 Primary pollutants and
 Secondary pollutants
Primary Pollutants; pollutants which are directly emitted into the
atmosphere There are five primary pollutants which together contribute
more than 90% of global air pollution. These are:
 Carbon monoxide, CO
 Nitrogen oxides, NOx
 Hydrocarbons. HC
 Sulphur oxides, S02
 Particulates, part
Secondary pollutants; pollutants which are derived from the primary
pollutants due to chemical and photo chemical reactions in the
atmosphere, eg. Ozone, Peroxy-acyle nitrate, photochemical smog etc
According to chemical composition;
Organic pollutants, e.g.
 Hydrocarbons
 aldehyde
 ketones
 alcohols etc.
Inorganic pollutants;
 carbon compounds
 Nitrogen compounds
 Sulphur compounds
 Halogen compounds
 Oxidising compounds
Carbon Monoxide
It is a colourless, odourless and tasteless gas above -192°C (-314°P). It is
96.5%as heavy as air and is not soluble in water. The basic chemical
reactions yielding CO are:
 Incomplete combustion of fuel or carbon-containing compounds:
2C + O2 2CO
 Reaction between CO2 and carbon containing materials at elevated
temperatures in industrial processes, e.g. in blast furnaces
CO2 + C 2CO
 . Dissociation of CO2 at high temperatures
CO2 CO+O

Sources and Sinks of CO Pollution

Natural processes, e.g. volcanic action, natural gas emission, electrical

discharge during storms, seed germination, marsh gas production, etc.
contributes in a small measure to CO in the atmosphere. The significant
contribution is from human activities.
The annual emission on a global scale is 350 million tonnes (human
source 275 and natural 75 million tonnes), of which the USA alone
releases more than 100 million tonnes of CO into the atmosphere. (a)
Transportation contributes about 64% of CO-motor vehicles, 59.2%
aircrafts 2.4%; and railroads 0.1 %. (b) Next in magnitude is
miscellaneous sources, 16.9%-the main components are forest fires, 7.2%
and agricultural burning, 8.3%. Agricultural burning implies controlled
burning of forest debris, crop residues, brush, weeds and other vegetation.
(c) Industrial processes, mainly iron and steel industries and petroleum
and paper industries, constitute the third largest contributor of CO (9.6%)
to the air. The atmospheric background of CO is 0.1 ppm.
Sinks-The annual input of CO into the atmosphere by human activities is
expected to double its concentration in the ambient (surrounding)
atmosphere every five years. But the actual increase in ambient global
CO concentration is much less. The major CO sink is some soil micro-
organisms. A potting soil sample weighing 2.8 Kg completely removed,
in three hours, 120 ppm CO from ambient air.
The same soil sample, when sterilised, failed to remove CO from air.
Of 200 micro-organisms isolated from the soil and cultured, 16 fungi
were found to be active in the removal of CO.

The soil sinks can take care of atmospheric CO, but it still exists in
significant concentrations in the atmosphere. This is because neither CO
nor the soil sink is distributed uniformly. As a matter of fact, the largest
CO producing areas often have the least amount of soil sink available.
Since the automobile remains the largest single source of CO pollutant
(59.2%), highly populated urban areas have the highest ambient CO
concentrations. Figure 6.1 shows the typical CO concentration profile in a
busy downtown street of Manhattan, USA.
CO concentrations, averages over 8-hour periods, are given in Table 6.2
for locations with increasing distance from traffic. An 8-hour period is
used as the body absorbs and des orbs CO slowly. At low levels of CO, 4
to 12 hours are required so that an equilibrium can be established between
the concentration of COHb in the body and the average CO concentration
of the inhaled air. The first two locations in Table 6.2 are applicable to
taxi, and bus drivers and traffic policemen, while the last two locations
apply to the average citizen.
Control of CO Pollution
The transportation sources are responsible for 74% of all CO emissions
and gasoline-fed internal combustions (Table 6.1) are primarily
accountable for it. Hence, the considerable efforts for control of CO
pollution are mainly directed automobiles. Use of catalytic converters in
two stages helps in eliminating pollutants from exhaust gases before they
are discharged into the atmosphere.
In the first converter (NO)x is reduced to Nz (+ NH3) in the presence of
finely divided Pt, as catalyst, and the reducing gases, CO and
hydrocarbons. The production of NH3 is kept at a minimum under
carefully controlled conditions.
In the second converter, air is introduced to provide an oxidising
atmosphere for complete oxidation of HC and CO into HzO and COz in the
presence of finely divided Pt catalyst. One problem of the Pt catalyst is
that it is liable to be poisoned by heavy metals (e.g. Pb) present in
gasoline itself. Hence Pb-free gasoline must be used for proper function
of catalytic converters.

CO level (ppm) Effects on humans

Impairment of judgement and
10
visual perception
100 Headache, dizziness, weariness
250 Loss of consciousness
750-1000 Death

The soil micro-organisms act as a major sink for carbon monoxide from
ambient atmosphere. But still it exists in significant concentrations in the
atmosphere, because the largest CO-producing areas have the least
amount of soil sink available around them.
The following efforts have been directed towards controlling carbon
monoxide emission from transportation section:
 Fuel modification
 Development of substitute fuels,
 Modification of engine design
 Treatment of exhaust gases.

Oxides of Nitrogen (NOx)

NO and NO2 are mostly responsible for air pollution and they are jointly
represented as NOx is formed by photolytic reactions in the atmosphere.
Oxides of nitrogen may also be formed by natural or artificial fixation of
nitrogen from the atmosphere or from nitrogen compounds present in
organic matter . NOx can also be produced by the combustion of coal,
oil, natural gas and other organic matter. hence, NOx is introduced
into the atmosphere from incinerators, automobile exhausts, coal based
power plants etc. Some of the involved reactions are:

1210 - 1765° C
N2+O2  2NO
2NO+O2 2NO2
The most important primary photochemical reaction is the dissociation of
NO2,
NO2+hv(398nm) NO+O

The NO so formed may be oxidized by O3 (or more slowly by O2), thus

leading to cyclic chain reaction. When the NO 2 is completely converted
into HN03 by hydration and catalytic oxidation in presence of aerosols,
fog or photochemical smog, the~ain may be broken.
NO + O3  NO2 + O2
NO2 + O3  N2O5 + O2
4 NO2 + O2 + 2 H2O  4 HNO3
N2O5 + H2O  2HN O2

HNO2 and HNO3 may also undergo photochemical dissociation as

follows:

HNO2 + h NO2+H
HNO2 + h  NO+HO',
HNO2 + h  NO2+ HO'( in stratosphere)
NO2+OH'  HNO3
The nitric acid (HNO3) so formed is removed as acid rain because it gets
precipitated as nitrates during rainfall.It is also important to note that
photochemical and chemical reactions involving NO2and hydrocarbons
induced by sunlight can lead to the formation of photochemical smog.
The following efforts have been directed in controlling NOx emissions
from various sources:
(a) Use of two stage catalytic converters in automobiles,
(b) Use of a two-stage combustion process in power plants

Sulphur dioxide
(SOX A mixture of SO2 and SO3 is commonly represented as SOx
The sources of SOx pollution are summarized below:
 Volcanic activity,
 Combustion of any sulphur-bearing materials, say in coal-fired
power stations
 and refineries,
  Transportation,
 Smelting of sulphide ores in metallurgical operations,
Atmospheric sulphur dioxide absorbs solar radiation in the range of 300-
400 nm and produces electronically excited states of SO2, { SO2  SO2*.
This undergoes oxidation to SO3

SO2* + O2  SO4*
SO4* + O2  SO3 + O3

SO3 in presence of water vapour gets converted to H2SO4 .

The overall reaction may be represented as

SO2 + 1/2 O2 + H2O  H2SO4  (H2SO4)n

aerosol

The above reaction is catalysed by olefinic hydrocarbons and oxides of

nitrogen.The droplets of H2SO4 aerosol can give rise to acid-rain. H 2SO4
and (H2SO4)naerosols present in the urban air can easily reach the
pulmonary region of lungs,causing serious respiratory problems
(particularly in older peoples).
The following efforts have been directed in controlling
SOx emissions from the anthropogenic activities:
 The use of Low-sulphur fuel, ,'
 Discouraging power generation by fossil-fuel based thermal power
plants

Hydrocarbons
There are mainly three sources which emit hydrocarbons in the
atmosphere. They are
 solvent evaporation
 automobile exhausts and
 burning of wood, coal, oil and refuse
Methane is mainly emitted into the atmosphere by natural activities such
as anaerobic decomposition of organic matter in Water, soil and
sediments by micro organisms. Ethane, n-butane, n-pentane etc. 3.rle
other hydrocarbons which have been detected in atmosphere in areas of
heavy vehicular traffic.
These hydrocarbons gets oxidised in the atmosphere by a series of
chemical and photochemical reactions. This results in formation of CO2,
solid organic particulates and water soluble acids and aldehyde.
The hydrocarbons also lead to the formation o£ photochemical smog.
Particulates
Volcanic eruptions, wind and dust storms, salt spray etc. are natural
sources of particulate constituents of the atmosphere.
Burning of coal, oil, wood, gaseous fuels; Industrial processes; Smelting
and mining operations; fly-ash emissions from power plants , burning of
coal refuse and agricultural refuse are man-made activities whicl\1
release considerable tonnage of particulate matter in atmosphere.
Particulate matter has large surface areas hence they provide excellent
sites for absorption of various organic and inorganic species .They also
scatter right and reduce visibility.The typical particulate air pol1utants
their sources and effects are summarized below in;

Particulate Sources Effects

Dust Asbestos and Causes respiratory
cement factories and allergic
 diseases
Smoke In complete Causes skin
oxidation of fuels in diseases
automobiles
Lead dust lead batteries and
Causes lead
automobile
poisoning
exhausts

Particulate matter can be removed from industrial gaseous effluents with

the help of following devices; cyclone collectors, electrostatic
precipitators, wet scrubbers and settling chambers.

Indoor pollution

Indoor pollution is defined as "the presence of physical, chemical or biological

contaminants in the air of confined environments, which are not naturally present in
high quantities in the external air of the ecological systems."(Italian ministry for the
Environment, 1991)
In the last thirty years much attention has been paid to reducing the outdoor pollution,
but only recently has the international scientific community worried about reducing
the contamination of the air of closed environments. If we consider the amount of
time a person spends in a closed environment (90%) we will understand that the issue
of indoor pollution is of primary importance.
The atmospheric composition inside an edifice is fundamentally the same we find
outside, but the amounts and types of contaminants differ. To the pollutants present
outside one must add all the polluting agents generated within the edifices.
In the developing countries It is the rural area that face the greatest threat from indoor
pollution, where the people continue to rely on traditional fuels such as firewood,
charcoal, and cow dung for cooking and heating. Concentration of indoor pollutants in
households that burns tradition fuels are alarming’

Burning such fuel produce large amount of smoke and other air pollutants in the
confined space of home resulting in the high exposure. Women and children are the
most vulnerable group as they spend more time indoor and are exposed to smoke.

In urban area , exposure to indoor pollution has increased due to variety of reasons
including construction of more tightly sealed buildings, reduced ventilation, use of
synthetic materials for building and furniture and use of chemical products,
pesticides ,and household care products .

The main sources of indoor pollutants are:

 Construction materials

 Heating, air-conditioning devices, and cooking apparatuses etc.

 Furniture

 Coatings (wall paint, varnish, floors etc.)

 Maintenance and cleaning products (detergents, pesticides etc.)

 Use of space and activities done within it

The study of the effects of air pollution on the human health is complex for the
symptoms are not specific and many pollutants can be responsible for the same
disease. Furthermore there are also the effects caused by stress and climatic
discomfort. The fact that different people react differently to the same conditions must
be considered as well.

Following are the some of the main compounds for indoor pollutants
  Volatile organic compounds

 Pesticides

 Biological pollutants

 Formaldehyde

 Asbestos

 Radon

The main observed effects are:

 Respiratory

 Dermal and mucous irritation

 Effects on the nervous system

 Cardiovascular

 Effects on the gastrointestinal apparatus

 Effects on the reproductive system

 Infections and intoxication

Earth's Radiation Budget

Most input of the Earth energy is received from the Sun. The solar energy
is short-wave radiation. Although the Earth also receives electromagnetic
energy from the other bodies in space, it's negligible, compared with solar
energy The incident solar energy (short-wave) may be reflected and
absorbed by the Earth's surface or the atmosphere. And Earth's surface
and atmosphere also emit the radiation (longwave).The Earth Radiation
Budget is the balance between incoming energy from the sun and the
outgoing long wave (thermal) and reflected short-wave energy
The Earth's Radiation Budget is a concept used for understanding How
much energy the Earth gets from the Sun and How much energy the
Earth-system radiates back to outer space as invisible light.

Absorbed sunlight raises the Earth's temperature. Emitted radiation or

heat lowers the temperature. When absorbed sunlight and emitted heat
balance each other, the Earth's temperature doesn't change - the radiation
budget is in balance

Light from the Sun shines on Earth. Some of that light reflects off clouds
back into space. Some of the light makes it to the ground and warms our
planet. The warm ground and oceans give off infrared (IR) radiation,
which we feel as heat. That IR "light" moves back up through the
atmosphere. Most of it is trapped by greenhouse gases, which keep Earth
warm. After a while, the IR radiation leaks back out into space. Scientists
call this cycle of incoming and outgoing energy “Earth’s radiation
budget”.

The picture on this page shows a lot of details about Earth's radiation
budget. This kind of radiation isn't the kind from atom bombs or nuclear
power plants. Instead, it is electromagnetic radiation. It is mostly visible
light and infrared radiation. Scientists measure it in units of watts per
square meter (W/m2 or W·m-2). Imagine laying out a one meter by one-
meter square on the ground. Now measure how much solar energy falls
on that square each second. That's what we're talking about here. The
average energy from sunlight coming to the top of Earth's atmosphere is
around 341.3 W/m2.

Less than half of the incoming sunlight heats the ground. The rest is
reflected away by bright white clouds or ice or gets absorbed by the
atmosphere. The warm ground gives off IR radiation. The right side of
the picture shows that. Our atmosphere has greenhouse gases in it. They
let normal light pass through, but trap IR "light". It is sort of like having a
blanket covering Earth. Our planet would be about 30° C (54° F) colder if
there wasn't a greenhouse effect! After a while, the IR "light" slowly
leaks back out into space.

For the most part, the energy coming to Earth as sunlight equals the
energy leaving as IR "light". If it didn't, Earth would heat up or cool
down. These days the balance is a little off. Humans have added lots of
greenhouse gases to the atmosphere. Earth's climate is slowly warming
up. That's why scientists are really interested in Earth's radiation budget.
It helps them understand global warming

Smog-photochemical and sulphurous

The name smog is derived from a combination of smog and fog. This is of two types.

1. Classical Smog (sulphurous smog) or London smog

2. Photochemical smog or Los Angeles smog

In the presence of smog, the atmospheric visibility is partially obscured by a haze

consisting of solid particulates and/or liquid aerosols.

Photochemical Smog
Mechanism
Formation of hydroxyl radical
The NO2 absorbs visible and UV radiations from sunlight in the
atmosphere. So the photolysis takes place and ground state oxygen is
formed.

NO2 + hv NO + O

This atomic oxygen reacts rapidly with O2 in the presence of a third body
M (O2 or N2) and produce ozone.
O + O2 + M O3 + M

This ozone undergoes photolysis by UV radiations from sunlight to form

oxygen molecule and oxygen atom, both in the excited state.

O3 + hv O2* + O*

It reacts with water vapour to form *OH radicals.

H2O + O* 2 •OH

Oxidation of hydrocarbons

•OH + RCH3 •RCH2 + H2O

•RCH2 + O2 + M RCH2OO• + M
peroxyacetyl radical

RCH2OO• + NO RCH2O• + NO2

Alkoxyl radical

RCH2O• + O2 RCHO + HOO•

Hydroperoxyl
radical

HOO• + NO NO2 + • HO

In order to reduce the concentration of hydroxyl radicals from the

atmosphere, several termination reactions act to remove • HO radical, its
precursor NO2 and the HOO• radical.

•NO2 + • HO + M HNO3 + M

2 HOO• H2O2 + O2

HOO• + • HO H2O + O2

The nitric acid and hydrogen peroxide are water-soluble and are removed
from the atmosphere by precipitation.

Some secondary reactions are also occurred simultaneously with the

oxidation of hydrocarbons. Like
NO2 + hv NO + O

O + O2 + M O3 + M

Other reactions as CH3CHO an example

CH3CHO + • HO CH3CO • + H2O

CH3CO • + O2 + M CH3COOO •
Acetoperoxy radical

CH3COOO • + •NO2 CH3COOONO2

Peroxyaceticnitric anhydride (PAN)

Sulphurous Smog

Sulphurous smog consists of carbon-based soot, other solid particulates

and high levels of SO2 .The most important source of this smog is
combustion of coal. The other sources are automobile exhausts,
industries, burning of wood and agricultural waste. The most severe air
pollution due to sulphurous smog was first observed in London, in 1952.
So this is also called London smog.

Mechanism

It is generally worst in early hours of morning and appears to worsen

shortly after sunrise, perhaps because of photochemically induced
oxidation of SO2 into sulphur trioxide followed by combination with
moisture to give aerosol.

S + O2 SO2

SO2 + ½ O2 SO3

The second reaction takes place in the presence of sunlight or particulate

matter. Sulphur dioxide combines with moisture from fog to form
sulphurous acid (H2SO3), the oxidation of which is very rapid and more
rapid in the presence of metal salts.
SO2 + H2O H2SO3

H2SO3 + ½ O2 H2SO4
Metal salt

H2SO4 + 2NH3 (NH4)2SO4

or SO2 combines with NH3 in moist air.

SO2 + 2NH3 + H2O + ½ O2 (NH4)2SO4

Harmful effects

Sulphurous smog produces more dangerous effects than the sum total of
SO2 and particulates. Sulphate haze is considered as a greenhouse gas.
Now, this is the reason of climate cooling. It creates acid rain and
depletes ozone layer. This smog is characterized by bronchitis irritation.

Preventive measures

The control of primary pollutants, such as NOx and hydrocarbons will

ultimately control the secondary pollutants. The techniques, like
incineration, absorption, adsorption and condensation are used to control
hydrocarbon emissions from stationary sources.

1. Incineration method

For hydrocarbon removal the flame after burner is used, in which flame is
used to complete the oxidation of hydrocarbon into CO 2 and H2O. The
other device is used for this, is the catalytic after burner in which the
catalyst oxidizes the hydrocarbon at a lower temperature.

2. Adsorption method

In this method, exhaust gases are passed through a bed of granulated

adsorber consisting of activated carbon. Hydrocarbon vapours are
adsorbed on the surface of activated carbon. The hydrocarbons are then
condensed to liquids and can be used for further purpose.

3. Absorption method
Liquid containing dissolved hydrocarbon is brought in contact of exhaust
gases. The contact between absorbing liquid and exhaust gases is carried
in tall scrubbing towers.

4. Condensation method

Smog forming pollutants are condensed to liquids, which are collected

and reused.

The control of hydrocarbon emissions coming out from automobiles is carried out by
the use of oxidizing catalyst, which convert CO and hydrocarbons to CO 2 and H2O
while the reducing catalyst convert NOx to N2.

Acid Rain

Normal rainwater is slightly acidic because of that, CO 2 present in the

atmosphere gets dissolved in it and form carbonic acid, H 2CO3. But in the
atmosphere, the SO2 and NO2 gases are also present as air pollutants.
These gases forms the sulphuric acid and nitric acid and further, lowered
the pH of the rain. When the pH of rain is 5 or below, is known as acid
rain.

Mechanism

Acid rain can either be wet or dry. Acid rain, snow, dew, fog, frost and
mist are the wet form of deposition, while dust particles containing
sulphates and nitrates are called dry deposition. (Mechanism as in
sulphurous smog and in photochemical smog)

Factors responsible

Factors responsible for acid rain are mainly human activities – cars,
homes, factories, power stations, transport and subsequent deposition of
oxides of sulphur, nitrogen and their oxidative products. Other factors are
volcanoes, combustion of fossil fuels, smelters, swamps and planktons in
the ocean.

Effects
Acid rain affects on materials, terrestrial ecosystems and aquatic
ecosystems etc. Acids degrade building materials, especially limestone,
marble, various commonly used metals such as galvanized steel and
certain paints. The increased rate of weathering and erosion of building
surfaces and monuments are also the adverse impacts of acid rain.

CaCO3 + H2SO4 CaSO4 + CO2 + H2O

Air Quality Standards

The Clean Air Act requires the EPA to establish both air quality standards
(NAAQS) and emission standards (NSPS). National Ambient Air Quality
Standards (NAAQS) are acceptable concentrations of pollution in the
atmosphere, while emission standards (NSPS) are allowable rates at
which pollutants can be released from a source.

EPA has established the National Ambient Air Quality Standards

(NAAQS) at two levels: primary and secondary.

Primary standards are set at levels that will protect public health and
include an “adequate margin of safety,” regardless of whether the
standards are economically or technologically achievable. Primary
standards must protect sensitive individuals, including the elderly and
those already suffering from respiratory and cardiopulmonary
disorders.

Secondary standards are established to protect public welfare e.g.

structures, crops, animals, fabrics etc.

National Ambient Air Quality Standards (NAAQS) are for six criteria
pollutants. These pollutants are carbon monoxide, lead, nitrogen
dioxide, ground-level ozone, sulphur dioxide and particulate matter.

Table: National Ambient Air Quality Standards (NAAQS)

S.No. Pollutants Averaging Federal Federal Most Relevant

 Time Primary Secondary Effects
1. Carbon 8 hr 9 ppm (10 None Aggravation of
monoxide mg/m3) angina pectoris;
(CO) decreased
1 hr 35ppm(40 None
mg/m3) Exercise tolerance;
possible risk to
fetuses
2. Nitrogen Annual 0.053 ppm Same Aggravation of
dioxide mean ( 100 respiratory disease;
(NO2) micro atmospheric
3
gm/m ) discoloration
1hr None None
3. Ground 8 hr 0.08 ppm Same Decreased
level (155 pulmonary
ozone micro function; surrogate
(O3) gm/m3) for eye irritation;
materials and
vegetation damage
4. Sulfur Annual 0.03 ppm None Wheezing,
dioxide mean (80micro shortness of breath,
(S O2) gm/m3) chest tightness;
24 hr 0.14 ppm None plant damage and
(365micro odor
3
gm/m )
3 hr None 0.50ppm
1 hr None 0.25ppm

5. PM 10 Annual 50 micro Same Exacerbation of

gm/m3 respiratory mean
24 hr 150 micro Same disease symptoms;
gm/m3 excess deaths;
visibility
6. PM 2.5 Annual 15 micro Same
gm/m3
24 hr 65 micro Same
gm/m3
7. Lead (Pb) 1 month None None Impaired blood
3 months 1.5 micro Same formation; infant
gm/m3 development.

The NAAQS forms the basis for an air pollution index, called the
Pollutant Standards Index (PSI). It has been developed by the EPA and
used by all metropolitan areas in the United States to report to the public
an overall assessment of a given day’s air quality. The PSI integrates air
quality data for five of the criteria pollutants (except lead) into a single
number that represents the worst daily air quality in an urban area.
 Human health effects-Bhopal gas tragedy

The Bhopal gas tragedy took place in Bhopal, Madhya Pradesh, India on
December 3rd, 1984. Which was due to the gas released from a pesticide
manufacturing plant (Carbamate pesticide) of Union Carbide Factory,
caused death of approximately 3200 persons. The methyl
isocyanate was used for the manufacturing of Carbamate pesticide.
MIC was stored under refrigeration in an underground tank at the
Bhopal plant site. The leakage of MIC was due to the refrigeration
units were out of order for several months and the two safety
measures for neutralizing leaking MIC viz. the vent gas scrubber and the
flare tower were also non-functional.

Exposures to MIC lead to chest tightness, breathing troubles and eyeache

and also cyanide generation in the body, which ultimately turns fatal.

Non-Dispersive Infrared and Gas Filter Correlation

Infrared gas analysis is one of the most basic techniques of gas detection. All
gases absorb infrared light energy of various wavelengths. Multiple gases  
  
 
and gases with very complicated absorption spectra may be accurately
 
quantified using variations of and enhancements to this simple technique.  
 
   

Infrared Gas Analyzers: Non-Dispersive Infrared (NDIR) techniques for the measurement of various
gases rely on the energy absorption characteristics of a particular gas in the infrared region. In a simple
NDIR instrument, Infrared energy passes through two identical tubes and falls on a detector. The first tube
is the reference cell and is filled with a non-absorbing gas such as nitrogen. The second tube is the
measurement cell and contains the gas sample to be analyzed. Energy in the region of interest is absorbed
by the gas in the measurement cell, attenuating the energy passing through the cell and falling on the
detector. This attenuated energy is compared to the unattenuated signal from the reference cell. The
difference is proportional to the amount of absorbing gas in the measurement cell.

Application Techniques: A simple method to make the comparison easily with analog electronics is to
use a "chopper wheel" assembly which prevents the energy from both cells from falling on the detector
simultaneously. As the wheel spins, energy from the reference and measurement cells fall on the detector
alternately, producing an AC signal with a magnitude proportional to the diference in energy.

   

An important enhancement to this basic technique is Gas Filter Correlation (GFC). A rotating, gas-filled
filter wheel contains two chambers. One chamber is filled with the species of interest while the other
contains an optically inert gas (i.e. Nitrogen). This filter wheel is interposed between the IR source and the
single sample chamber. As the wheel rotates, the light passes through one side, then the other as well as
the sample chamber. IR energy in the region of interest is attenuated by one side of the wheel, but not the
other. As a result, the difference in energy is inversely proportional to the amount of the species in the
sample chamber. This has the advantage of providing more sensitivity at lower measured concentrations.
Interferent species present in the gas sample attenuate both the sample and reference signals equally and
will not be measured.

A further enhancement of the GFC technique employs multiple filter wheels which align in combinations to
permit the detection of multiple species within the same instrument.

 
  
Detector Types: Over the years, various detectors have been developed for use with infrared gas
analyzers. While most modern instruments employ a solid state, photo-conductive detector, Luft-type and
microflow detectors are commonly encountered.

Generally, all detectors translate the difference in infrared energy into a sine wave that has a frequency
derermined by the chopping rate and a magnitude proportional to the energy difference.

The solid state detector is constructed of a material that changes its electrical conductance in response to
IR light energy falling on it. Changes in current flowing through the detection circuit are proportional to the
difference in transmitted IR energy. The solid state detector has the advantage of being insensitive to
external mechanical vibration. In addition, careful selection of detector material allow for simplified optical
filter design. The Signal Model 7000FM GFC/IR

The Luft type detector is the oldest type found in common use. It is found in dual beam analyzers and uses
a pair of chambers that are filled with the adsorbing gas interest. One chamber recieves light through the
inert gas-filled reference cell, the other recieves light through the sample gas-filled cell. The chambers are
seperated by a capacitive diaphragm which distends in response to the difference in adsorption-induced
gas expansion between the two detector chambers. This detector is extremely sensitive and selective, but
is expensive to produce. The Signal Model 418 uses a variation of the luft detector.

The Microflow detector is similar to the Luft detector, but employs a small orifice between the two detection
chambers. Instead of differential pressure, the resulting flow is measured. A thermocouple arrangement in
the orifice is used for this purpose. This detector is relatively immune to mechanical vibration, but is not as
simple as the solid state type.

Interferences: Many species of gas have overlapping infrared absorption spectra which can cause cross-
interference in the basic technique. Example are water vapor, CO, CO 2, NO, NO2, NH3 and SO2. Selectivity
and interference rejection in NDIR analyzers is achieved either through the addition of optical band-pass
filters, or gas-filled cells. More advanced examples of this technique, employ multiple filters in combination
on rotating wheels, which align to allow the detection of several different gases within the same instrument.