Introduction: AIR POLLUTION

Main Cause of Air Pollution

The main pollution is air pollution. Pollution of air is very common and
dangerous. There are many sources of air pollution but the obvious ones are two fuel
consumption and vehicular exhaust. The sources of air pollution are natural as well as
anthropogenic. Its main cause is suspended particles in air, pollen of plants, smoke
substances spread during vocanic eruption etc. can be considered natural air pollutants.
Amongst anthropogenic sources – smoke from the chimneys of industrial establishments;
thermal power stations; vehicles and domestic usage can be considered.
Industrial sources:
The main causes, several industries have become important sources of air
pollution. Mainly, petroleum refineries and fertilizer factories are responsible for the
emission of SO2, and NO2 in air.
The smelting factories, paper mills, sugar factories and units associated with
manufacture of cotton and cloth, and rubber factories are other major sources of air
pollution. Stone quarries; cement industry and asbestos factories also cause pollution.

Thermal power station:

Power stations producing electricity using coal also give off smoke that contains
flyash, SO2, CO2, NO2, aldehydes, and hydrocarbons are pollutants.

The main cause of air pollution are tabulated below

Pollutant Source Effect of human life
Ammonia Dye - chemical industry. Irritation of respiratory tract.
Fire crackers, polish, fertilizers.
Carbon monoxide Vehicular exhaust, smoking, coalReduces O2 carrying capacity
burning of blood.
Arsenic substances Arsenic – based processes. RBC get degraded. Injures
kidney
Chlorine compoundsBleaching processes and otherDamage eye membranes and
chemical processes. respiratory system.
Hydrogen fluorides Petroleum refineries, glass industry,Damage passage of all body
aluminum, and fertilizer industries. organs.
Hydrogen cyanides Insecticides, furnances, metal plating,Neurons gets damage. Cause
chemical industry. throat dryness, headache, and
blurred vision.
sulphur Burning of coal and oil. Suffocation in chest,
headache, vomiting.
Oxides of nitrogen Burning of raw coal a vehicularCause disease of lungs and
exhaust. heart.
Hydrogen sulphide Refineries and chemical industries Burning sensation of throat
and eyes. Vomiting feeling.
Suspended particles Chimneys: industries, constructionCause diseases of eyes;
work: pollen: dust mites. allergy; lung disease; asthma;
probability of cancer.

CHEMISTRY OF CARBON OXIDES:

Carbon has a variable valency of 2 and 4, and as a result, produces two important kinds of oxides
namely carbon monoxide and carbon dioxide. Both these oxides are gases at room temperature.

CARBON MONOXIDE:
PHYSICAL PROPERTIES :

Nature Carbon monoxide is colorless, almost odorless and tasteless gas.

CHEMICAL PROPERTIES:
Stability:
It is very stable and cannot be decomposed by heat.
Combustibility
It is a combustible gas. It burns well in air or oxygen to form carbon dioxide.

Combination with chlorine

Carbon monoxide combines with chlorine in presence of sunlight and charcoal as catalyst, to form carbonyl
chloride, commonly called as phosgene.

Combination with sodium hydroxide:

Carbon monoxide when heated under a pressure of six atmosphere, combines with sodium hydroxide and
flakes to form sodium formate.

Reducing property
Carbon monoxide is a powerful reducing agent.
Combination with metals:
When carbon monoxide is passed over heated metals under pressure, metal carbonyls are formed.

PHYSIOLOGICAL ACTION OF CARBON MONOXIDE:

Carbon monoxide is an extremely poisonous gas as a result of its physical properties, which add to
the deadly nature of the gas. As the gas is almost odourless, its presence cannot be detected. Also its
vapour density is almost equal to that of air. Hence it mixes easily with air. It neither goes up like ammonia
nor goes down like chlorine.
When carbon monoxide is breathed in, it combines with the haemoglobin of the blood, to form a
very stable compound, called carboxy haemoglobin. This compound being stable cannot carry oxygen to the
cells. As a result, haemoglobin stops functioning as the oxygen carrier. Within a short time, all the
haemoglobin becomes carboxy haemoglobin and gets destroyed, resulting in death.

CARBON DIOXIDE:
PHYSICAL PROPERTIES :
Density Carbon dioxide is heavier than air. Its vapour density is 22 (Vapour density of air = 14.4).
Hence, it is 1.5 times denser than air. So it tends to move downwards. Certain caves and valleys, which
contain carbon dioxide may be fatal to animals, as they get choked to death.

CHEMICAL PROPERTIES:
Carbon dioxide is slightly acidic.
Stability
It is very stable gas at ordinary temperature and pressure.
Combustibility
Carbon dioxide is neither combustible, not a supporter of combustion.but metals
like potassium, sodium, magnesium etc. continue to burn in carbon dioxide.

At the temperature of ignition, these metals are able to reduce the carbon dioxide
to carbon by taking away the oxygen
Reaction with water
Carbon dioxide dissolves in water only to a very small extent. This small quantity
of the gas combines with the water to form carbonic acid.

Action with basic oxides

 Carbon dioxide reacts with basic oxides such as potassium oxide, sodium oxide
and calcium oxide to form carbonates.

Action with alkalis

Carbon dioxide is readily absorbed by alkalis such as sodium hydroxide and
potassium hydroxide, to form their respective carbonates.

The above reaction of carbon dioxide with potassium hydroxide is used to purify air.
Action on heated carbon
When carbon dioxide is passed over red-hot carbon in the form of coke charcoal,
etc., the carbon dioxide loses one of its two atoms of oxygen. As a result, carbon dioxide
gets reduced and becomes carbon monoxide. At the same time the hot carbon also gets
converted to carbon monoxide.Carbon monoxide is a neutral oxide. It is neither acidic
nor basic.
Carbon monoxide
Property Carbon dioxide(CO2)
(CO)
Physiological Highly poisonous gas, death occurs
Non poisonous gas, but death may occur due to asphyxiation
action due to the poisonous nature
Redox reaction Acts as a powerful reducing agent Can oxidize active metals
No action at room temperature but
Action on alkalis Reacts to form carbonates
at high temperatures, forms formates
Action on lime
No change takes place Turns lime water milky
water
Combustible, but not a supporter of
Combustibility Non combustible and non- supporter of combustion
comb ustion
Chemical nature Neutral Acidic
Physical nature Colorless, odorless and tasteless gas Colorless, odorless gas with a slight acidic taste
Fairly soluble in water. 1 volume of water dissolves one
Almost insoluble in water even at
Solubility volume of the gas at 59°F; solubility increases drastically at
high pressure
higher pressures
Almost as dense as air: Vapour
Vapour density density = 14: (Vapour density of air 1.5 times as dense as air; Vapour density = 22
14.4)
CHEMISTRY OF SULPHUR OXIDES:

Sulphurdioxide:
PHYSICAL PROPERTIES :
Vapor density : Its vapor density is 32, while the vapor density of air is 14.4. Hence sulphur
dioxide gas is 2.2 times denser than air.

CHEMICAL PROPERTIES:
In the presence of moisture, sulphur dioxide acts as a powerful reducing agent. On reaction with
water it forms sulphurous acid.

The reducing action of sulphurous acid is of two types:

(i) Reduction by addition of nascent hydrogen

On reaction with water, sulphurous acid liberates nascent hydrogen, which gets added to the other
substance thereby reducing it.

(ii) Reduction by removal of oxygen atom

On reaction with the other substances, sulphurous acid takes away an atom of oxygen from them,
thereby reducing these substances.

With Halogens in Water

Sulphur dioxide reduces halogens to the corresponding hydracids e.g. chlorine is converted to hydrochloric
acid.

With Ferric Chloride

Sulphur dioxide reduces iron (III) salts to iron (II) salts.

With Nitric Acid

Sulphur dioxide reduces hot concentrated nitric acid to nitrogen dioxide, a reddish brown color gas.

Sulphurtrioxide:
Physical properties:
Sulphur trioxide is a silken white transparent crystalline solid.
Sulphur trioxide sublimes on heating.

Chemical properties:
Action of heat:
When heated to about 500oC, sulphur trioxide decomposes to give sulphur dioxide and oxygen.

Action with Water

Sulphur trioxide and water combine very vigorously with a hissing sound. This reaction evolves a
lot of heat and produces sulphuric acid. Hence sulphur trioxide is the anhydride of sulphuric acid.

during the reaction, the heat produced is enough to sublime the trioxide to form fumes of sulphur
trioxide . Hence this method is not used to prepare sulphuric acid. If sulphur trioxide is mixed with 88%
sulphuric acid, pure sulphuric acid can be obtained.
Acidic Nature
Sulphur trioxide combines with bases to form salts.
a) With Basic Oxides
Sulphur trioxide combines directly with metallic oxides to form their respective sulphates.

b)With Alkalis
Sulphur trioxide reacts with alkalis to form their respective sulphate salt and water.

With Concentrated Sulphuric Acid

Sulphur trioxide dissolves in concentrated sulphuric acid to form fuming sulphuric acid or pyro sulphuric acid
or oleum.
HYDROGEN SULPHIDE:

Hydrogen sulphide turns wet blue litmus paper red. It is a weak dibasic acid.
Combustibility
It is a combustible gas, and burns with a blue flame. In a limited supply of oxygen
or air, the products are water and sulphur. In excess of air or oxygen, the products are
water and sulphur dioxide.

Reducing Property
Hydrogen sulphide acts as a powerful reducing agent.
a) With concentrated sulphuric acid
When passed through concentrated sulphuric acid, it reduces the acid to sulphur.
b) With sulphur dioxide
Hydrogen sulphide reduces sulphur dioxide to sulphur.

Precipitation of Sulphides
When hydrogen sulphide is passed through aqueous solutions of metallic salts, the
sulphides of the respective metals get precipitated. These sulphides have characteristic
colours.

Nitric oxide:

The chemical compound nitric oxide is a gas with chemical formula NO. It is an
important signaling molecule in the body of mammals including humans, one of the few
gaseous signaling molecules known. It is also a toxic air pollutant produced
by automobile engines and power plants.

The nitric oxide molecule is a free radical which makes it very reactive and
unstable. In air, it quickly reacts with oxygen to form the poisonous nitrogen dioxide.

Production and environmental effects

At high temperatures molecular nitrogen and oxygen can combine to form nitric
oxide. A major natural source is lightning. Human activity has drastically increased the
production of nitric oxide in combustion chambers. One purpose of catalytic
converters in cars is to partially reverse this reaction.

Nitric oxide in the air may later convert to nitric acid which has been implicated
in acid rain. Furthermore, both NO and NO2 participate in theozone layer depletion.

Nitrous oxide

Nitrous oxide, also known as dinitrogen oxide ordinitrogen monoxide, is

a chemical compoundwith chemical formula N2O. Under room conditions it is a
colourless non-flammable gas, with a pleasant slightly sweet odor. It is commonly known
as laughing gas due to the exhilarating effects of inhaling it. It is used in surgery
anddentistry for its anaesthetic and analgesic effects. Nitrous oxide is present in
the atmosphere where it acts as a powerful greenhouse gas.
Chemistry

The structure of the nitrous oxide molecule is a linear chain of a nitrogen atom
bound to a second nitrogen, which in turn is bound to an oxygen atom. It can be
considered a resonance hybrid of

and

Nitrous oxide can be used to produce nitrites by mixing it with boiling alkali
metals, and to oxidizeorganic compounds at high temperatures.

Nitrous oxide in the atmosphere:

Nitrogen oxides, nitrous oxide included, in the greenhouse gasses; nitrous oxide
has 270 times the effect of carbon dioxide for producing global warming. Nitrous oxide is
naturally emitted from soils and oceans. Human activity contributes to the release of the
gas through the cultivation of soil and the use of nitrogen fertilizers, the production of
nylon, and the burning of fossil fuels and other organic matter.

RADIOACTIVE POLLUTANTS:

Introduction:
Radioactive pollution is nothing but the release of radioactive substances to
the atmosphere either in air, water or soil due to accidents or by any human activity.
Radioactive substances are highly toxic so that it can affect the living beings and pollute
the atmosphere. Mostly of the effects caused by these substances are uncured.
Explanation:
Radioactive pollution is caused by releasing radioactive substances in which in
turn they release radiations which are harmful to living beings. These rays damage our
human cells and cause severe affect. The radioactive material is highly unstable it will
release enormous amount of energy.
The sources of radioactive pollution are as follows,
• Nuclear fuels used in nuclear power plants
• Nuclear weapon testing
• Disposal of radioactive substances from nuclear plants.
• Due to transportation of nuclear materials.
There are three types of radiations in radioactive pollution are as follows,
• Alpha rays
• Beta rays
• Gamma rays
Alpha rays:
• It is also one of the forms of radioactive pollution.
 • The lowest level of radioactive pollution is alpha rays.
• Alpha rays can be blocked by our human skin, no need of any protection for this
type of radiation.
Beta rays:
• It is also one of the forms of radioactive pollution.
• It is the next level of radioactive pollution.
• Beta rays cannot be blocked by our human skin; it can penetrate through our skin,
so we should use some metals and glass materials for protection.
Gamma rays:
• It is the complex part of radioactive pollution.
• It is the highly dangerous level of radioactive pollution.
• Gamma rays cannot be blocked by any materials completely. We may try using
thick layers of concrete or high density layers of lead for protection.
• A small exposure to these rays may lead to even death and cause cancers.
If the radioactive pollution is not controlled properly, it will lead to drastic
effects in environment. Even a small amount of release of those materials will cause
serious threats. Radioactive Pollution should be controlled using preventive
techniques.
Global Warming

The process of increase in the level of green house gases in the atmosphere is the
global warming which is the major environmental issues. The temperature of the earth is
increased in the level of 0.60 C. The control of global warming are,
1) Reducing deforestation
2) Planting more trees
3) Slowing down the growth of green house gases into atmosphere
4) Improving the efficiency of energy usage
5) Cutting down use of fossil fuel
Ozone Depletion:
The ozone layer depletion is also the major environmental issue. The ozone is
formed in the upper part of the atmosphere is called the atmosphere. The thickness of
ozone in a column of air from the ground to the top of atmosphere is measured in terms
of Dob-son Units (DU). Ozone layer protects the living beings from harmful effects of
UV radiations. Ozone gas is formed by the action of UV rays on major molecular
oxygen. This depletion of ozone is marked over Antarctic region. From
chlorofluorocarbons active chlorine is separated in the presence of UV. This thinning of
the ozone layer is called ozone hole.
Green House Effect:
The process of keeping the earth warm due to presence of certain gases in
atmosphere is called as green house effect. Green house gases allow the solar radiations
to enter but prevent the escape of heat radiations of longer wave length. Such green
houses are used for growing tropical plants in temperate regions. Green house effect is
the major environmental issue in atmosphere. The incoming solar radiation is reflected by
the atmosphere by the atmospheric gases and clouds and only half of incoming solar
radiation falls on the earth’s surface heating it and only a small portion is reflected back.

Local air quality is significantly influenced by the rate of mixing of pollutants

which are emitted and issues such as wind speed and atmospheric stability. In general,
low wind speeds result in high pollutant concentrations and vice versa. If we imagine the
wind blowing across the top of a chimney emitting smoke at a constant rate, the volume
of air into which the smoke is emitted is directly proportional to the wind speed. The
concentration of smoke in the air is thus inversely proportional to the wind speed. The
concentration of pollutants in the hypothetical box of air into which the pollutants are
mixed is proportional to the emissions rate and inversely proportional to the wind speed.
The wind speed at groundlevel tends to drop overnight and rise again during the morning,
especially during cloud-free conditions. Of course, emissions also tend to drop overnight
fewer fires, boilers and furnaces are alight, fewer cars are on the roads. So some of the
highest pollution levels occur in the morning when emissions increase rapidly before the
wind speed picks up and dispersion conditions improve.
Atmospheric Stability:
In addition to wind direction, the extent of vertical mixing in the atmosphere also
affects pollutant concentrations. This is related to the stability of the atmosphere which is
dependent on many factors such as the time of day, the synoptic weather conditions, the
nature of the earth's surface, etc.
The Lapse Rate.
The roughness of the ground produces a certain amount of turbulence in the lowest
layer (boundary layer) of the atmosphere which promotes the mixing and dispersion of
pollutants.This effect increases with the scale of the surface roughness and is greater for a
city with large buildings than for open ground with few obstructions. However the major
factor affecting atmospheric stability and turbulence is thermal buoyancy. The pressure in
the atmosphere decreases exponentially with height. Ascending air expands as the
pressure decreases and as it expands it cools. A simple calculation based on the properties
of gases leads to the conclusion that we should expect a decrease in temperature with
height of 9.86 0 C km"1 or about 10 0 C for every 100 m of dry air. The variation of
temperature with height is called the lapse rate and the calculation for the ideal case leads
to what is known as the adiabatic lapse rate (a.l.r.).

Case (a). Temperature decreases with height more rapidly than the a.l.r., Figure 7a. Air
that is slightly warmer than its surroundings starts to rise and to cool at the a.l.r. The
temperature difference between the rising parcel of air and its surroundings increases
with height, thus the upward movement due to thermal buoyancy continues and is
magnified. The atmosphere is unstable. Upcurrents in one location are balanced by
downcurrents elsewhere and rapidvertical mixing of air occurs, promoting rapid
dispersion of pollutants.
Case (b). Temperature decreases with height less rapidly than the a.Lr. or actually
Increases with height, Figure 7b. Air that is slightly warmer than its surroundings starts to
rise and cool at the a.l.r. and the temperature difference between the rising parcel of air
and its surroundings soon decreases to zero. Upward movement due to thermal buoyancy
ceases.The atmosphere is stable since any vertical movement of air tends to be damped
out. Lower polluted layers stay near the ground and pollutant concentrations will be high.

Unstable situations occur with bright sunlight warming the ground to a temperature above
that of the air. The air adjacent to the ground is subsequently warmed and rises due to its
buoyancy. Such situations are common during daytime in summer, especially when the
wind speed is low. High wind speeds tend to lead to neutral conditions with the lapse
rate close to the adiabatic value (Figure 7c).
Temperature Inversion:
 Stable situations occur when the lowest layer of air is cooled by the ground
beneath. The most common cause is overnight radiative cooling of the ground which
often leads to low level temperature inversions on clear nights. The temperature profile,
in Figure 7c which may represent late afternoon, gradually changes into profile 7d
overnight. The effect is that ground level emissions become trapped in the stable
inversion layer which may not be more than 100-200 m deep. Emissions from tall
industrial chimneys however may be above the inversion layer and be vertically dispersed
by relatively good mixing conditions aloft. The following day the inversion layer is
gradually eroded by the warming effect of the sun until, by mid-morning, the temperature
profile has returned to that of neutral conditions (Figure 7c) and the trapped pollutants are
effectively released to be dispersed to higher levels.Another factor contributing to high
pollution levels during inversion conditions is the lowered wind speed. Since high level,
faster moving air does not mix with low level air, there is no mechanism for the
downward transport of momentum. The lowest level air therefore becomes stagnant, In
the low temperature conditions, dew, frost, or fog formation may occur. Fog adds to the
problem by slowing down the break-up of the overnight inversion layer because the sun's
energy is reflected by its upper surface and does not reach the ground. The ground
therefore stays cool rather than warming. In extreme cases fog may persist for several
days as happened in the London 1952 smog. Polluted fogs are more persistent than clean
fogs because the chemicals dissolved in the water droplets prevent complete evaporation
even when the relative humidity drops well below 100%.The other main type of inversion
occurs during anticyclonic conditions and is described as a subsidence inversion. Within
an anticyclone,air is diverging from a high pressure region and at the centre subsides
from a high level to lower levels of the atmosphere. As it subsides it progressively warms
with decreasing height resulting in the development of an elevated inversion layer as
illustrated in Figure 7e. Below the inversion layer the air may be neutral or even unstable
so that good mixing occurs but only up to the inversion height. Local urban pollution
Levels are rarely as great under such conditions as during ground level inversions.
However, subsidence inversions are often associated with warm, dry weather and they
provide the ideal conditions for a long range transport of pollution. Summer haze
conditions, in which the UK receives already polluted air from Europe before the addition
of our own emissions, can lead to particulate pollution levels as high as those on the most
polluted winter days. At the same time the levels of photo-chemical oxidants such as
ozone are also high as shown in Plate 3.In the discussion so far, no reference has been
made to the geographical situation in which air pollution levels are being considered.
Towns situated in valleys are particularly susceptible to pollution problems. Cool air will
tend to flow downhill into the valley so aggravating the problem of low level inversions.
Mixing between the air in the valley and the air above is reduced. Fogs will persist
longer. Often in winter, a layer of polluted air over the town with cleaner air above can be
clearly seen from the higher ground. Towns situated by the sea may be subject to sea
breezes. The proximity of relatively warm ground to the cool water surface results in a
circulation of air from sea to land. The sea breeze will be cooler than the overlying air,
another example of inversion conditions, so in polluted areas conditions will be worse
than for a corresponding inland site. Sea mists may blow inland aggravating the general
discomfort. Los Angeles is one example of a city whose geographical location
exaggerates pollution problems caused by high emissions. It is situated in a basin area
surrounded by large hills which inhibit mixing out of the city. Inversions are also
common due to the presence of subsidence conditions over the Pacific.

EFFECT OF SOLAR RADIATION ON POLLUTANTS

Photons of ultraviolet light provide a means of initiating chemical reactions which

would otherwise not take place. In addition to stable molecules, photochemical reactions
involve free radicals such as hydroxyl OH*, hydroperoxy HO*2 and methyl CH 3.
Free radicals are extremely reactive and have very short lifetimes. Their concentrations in
the atmosphere are small but none the less significant. For example, OH* concentrations
in polluted atmospheres may be in the range 106-107 radicals cm"3, i.e. one radical for
every 1013 nitrogen molecules.One of the most important overall processes we have to
describe is oxidation, that is, the combination of atmospheric oxygen with the primary
pollutants. For the three commonest inorganic pollutants the overall results are

For organic hydrocarbon species there may be a number of intermediate stable

molecules formed, but the overall process is rather like combustion with the end product
being carbon monoxide; for example
methane CH4 -> formaldehyde HCHO -> carbon monoxide
although the time taken to complete this process can be very long. In all these cases the
main species initiating the sequence of reactions is the hydroxyl radical:

In the case of nitric acid formation, there are no remaining free radicals to continue the
chain of reactions. In the other cases the hydroxyl radical is eventually regenerated but
only after several further steps which interlink the chemistries of the various species
(Table ). Carbonmonoxide oxidation is a slow process and the lifetime of CO in the
atmosphere is several years. The oxidation rate of SO2 can be around 1 % h ~l resulting in
an overall lifetime of a few days. Radicals other than OH* such as HO2, CH3O2, or
other hydrocarbon peroxy radicals will also attack SO2 but at a slower rate and their
contribution to the overall oxidation is thought to be relatively small.

Chemical reactions for the atmospheric oxidation of CO, SO2, CH4

Formation of physical processes of pollutants in the atmosphere

Acid Rain:

Rainwater Composition. Even in the absence of air pollutants,rain-water is lightly

acidic (pH 5.6) due to atmospheric carbon dioxide.'Acid rain' therefore refers to rain with
a pH below about 5. The acid has been partially neutralized by ammonia and other ions
such as Ca2+ which may have originated as calcium carbonate, CaCO3. The sulfate
contribution to the acidity is larger than that of nitrate but the last decade has seen a
progressive increase in the relative importance of nitrate due to the greater reductions in
SO2 emissions than NOx emissions. This trend is expected to continue.

Effects:
Three particular effects have received most attention.
 The first of these was the increased acidification of lakes and streams, leading to
the loss of fish and other aquatic organisms. This was attributed to the acidity of
rain polluted by sulfur and nitrogen oxides.
 The second type of environmental damage is damage to forests.
• The effect of ozone initiating an attack on cell walls, with subsequent
deterioration being due to acid rain or acid mists and fogs. leaching
nutrients and resulting in the breakdown of chlorophyll. Reduced root
growth and nutrient uptake follow.

• Acidification of the ground with consequent effects on the soil chemistry

including elevation of mobile aluminum levels which can damage the
roots.

• Excess deposition of nitrogen (as nitrate and ammonium) which can have
a variety of effects. In the ground NH4" can release H+ during the process
of being oxidized to NO3" by bacteria. The H+ can then be leached out.
From the point of view of acidification phenomena, ammonia should
therefore not be regarded as an ally even though, prior to its
transformation to nitrate, it reduces the rain-water acidity.

 The third problem associated with acid rain is the attack on

stonework and the decay of famous cathedrals and other
buildings constructed of limestone. Both wet and dry depositions of sulfur dioxide
are involved. Under moist conditions SO2 or sulfuric acid will convert calcium
carbonate to gypsum, CaSO4.2H2O. Since the sulfate is more soluble than the
carbonate, the reacted stone can be removed by dissolution. The solid gypsum
also occupies a larger volume than the original carbonate and this leads to spalling
of material from the surface.

ACID DEPOSITION:
Liquid water occurs in the atmosphere as clouds, mists, and fog within which the
concentration of water can be up to 1 g m~3. Water droplets can accumulate pollutants by
adsorption of either gases or particles and within the droplets chemical reactions can
proceed, changing the nature of the adsorbed species. Solution of SO 2 into water results
in a mixture of the species SO23" (sulfite), HSO-3 (bisulfite) and H2SO3 (undissociated
sulfurous acid) depending on the pH.

In the case of nitrogen oxides the routes for nitrate formation in clouds are
dissolution of nitrate-containing particles into droplets by absorption of nitrogen oxides
or nitrous acid, HONO, into droplets followed by oxidation of nitrite ions NO-2by
oxidants such as H2O2.

Dry Deposition of Gases:

The life cycle of an air pollutant normally involves emission, dispersion and
transport, chemical transformation and finally deposition to the ground. Experimentally
we can measure the concentration of the pollutant and the total rate of deposition. The
higher the ground level concentration, the more rapid the dry deposition but the ratios of
these two quantities give a useful measure of the efficiency of the deposition process. It is
called the deposition velocity.

Different surfaces (water, soil, ice, etc.) will have correspondingly different deposition
velocities.
Wet Deposition:
The term 'wet deposition' is used to describe pollutants brought to ground either
by rainfall or by snow. This mechanism can be further subdivided depending on the point
at which the pollutant was absorbed into the water droplets. In-cloud absorption followed
by precipitation is termed 'rain-out'; below cloud absorption, i.e. pollutants collected as
the raindrops fall, are termed 'wash-out'. The rate of removal of a pollutant by wash-out
will increase in proportion to the rainfall rate.

Effect of gravitational force on pollutants

The mechanism of deposition of particles depends on the particle size. Large

particles with diameter greater than 10µm fall slowly by gravitational settlement. The
larger the particles, the more rapidly they fall. The sedimentation velocities for particles
of density 2 g cm3are as follows:

Particles larger than 150 jam diameter, falling at over 1 ms-1, remain airborne for
such a short time that they do not need to concern us as air pollutants. Particles less than
5µm have sedimentation velocities which are so low that their movement is determined
by the natural turbulence of the air, just as for gases. Intermediate particles, between 1
and 10µm diameter, can be removed by impaction onto leaves and other obstacles.
Particles in the 0.1 to 1µm range, which include most of the nitrates and sulfates, are only
removed very slowly by dry deposition. The deposition velocities are of the order of 1
mms-1, much lower than for SO2. The most likely route for their removal is rain-out
following water vapour condensation and droplet growth in clouds. Wash-out is not very
efficient for these fine particles although it becomes more significant for larger particles
such as coarse dust.
Scrubbers:
A venturi scrubber passes gas through a converging section, throat, and diverging
section as shown in Figure. Injection of the scrubbing liquid at right angles to incoming
gas breaks the liquid into very small droplets, which are ideal for scavenging particles
from the gas stream. In the reduced-pressure (expanding) region of the venturi, some
condensation can occur, adding to the scrubbing efficiency. In addition to removing
particles, venturis can serve as quenchers to cool exhaust gas and as scrubbers for ollutant
gases.

NITROGEN OXIDES IN THE ATMOSPHERE

The three oxides of nitrogen normally encountered in the atmosphere are nitrous
oxide (N2O), nitric oxide (NO), and nitrogen dioxide (NO2). Microbially generated
nitrous oxide is relatively unreactive and does not significantly influence important
chemical reactions in the lower atmosphere. Its levels decrease rapidly with altitude in the
stratosphere due to the photochemical reaction.

and some reaction with singlet atomic oxygen:

These reactions are significant in terms of depletion of the ozone layer. Increased global
fixation of nitrogen, accompanied by increased microbial production of N2O,could
contribute to ozone layer depletion.Colorless, odorless nitric oxide (NO) and pungent
red-brown nitrogen dioxide(NO2) are very important in polluted air. Collectively
designated NOx, these gases enter the atmosphere from natural sources, such as lightning
and biological processes,and from pollutant sources. The latter are much more significant
because of regionally high NO2 concentrations, which can cause severe air quality
deterioration. Practically all anthropogenic NO2 enters the atmosphere as a result of the
combustion of fossil fuels in both stationary and mobile sources. At the very high
temperatures in an automobile combustion chamber, the following reaction occurs
High temperatures favor both a high equilibrium concentration
and a rapid rate of formation of NO.

Atmospheric Reactions of NOx:

Atmospheric chemical reactions convert NOx to nitric acid, inorganic nitrate salts,
organic nitrates, and peroxyacetyl nitrate.The principal reactive nitrogen oxide species in
the troposphere are NO, NO2, and HNO3. These species cycle among each other, as
shown in Figure 15.9. Although NO is the primary form in which NOx is released to the
atmosphere, the conversion of NO to NO2 is relatively rapid in the troposphere.

Nitrogen dioxide is a very reactive and significant species in the atmosphere. It

absorbs light throughout the ultraviolet and visible spectrum penetrating the troposphere.
At wavelengths below 398 nm, photodissociation to oxygen atoms occurs,

giving rise to several significant inorganic reactions, in addition to a host of atmospheric

reactions involving organic species. The reactivity of NO2 to photo dissociation is shown
clearly by the fact that in direct sunlight the half-life of NO2 is much shorter than that of
any other atmospheric component (only 1 or 2 minutes).

Oxidizing properties of air pollutants

The formation of OH is the initiator of radical chain oxidation. Photolysis of

Though atmospheric composition is dominated by both oxygen and nitrogen, it is not the
amount of oxygen that defines the capacity of the troposphere to oxidise a trace gas. The
total atmospheric burden of O3, OH and H2O2 determines the oxidizing capacity of the
atmosphere. As a result of the multiple interactions among the three oxidants and the
multiphase activity of H2O2, there is no single expression that defines the earth’s
oxidizing capacity.
Ozone by UV light in the presence of water vapour is the main source of hydroxyl
radicals in the troposphere. Two important features of OH chemistry make it critical to
the chemistry of the troposphere. The first is its inherent reactivity; the second is its
relatively high concentration given its high reactivity. The main fate for the hydroxyl
radical is reaction with either carbonmonoxide or methane to produce peroxy radicals
such as HO2 and CH3O2, viz

In low-NOx conditions, HO2 can react with ozone leading to further destruction
ozone in a chain sequence involving production of hydroxyl radicals.

Alternatively, it can recombine to form hydrogen peroxide

or react with organic peroxy radicals such as CH3O2 to form organic hydro peroxides,

In more polluted conditions (high-NOx), peroxy radicals catalyse the oxidation of NO to

NO2

Hydroxyl radicals produced can go on to form more peroxy radicals

The resulting methoxy radical reacts rapidly with O2 to form formaldehyde and HO2.
The oxidation of methane is summarized schematically in fig