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AIR POLLUTION MANAGEMENT

Unit : 1
Definition:
Air pollution may be defined as the presence in the air (outdoor atmosphere) of one
or more contaminants or combinations thereof in such quantities and of such durations as
may be or tend to be injurious to human, animal or plant life, or property, or which
unreasonably interferes with the comfortable enjoyment of life or property or conduct of
business. Air pollution is any atmospheric condition in which certain substances are
present in such concentrations that they can produce undesirable effects on man and his
environment.
Substances like gases, radioactive materials and many others,
a) Example for gases substances like sulphur oxides, nitrogen oxides, carbon
monoxide, hydrocarbons etc.,
b) Example for particulate matter like smoke, dust, fumes, aerosols.

Most of these substances are naturally present in the atmosphere in low
(background) concentration and usually considered to be harmless.
Particulate substance can be considered an air pollutant only. When its
concentration is relatively high compared with the background value and causes
adverse effects.

For e.g. sulphur dioxide, if present in the atmosphere in concentration greater than
the background value of 2x10
-4
ppm and cause measurable effects on humans,
animals, plants or property, then only it is clarified as a air pollutant.


Classification of air pollutants:
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The variety of matter emitted into the atmosphere by natural and anthropogenic
sources. Its classified into two categories,

a) Primary pollutants
b) Secondary pollutants

a) Primary pollutants:

Those that are emitted directly from the sources. Typically pollutants included under
this category,
Particulate matter for eg, ash, smoke, dust, fumes, mist and spray.
Inorganic gases such as sulphur dioxide, hydrogen sulphide, nitric
oxide, ammonia, carbon monoxide, carbon dioxide and hydrogen
fluoride, olefinic and aromatic hydrocarbons.
Radioactive compounds.

b) Secondary pollutants:

Those that are formed in the atmosphere by chemical interactions.
Among primary pollutants and normal atmospheric constituents.
Secondary pollutants such as ,

Sulphur trioxide, Nitrogen dioxide, PAN (peroxyacetyl nitrate), Ozone,
Aldehydes, Ketones, and various Sulphate and Nitrate salts are
included in this category.





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Particulate Matter and Gaseous Pollutants:

Particulate Matter:

In general the term particulate refers to all atmospheric substances that are not
gases. They can be suspended droplets or solid particles or mixtures of the two.
Particulates can be composed of inert or extremely reactive materials ranging in size from
100 m down to 0.1m and less. The inert materials do not react readily with the
environment not do they exhibit any morphological changes as a result of combustion or
any other process, Where as the reactive materials could be further oxidized or may react
chemically with the environment.

The classification of various particulates may be made as follows;

Dust :
It contains particles of the size ranging from 1 to 200m. These are formed by
natural disintegration of rock and soil or by the mechanical processes of grinding and
spraying.
They have large settling velocities and are removed from the air by gravity and
other inertial process Fine dust particles at act as centers of catalysis for many of the
chemical reactions taking place in the atmosphere.

Smoke :
It contains fine particles of the size ranging from 0.01 to 1 m which can be
liquid or solid, and are formed by combustion or other chemical process. smoke may
have different colours depending on the nature of materials burnt.

Fumes:
There are solid particles of the size ranging from 0.1 to 1m and are normally
released from chemical or metallurgical processes.

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Mist:
It is made up of liquid droplets generally smaller than 10m which are
formed by condensation in the atmosphere or are released from industrial
operations.

Fog:
It is the mist in which the liquid is water and is sufficiently dense to obscure
vision.

Aerosols:

In this category are included all air borne suspensions ether solid or liquid,
these are generally smaller than 1 m.

Particles in the size range 1 to 10m have measureable settling velocities but
are readily stirred by air movements, whereas particles size 0.1 1 m have small
settling velocities. These below 0.1m, a submicroscopic size found in urban air,
undergo random Brownian motion resulting from collisions among individual
molecules.


Fig 2.1 compares the size of atmospheric particulates from various sources.
Most particulates in urban air have sizes in the range 0.1- 10m. The finest and the
smallest particles are the ones which cause significant damage to health.



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Virus




(Aitken


Tobacco




Deposition In


carbon
Oil


Sea

Combustion nuclel

Nucles)
Condensation


Smoke




respiratory
Mist, fog,

Black
smoke


Salt nuclel



(Large
Nuclel


Coal
Fly

Cement

track
cloud

insecticide

Bacteria





Particles)


Dust
Ash
Pollen
Dust


droplets

dust
0.001 0.01 0.1 1.0 10 100





Fig 1.1. Sizes of Atmospheric particulate matter.
SMOG
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Gaseous pollutants:

Of all the different types of particulates in the atmosphere, the presence of trace
elements such as cadmium, lead, nickel and mercury may constitute the greatest health
hazard. Many of the trace metals are toxic and are concentrated in the finest of particulate
matter in a variety of combined forms such as oxides, hydroxides, sulphates and nitrates.

Oxides of Sulphur:

i) The most important oxide emitted by pollution sources is sulphur dioxide
(So2).
ii) So2 is a colourless gas with characteristics, sharp, pungent odour.
iii) It is moderately soluble in water (11.3 g/100ml) forming weakly acidic
sulphurous acid (H2So3).
iv) In a polluted atmosphere, So2 reacts photochemically or catalytically with
other pollutants or normal atmospheric constituents to form sulphur
trioxide, sulphuric acid and salts of sulphuric acid.
v) Sulphur trioxide (S02) is generally emitted along with S02, at about 1 5
percent of the S02 concentration.So3 rapidly combines with moisture in the
atmosphere to form sulphuric acid which has a low dew point.
vi) Both S02 and S03 are relatively quickly washed out of the atmosphere by rain
or settle out as aerosols.

Nitrogen oxides:

i) Of the six or seven oxides of Nitrogen, only three Nitrous oxide (N2O), Nitric
oxide (NO), and Nitrogen dioxide (NO2) are formed in any appreciable
quantities in the atmosphere.
ii) Often NO and NO2 are analysed together in air and are referred to as NOx.
iii) Nitric oxide is a colourless, odourlessgas produced largely by fuel
combustion. It is oxidized to NO2 in a polluted atmosphere through
photochemical secondary reactions.
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iv) Nitrogen dioxide is a brown pungent gas with an irritating odour which can
be detected at concentrations of about 0.12ppm.
v) It absorbs sunlight and initiates a series of photochemical reactions.
vi) NO2 is probably produced by the oxidation of NO by ozone. Nitrogen dioxide
is of major conern as a pollutant.It is emitted by fuel combustion and Nitric
acid plants.

Carbon monoxide:

i) It constitutes the single largest pollutant in the urban atmosphere.
ii) CO is colourless, odourless and tasteless and has a birling point of 192c.
iii) It has a strong affinity towards the hemoglobin of the bloodstream and is a
dangerous asphysciant.
iv) Carbon monoxide is present in small concentrations (0.1 ppm) in the natural
atmosphere and has a residence time of about six months.
v) The main sources of CO in the urban air smoke and exhaust fumes of many
devices burning coal, gas or oil.

Hydrocarbons:

i) The gaseous and volatile liquid hydrocarbons are of particular interest as air
pollutants.
ii) In the saturated class methane is by far the most abundant hydrocarbons
present in an urban atmosphere.
iii) The hydrocarbons in air by themselves alone cause no harmful effects. They
are of concern because the hydrocarbons undergo chemical reactions in the
presence of sunlight and nitrogen oxides forming photochemical oxidants of
which the predominant one is ozone.
iv) Methane has very low photochemical activity as compared to that of other
hydrocarbons. For this reason, it is the non- methane hydrocarbon
concentration that is of interest while considering air pollution.

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Sources of Air pollution
Sources of air pollution refer to the various locations, activities or factors which are
responsible for the releasing of pollutants into the atmosphere. These sources can be
classified into two major categories which are:
Anthropogenic sources (human activity) mostly related to burning different kinds of fuel
"Stationary Sources" include smoke stacks of power plants, manufacturing
facilities (factories) and waste incinerators, as well as furnaces and other types
of fuel-burning heating devices
"Mobile Sources" include motor vehicles, marine vessels, aircraft and the effect
of sound etc.
Chemicals, dust and controlled burn practices in agriculture and forestry
management. Controlled or prescribed burning is a technique sometimes used in
forest management, farming, prairie restoration or greenhouse gas abatement.
Fire is a natural part of both forest and grassland ecology and controlled fire can
be a tool for foresters. Controlled burning stimulates the germination of some
desirable forest trees, thus renewing the forest.
Fumes from paint, hair spray, varnish, aerosol sprays and other solvents
Waste deposition in landfills, which generate methane. Methane is not toxic;
however, it is highly flammable and may form explosive mixtures with air.
Methane is also an asphyxiant and may displace oxygen in an enclosed space.
Asphyxia or suffocation may result if the oxygen concentration is reduced to
below 19.5% by displacement
Military, such as nuclear weapons, toxic gases, germ warfare and rocketry
Natural sources:
Dust from natural sources, usually large areas of land with little or no vegetation
Methane, emitted by the digestion of food by animals, for example cattle
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Radon gas from radioactive decay within the Earth's crust. Radon is a colorless,
odorless, naturally occurring, radioactive noble gas that is formed from the decay of
radium. It is considered to be a health hazard. Radon gas from natural sources can
accumulate in buildings, especially in confined areas such as the basement and it is
the second most frequent cause of lung cancer, after cigarette smoking
Smoke and carbon monoxide from wildfires
Vegetation, in some regions, emits environmentally significant amounts of VOCs on
warmer days. These VOCs react with primary anthropogenic pollutants
specifically, NOx, SO2, and anthropogenic organic carbon compoundsto produce a
seasonal haze of secondary pollutants.
[6]

Volcanic activity, which produce sulfur, chlorine, and ash particulates
Emission inventory
An emission inventory is an accounting of the amount of pollutants discharged into
the atmosphere. An emission inventory usually contains the total emissions for one or
more specific greenhouse gases or air pollutants, originating from all source categories in a
certain geographical area and within a specified time span, usually a specific year.
An emission inventory is generally characterized by the following aspects:
Why: The types of activities that cause emissions,
What: The chemical or physical identity of the pollutants included,
Where: The geographic area covered,
When: The time period over which emissions are estimated,
How: The methodology to use.
Emission inventories are compiled for both scientific applications and for use in policy
processes.


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Effects of air pollution;

The pollutants are to overwhelm the natural scavenging ability of the atmosphere.
As a result, the concentrations of the pollutants persist at levels which are much higher
than the allowable background levels.

This is particularly true for urban and other industrial regions where the pollutants
adversely affect the health of humans and animals and cause plant and material damage.

Effects of Human Health:

Adverse effects of air pollution may be divided into two classes
i) Acute effects
ii) Chronic effects
Acute effects manifest themselves immediately upon short term exposure to air
pollutants at high concentrations, and chronic effects become evident only after continuous
exposure to low levels of air pollution.

Epidemiological studies are statistical surveys on the effects of air pollution on
human populations under natural conditions. Such studies are extremely important, but
due to the multiplicity of unknown factors it is not possible to establish a cause effect
relationship.

Toxicological studies are conducted in the laboratory under controlled conditions.
The effect of several variables such as pollutants concentration, exposure duration,
temperature, humidity, etc., can be experimentally studied.

Even though there experimental studies can clearly demonstrate a direct cause
effect relationship between certain pollutants and sickness or death, their relevance to
natural setting is sometimes questionable.

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Respiratory Effects:

Pollutants may enter the body by a number of ways. They can cause eye and skin
irritation. Certain particulates may be swallowed asa result of internal respiratory cleaning
action or certain pollutants could even be ingested. But the primary mode of pollutant
transfer into the human body is through the respiratory system.

The respiratory systemic composed primary of two lungs and the air passages
which lead to them. The air passages begin at the nose and mouth, and include windpipe
(trachea) and its two branches known as bronchi.

Particulate matter inhaled may be deposited in various regions of the respiratory
system depending on particle size. Particle above 10m are almost wholly retained in the
nose.

The health risk is primarily from the deposition of the particles smaller than 0.5m
in the alveoli where they cause damage to the respiratory organs.

Air pollution effects on Vegetation

The most obvious damage caused by air pollutants to pollutants to vegetation
occurs in the leaf structure. The surface of a leaf is covered by a waxy layer known as the
cuticle.

Its chief functions are the protection of the inner tissues from excessive moisture
loss and the admission of carbon dioxide and oxygen to these internal tissues. The leaf
surface is penetrated by a large number of openings called the stomatas.

The damage caused by air pollutants is of several types like necrosis, chlorosis and
epinasty. The dead areas on a leaf structures are referred to as necrosis. Chlorosis is the
loss or reduction of chlorophyll and lead to the yellowing of the leaf.
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Epinasty is a downward curvature of the leaf due to higher rate of growth on the
upper surface, and the dropping of leaves called abscission. Few plant species are spared
damage on exposure to one or more of the principle air pollutants.

In general, the pollutants enter the inner tissue through the stomata, where they
destroy the chlorophyll and disrupt photosynthesis. The adverse effects range from
reduction in growth rate to death of the plant. The effect of particulates on vegetation is not
well known. However, some specific dusts have been observed to cause damage.

Cement dust deposited on leaves, on combination with mist or light rain, forms
incrustation. Plugging of stomata may occur, resulting in plant damage.

Chemicals such as arsenic and fluorides when deposited on the leaves can poison
animals.

Effects of Air pollution on materials

The damage caused by atmospheric pollutants to materials is a well known
phenomenon. Particulates such as soot, dust and fumes soil painted surface, fabrics and
buildings, and because of their abrasive nature, particulates can cause damage to exposed
surface when they are driven by wind at high velocities. Through their own corrosiveness
or in the presence of SO2 and moisture, they can accelerate the corrosion of steel, copper,
zinc and other metals.

The most notorious pollutant responsible for metallic corrosion is sulphur dioxide.
It has been reported that corrosion of hard metals such as steel begins at annual mean
concentrations of 0.02ppm (52g /m3).

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SO2 is readily absorbed by leather and causes its disintegration. Paper is also
discolored by SO2 and becomes brittle and fragile. Sulphuric acid mist in the atmosphere
causes deterioration of structural materials such as marble and limestone.

Ozone is a very reactive substance. Much of the degradation of materials, such as
fabrics and rubber, now attributed to weathering is caused primarily by ozone.

The fading of fibers and the cracking of rubber are attributed to ozones oxidizing
ability. Nitrogen oxides, although less widely published them ozone, are known to cause
fading in acetate, cotton and rayon fibers at levels of 0.6 -2 ppm over 2 3 month period. It
has been observed that particulate Nitrates attack and damage nickel brass alloys in the
presence of moisture.

Global warming
Global warming refers to the rising average temperature of Earth's atmosphere and
oceans and its projected continuation. In the last 100 years, Earth's average surface
temperature increased by about 0.8 C (1.4 F) with about two thirds of the increase
occurring over just the last three decades. Warming of the climate system is unequivocal,
and scientists are more than 90% certain most of it is caused by increasing concentrations
of greenhouse gases produced by human activities such as deforestation and burning fossil
fuels. These findings are recognized by the national science academies of all the major
industrialized countries.
Climate model projections are summarized in the 2007 Fourth Assessment Report
(AR4) by the Intergovernmental Panel on Climate Change (IPCC). They indicate that during
the 21st century the global surface temperature is likely to rise a further 1.1 to 2.9 C (2 to
5.2 F) for their lowest emissions scenario and 2.4 to 6.4 C (4.3 to 11.5 F) for their
highest. The ranges of these estimates arise from the use of models with differing
sensitivity to greenhouse gas concentrations.
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An increase in global temperature will cause sea levels to rise and will change the
amount and pattern of precipitation, and a probable expansion of subtropical deserts.
Warming is expected to be strongest in the Arctic and would be associated with continuing
retreat of glaciers, permafrost and sea ice. Other likely effects of the warming include more
frequent occurrence of extreme weather events including heat waves, droughts and heavy
rainfall events, species extinctions due to shifting temperature regimes, and changes in
agricultural yields. Warming and related changes will vary from region to region around
the globe, with projections being more robust in some areas than others.
[12]
In a 4 C world,
the limits for human adaptation are likely to be exceeded in many parts of the world, while
the limits for adaptation for natural systems would largely be exceeded throughout the
world. Hence, the ecosystem services upon which human livelihoods depend would not be
preserved.
Initial causes of temperature changes (external forcings)


Greenhouse effect schematic showing energy flows between space, the atmosphere,
and earth's surface. Energy exchanges are expressed in watts per square meter (W/m
2
).

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This graph, known as the "Keeling Curve", shows the long-term increase of
atmospheric carbon dioxide (CO2) concentrations from 19582008. Monthly CO2
measurements display seasonal oscillations in an upward trend; each year's maximum
occurs during the Northern Hemisphere's late spring, and declines during its growing
season as plants remove some atmospheric CO2.
External forcing refers to processes external to the climate system (though not
necessarily external to Earth) that influence climate. Climate responds to several types of
external forcing, such as radioactive forcing due to changes in atmospheric composition
(mainly greenhouse gas concentrations), changes in solar luminosity, volcanic eruptions,
and variations in Earth's orbit around the Sun. Attribution of recent climate change focuses
on the first three types of forcing. Orbital cycles vary slowly over tens of thousands of years
and at present are in an overall cooling trend which would be expected to lead towards an
ice age, but the 20th century instrumental temperature record shows a sudden rise in
global temperatures.
Mitigation
Reducing the amount of future climate change is called mitigation of climate change.
The IPCC defines mitigation as activities that reduce greenhouse gas (GHG) emissions, or
enhance the capacity of carbon sinks to absorb GHGs from the atmosphere. Many countries,
both developing and developed, are aiming to use cleaner, less polluting, technologies.
:192

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Use of these technologies aids mitigation and could result in substantial reductions in CO2
emissions. Policies include targets for emissions reductions, increased use of renewable
energy, and increased energy efficiency. Studies indicate substantial potential for future
reductions in emissions.
To limit warming to the lower range in the overall IPCC's "Summary Report for
Policymakers" means adopting policies that will limit emissions to one of the significantly
different scenarios described in the full report. This will become more and more difficult,
since each year of high emissions will require even more drastic measures in later years to
stabilize at a desired atmospheric concentration of greenhouse gases, and energy-related
carbon-dioxide (CO2) emissions in 2010 were the highest in history, breaking the prior
record set in 2008.
Since even in the most optimistic scenario, fossil fuels are going to be used for years
to come, mitigation may also involve carbon capture and storage, a process that traps CO2
produced by factories and gas or coal power stations and then stores it, usually
underground

Ozone depletion


Image of the largest Antarctic ozone hole ever recorded (September 2006), over the
Southern pole
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Ozone depletion describes two distinct but related phenomena observed since the
late 1970s: a steady decline of about 4% per decade in the total volume of ozone in Earth's
stratosphere (the ozone layer), and a much larger springtime decrease in stratospheric
ozone over Earth's Polar Regions. The latter phenomenon is referred to as the ozone hole.
In addition to these well-known stratospheric phenomena, there are also springtime polar
troposphere ozone depletion events.
The details of polar ozone hole formation differ from that of mid-latitude thinning,
but the most important process in both is catalytic destruction of ozone by atomic
halogens.
[1]
The main source of these halogen atoms in the stratosphere is photo
dissociation of man-made halocarbon refrigerants (CFCs, freons, halons). These
compounds are transported into the stratosphere after being emitted at the surface.
[2]

Both types of ozone depletion were observed to increase as emissions of halo-carbons
increased.
CFCs and other contributory substances are referred to as ozone-depleting
substances (ODS). Since the ozone layer prevents most harmful UVB wavelengths (280
315 nm) of ultraviolet light (UV light) from passing through the Earth's atmosphere,
observed and projected decreases in ozone have generated worldwide concern leading to
adoption of the Montreal Protocol that bans the production of CFCs, halons, and other
ozone-depleting chemicals such as carbon tetrachloride and trichloroethane. It is suspected
that a variety of biological consequences such as increases in skin cancer, cataracts, damage
to plants, and reduction of plankton populations in the ocean's photic zone may result from
the increased UV exposure due to ozone depletion.

Ozone cycle overview
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The ozone cycle Three forms (or allotropes) of oxygen are involved in the ozone-
oxygen cycle: oxygen atoms (O or atomic oxygen), oxygen gas (O2 or diatomic oxygen), and
ozone gas (O3 or diatomic oxygen). Ozone is formed in the stratosphere when oxygen
molecules photo dissociate after absorbing an ultraviolet photon whose wavelength is
shorter than 240 nm. This converts a single O2 into two atomic oxygen ions. The atomic
oxygen ions then combine with separate O2 molecules to create two O3 molecules. These
ozone molecules absorb UV light between 310 and 200 nm, following which ozone splits
into a molecule of O2 and an oxygen atom. The oxygen atom then joins up with an oxygen
molecule to regenerate ozone. This is a continuing process which terminates when an
oxygen atom "recombines" with an ozone molecule to make two O2 molecules.
O + O3 2 O2 chemical equation
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Global monthly average total ozone amount.

Layers of the atmosphere (not to scale)
The overall amount of ozone in the stratosphere is determined by a balance
between photochemical production and recombination.
Ozone can be destroyed by a number of free radical catalysts, the most important of
which are the hydroxyl radical (OH), the nitric oxide radical (NO), the atomic chlorine ion
(Cl) and the atomic bromine ion (Br). All of these have both natural and man-made
sources; at the present time, most of the OH and NO in the stratosphere is of natural
origin, but human activity has dramatically increased the levels of chlorine and bromine.
These elements are found in certain stable organic compounds, especially
chlorofluorocarbons (CFCs), which may find their way to the stratosphere without being
destroyed in the troposphere due to their low reactivity. Once in the stratosphere, the Cl
and Br atoms are liberated from the parent compounds by the action of ultraviolet light, e.g.
CFCl3 + electromagnetic radiation CFCl2 + Cl
The Cl and Br atoms can then destroy ozone molecules through a variety of catalytic
cycles. In the simplest example of such a cycle, a chlorine atom reacts with an ozone
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molecule, taking an oxygen atom with it (forming ClO) and leaving a normal oxygen
molecule. The chlorine monoxide (i.e., the ClO) can react with a second molecule of ozone
(i.e., O3) to yield another chlorine atom and two molecules of oxygen. The chemical
shorthand for these gas-phase reactions is:
Cl + O3 ClO + O2 The chlorine atom changes an ozone molecule to ordinary
oxygen
ClO + O3 Cl + 2 O2 The ClO from the previous reaction destroys a second ozone
molecule and recreates the original chlorine atom, which can repeat the first
reaction and continue to destroy ozone
The overall effect is a decrease in the amount of ozone. More complicated mechanisms have
been discovered that lead to ozone destruction in the lower stratosphere as well.
Atmosphere by chlorofluorocarbons (CFCs) yearly demonstrates how dangerous CFCs are
to the environment.


Lowest value of ozone measured by TOMS each year in the ozone hole.
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Reductions of up to 70% in the ozone column observed in the austral (southern
hemispheric) spring over Antarctica and first reported in 1985 (Farman et al. 1985) are
continuing. Through the 1990s, total column ozone in September and October have
continued to be 4050% lower than pre-ozone-hole values. In the Arctic the amount lost is
more variable year-to-year than in the Antarctic. The greatest declines, up to 30%, are in
the winter and spring, when the stratosphere is colder.
Reactions that take place on polar stratospheric clouds (PSCs) play an important
role in enhancing ozone depletion. PSCs form more readily in the extreme cold of Antarctic
stratosphere. This is why ozone holes first formed, and are deeper, over Antarctica. Early
models failed to take PSCs into account and predicted a gradual global depletion, which is
why the sudden Antarctic ozone hole was such a surprise to many scientists.
The ozone hole and its causes


Ozone hole in North America during 1984 (abnormally warm reducing ozone
depletion) and 1997 (abnormally cold resulting in increased seasonal depletion). Source:
NASA
The Antarctic ozone hole is an area of the Antarctic stratosphere in which the recent
ozone levels have dropped to as low as 33% of their pre-1975 values. The ozone hole
occurs during the Antarctic spring, from September to early December, as strong westerly
winds start to circulate around the continent and create an atmospheric container. Within
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this polar vortex, over 50% of the lower stratospheric ozone is destroyed during the
Antarctic spring.
As explained above, the primary cause of ozone depletion is the presence of
chlorine-containing source gases (primarily CFCs and related halocarbons). In the presence
of UV light, these gases dissociate, releasing chlorine atoms, which then go on to catalyze
ozone destruction. The Cl-catalyzed ozone depletion can take place in the gas phase, but it
is dramatically enhanced in the presence of polar stratospheric clouds (PSCs).
These polar stratospheric clouds(PSC) form during winter, in the extreme cold.
Polar winters are dark, consisting of 3 months without solar radiation (sunlight). The lack
of sunlight contributes to a decrease in temperature and the polar vortex traps and chills
air. Temperatures hover around or below 80 C. These low temperatures form cloud
particles. There are three types of PSC clouds; nitric acid trihydrate clouds, slowly cooling
water-ice clouds, and rapid cooling water-ice(nacerous) clouds; that provide surfaces for
chemical reactions that lead to ozone destruction.
[17]

The photochemical processes involved are complex but well understood. The key
observation is that, ordinarily, most of the chlorine in the stratosphere resides in stable
"reservoir" compounds, primarily hydrochloric acid (HCl) and chlorine nitrate (ClONO2).
During the Antarctic winter and spring, however, reactions on the surface of the polar
stratospheric cloud particles convert these "reservoir" compounds into reactive free
radicals (Cl and ClO). The clouds can also remove NO2 from the atmosphere by converting it
to nitric acid, which prevents the newly formed ClO from being converted back into
ClONO2.
The role of sunlight in ozone depletion is the reason why the Antarctic ozone
depletion is greatest during spring. During winter, even though PSCs are at their most
abundant, there is no light over the pole to drive the chemical reactions. During the spring,
however, the sun comes out, providing energy to drive photochemical reactions, and melt
the polar stratospheric clouds, releasing the trapped compounds. Warming temperatures
near the end of spring break up the vortex around mid-December. As warm, ozone-rich air
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flows in from lower latitudes, the PSCs are destroyed, the ozone depletion process shuts
down, and the ozone hole closes.
Most of the ozone that is destroyed is in the lower stratosphere, in contrast to the much
smaller ozone depletion through homogeneous gas phase reactions, which occurs primarily
in the upper stratosphere.
Effects on non-human animals
A November 2010 report by scientists at the Institute of Zoology in London found
that whales off the coast of California have shown a sharp rise in sun damage, and these
scientists "fear that the thinning ozone layer is to blame"
The study photographed and took skin biopsies from over 150 whales in the Gulf of
California and found "widespread evidence of epidermal damage commonly associated
with acute and severe sunburn," having cells which form when the DNA is damaged by UV
radiation. The findings suggest "rising UV levels as a result of ozone depletion are to blame
for the observed skin damage, in the same way that human skin cancer rates have been on
the increase in recent decades."
Effects on crops
An increase of UV radiation would be expected to affect crops. A number of
economically important species of plants, such as rice, depend on cyanobacteria residing on
their roots for the retention of nitrogen. Cyanobacteria are sensitive to UV light and would
be affected by its increase.
Sampling and analysis
Sampling is an important component of any piece of research because of the
significant impact that it can have on the quality of your results (or findings). If you are new
to sampling, there are a number of key terms and basic principles that act as a foundation
to the subject. This article explains these key terms and basic principles. Rather than a
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comprehensive look at sampling, the article presents the sampling basics that you would
need to know if you were an undergraduate or masters level student about to perform a
dissertation (or similar piece of research).
Principles of Sampling and Analysis
The components of an air pollution monitoring system include the collection or
sampling of pollutants both from the ambient air and from specific sources, the analysis or
measurement of the pollutant concentrations, and the reporting and use of the information
collected. Emissions data collected from point sources are used to determine compliance
with air pollution regulations, determine the effectiveness of air pollution control
technology, evaluate production efficiencies, and support scientific research.
The EPA Office of Research and Development (ORD) has developed Federal
Reference Methods (FRMs) and Federal Equivalent Methods (FEMs) for sampling and
analysis of pollutants in the ambient air and from emissions sources. As technology
changes, EPA updates and revises these methods. FRMs and FEMs can be either manual or
automated. Manual methods are specific techniques that must be followed when collecting
and analyzing an air pollutant sample. An automated method usually refers to an
instrument that has been approved by EPA as meeting the technical requirements for
accurate collection and analysis of a pollutant. In the monitoring stations used throughout
the country, automated methods are primarily used to collect and analyze ambient air on a
continuous basis.
The EPA has established ambient air monitoring methods for the criteria pollutants,
as well as for toxic organic (TO) compounds and inorganic (IO) compounds. The designated
ambient methods for the criteria pollutants are listed on the EPA Ambient Monitoring
Technology Center's (AMTIC) Ambient Air Monitoring Methods for Criteria Pollutants Web
page. In addition, the TO Compendium contains standardized methods for monitoring
VOC's and selected toxic organics, and the IO Compendium contains methods for
monitoring inorganic compounds.
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The methods specify precise procedures that must be followed for any monitoring
activity related to the compliance provisions of the Clean Air Act. These procedures
regulate sampling, analysis, calibration of instruments, and calculation of emissions. The
specific method chosen for an analysis depends on a number of factors, the most important
being the chemical characteristics and state of the pollutant. All the reference methods are
designed to determine the actual concentration of a pollutant in a sample. The
concentration is expressed in terms of mass per unit volume, usually micrograms per cubic
meter (g/m3).

Source and ambient air sampling

The sampling should be carried out long enough and at a rate that allows collection
of an analytically measureable sample. There are both gaseous and particulate air
pollutants whose concentrations occur at levels below are milligram per cubic metre of air.

A typical air sampling system consists of a sample collector, a flowmeter to measure
the airflow through the collector, and a pump to draw the air sampling equipment. The
flowmeter can be positioned either upstream or downstream from the sample collector if
the pressure drop across the collector is low, but when this is not the case the flowmeter
must be placed upstream of the sample as shown in Fig 1.1 (b). Otherwise, serious errors
can result in the airflow measurement as most of the flowmeters are designed to operate at
and are calibrated at atmospheric pressure.

(a)

Sample Collector Flowmeter Pump


(b)
Flowmeter Sample Collector Pump
Fig 1.1. Typical air sampling setup
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Individual sample collectors are generally grouped into two categories; those that
can be used to collect gaseous pollutants and those used for particulate pollutants.

Collection of Gaseous air pollutants:

Several methods are available for collection of gaseous air pollutants from ambient
atmosphere. The common ones are; the grab sampling, absorption in liquids, adsorption on
a solid material, and freeze out sampling.

Grab sampling:

In Grab sampling the sample is collected by filling an evacuated flask or an
inflatable bag. Plastic bags have been widely for grab sampling and for storage before
analysis.

Bag sampling is subject to losses caused by moisture condensation or diffusion
through the walls of the bag. The losses can be minimized by performing the analysis
immediately following collection.

Grab samples may be taken using rigid wall containers made from glass or stainless
steel. These containers are first evacuated and then filled by allowing air to enter.
Alternatively, a container may be filled with water and then used as a collector simply by
draining away the water which is replaced by the air sample.

Many problems associated with bag samplers are common to rigid containers also
and the containers are often heated by wrapping them with heating tapes or nichrome
wires to prevent condensation during sampling.

Absorbtion in Liquids:
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Absorbtion of gaseous pollutants into a liquid medium is probably the most
commonly employed method of collecting the samples. Absorbtion separates the desired
pollutant from air either through direct solubility in the absorbing medium or by chemical
reaction.

Many different types of collectors are in use, ranging from simple bubbles to
complex devices which provide a high degree of gas liquid contact.

Probably the most widely used collector is impinge. In the impinge the gas stream is
impinged at high velocity onto a flat surface thus providing good contact between the gas
and the liquid.

Adsorption on Solids:
This method is based on the tendency of gaseous to be adsorbed or the surface of
solid materials. The sample air is passes through o packed column containing a finely
divided solid adsorbent on whose surface the pollutants are retained and concentrated.

The most commonly used solid adsorbents are granular porous solids such as
activated charcoal and silica gel with very large surface area.

After adsorption, the sample gases are described for analysis. This may be
accomplished by heating the adsorbent to volatilize the trapped material or by washing it
with aliquid solvent.

Most organic vapours are analyzed by gas chromatographic technique which
directly uses the adsorption principle.
Freeze out sampling:
In freeze out sampling a series of cold traps,which are maintained at progressively
lower temperature,are used to draw the air sample where by the pollutants are condensed.

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The traps are brought to the laboratory,the samples are removed, and analyzed by
means of gas chromatographic,infrared or ultraviolet spectro photometry,mass
spectrometry,or by wet chemical means.
Gaseous Pollutants - Spectrophotometry
Spectrophotometry is one of the most useful and widely used tools available for
quantitative analysis. A spectrophotometer measures the amount of light that a sample absorbs.
The instrument operates by passing a beam of light through a sample and measuring the intensity
of light reaching a detector. Spectrophotometry relies on colorimetric principles and is
commonly used to measure sulfur dioxide (SO2) concentrations. In this method, dyes and
chemicals are combined with a solution containing SO2. The color of the solution results in
different amounts of light being absorbed. The amount of light absorbed indicates the amount of
sulfur dioxide present in the sample.


Figure: Schematic of a UV-VIS spectrophotometer


Ozone can also be analyzed using the monochromatic ultraviolet absorption
spectrophotometry principle. As ultraviolet light at 253.7 nm is passed through the optic
bench, a fixed quantity of "zero air" and ambient air are drawn into the bench. The intensity
of the ultraviolet radiation traversing the optics bench is attenuated by the ozone present
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in the ambient sample. This attenuated signal is detected and compared with the
unattenuated signal from the "zero air" cycle. This difference in intensity is electronically
translated into a reading of ozone present in the ambient air.
Gaseous Pollutants - Chemiluminescence



Figure: Chemical reaction to determine oxides of nitrogen by chemiluminescence

Chemiluminescence methods for determining components of gases originated with
the need for highly sensitive means for determining atmospheric pollutants such as ozone,
oxides of nitrogen, and sulfur compounds. Chemiluminescence is based upon the emission
spectrum of an excited species that is formed in the course of a chemical reaction. Oxides of
nitrogen can be determined by the gas phase reaction of NO with ozone (O3). An ambient
air sample is mixed with excess ozone in a special sample cell. A portion of the NO present
is converted to an activated NO2 which returns to a lower energy state and in the process
emits light. This phenomenon is called chemiluminescence. The intensity of this light can
be measured with a photomultiplier tube and is proportional to the amount of NO in the
sample. A second reaction measures the total oxides of nitrogen in the air sample and in
turn, the concentration of NO2 can be calculated.
Another important chemiluminescence method is used for monitoring atmospheric
ozone. In this instance, the determination is based upon the luminescence produced when
ozone reacts chemically with the dye rhodamine-B absorbed on an activated silica gel
surface or with ethylene. The chemical reaction creates light pulses, which are detected and
counted by a photomultiplier tube. The concentration of ozone is determined by comparing
the number of light pulses created by the sample with the number of light pulses created by
a sample having a known concentration of ozone.
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Gaseous Pollutants - Gas Chromatography (GC)

Figure: Schematic gas chromatography
Gas chromatography (GC) coupled with a flame ionization detector (FID) is
employed for qualitative identification and quantitative determination of volatile organic
compounds (VOCs) in air pollution monitoring. The gas chromatograph, or GC, consists of a
column, oven and detector. In the gas chromatograph, a sample goes to the column,
separates into individual compounds and proceeds through the hydrogen flame ionization
detector. The flame in a flame ionization detector is produced by the combustion of
hydrogen and air. When a sample is introduced, hydrocarbons are combusted and ionized,
releasing electrons. A collector with a polarizing voltage located near the flame attracts the
free electrons, producing a current that is proportional to the amount of hydrocarbons in
the sample. The signal from the flame ionization detector is then amplified and output to a
display or external device.
Gas Chromatography-mass Spectrometry
Gas chromatography-mass spectrometry (GC-MS) instruments have also been used for
identification of volatile organic compounds. Mass spectrometers use the difference in mass-to-
charge ratio (m/z) of ionized atoms or molecules to separate them from each other. Mass
spectrometry is useful for quantification of atoms or molecules and also for determining
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chemical and structural information about molecules. Molecules have distinctive fragmentation
patterns that provide information to identify structural components.

Gaseous Pollutants - Fourier Transform Infrared Spectroscopy (FTIR)

Figure: FTIR can directly measure both criteria pollutants and toxic pollutants in the ambient
air.

Figure: FTIR can directly measure both criteria pollutants and toxic pollutants in the ambient
air.
Fourier Transform Infrared Spectroscopy (FTIR)
Fourier Transform Infrared Spectroscopy (FTIR) can detect and measure both
criteria pollutants and toxic pollutants in ambient air. FTIR can directly measure more than
120 gaseous pollutants in the ambient air, such as carbon monoxide, sulfur dioxide, and
ozone. FTIR technology can also measure toxic pollutants, such as toluene, benzene, and
methanol. The technology is based on the fact that every gas has its own "fingerprint," or
absorption spectrum. The FTIR sensor monitors the entire infrared spectrum and reads the
different fingerprints of the gases present in the ambient air.
Carbon monoxide is monitored continuously by analyzers that operate on the infrared
absorption principle. Ambient air is drawn into a sample chamber and a beam of infrared light is
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passed through it. CO absorbs infrared radiation, and any decrease in the intensity of the beam is
due to the presence of CO molecules. This decrease is directly related to the concentration of CO
in the air. A special detector measures the difference in the radiation between this beam and a
duplicate beam passing through a reference chamber with no CO present. This difference in
intensity is electronically translated into a reading of the CO present in the ambient air, measured
in parts per million.


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