environmental pollution notes
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Environmental Pollution Control(ETZC362)
Dr. Jegatha Nambi Krishnan
Department of Chemical Engineering
11thJan. 2014
etzc362
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Air Pollution
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Air pollution:any atmospheric condition in which certain substances are present insuch concentrations that they can produce undesirable effects on manand environment
Gases - Sulphur oxides, nitrogen oxides, carbon monoxide,hydrocarbons etc.Particulate matter - smoke, dust, fumes, aerosols,Radioactive materials
Air pollutant is a particular substance -Its concentration is high
compared to the background value & cause adverse effects onhumans, animals, plants or property.
Ex. Sulphur dioxide - > 2 x 10 -4ppm
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1. Mass concentration, , defined as the ratio of the mass of
pollutant to the mass of air plus mass of pollutant
Where mp is the mass of pollutant and ma is the massof pure air in a given volume of air-pollutant mixture.
2. Volume concentration, , defined as the ratio of the volume
of pollutant to the volume of air plus volume of pollutant
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Scales of concentration
pa
p
p
mm
mw
pa
p
pvv
vy
3
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3. Volume concentration in parts per million (ppm),y ppm
4. Mass-Volume concentration, p (g of pollutant per cubicmetre of air), defined as the ratio of the mass of the
pollutant to the volume of air plus volume of pollutant
Assuming that perfect gas law hold for pollutants that areusually formed in the atmosphere
Scales of concentration
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610 pppm yy
pa
p
p vv
m
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Scales of concentration
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The relation between p and yppm :
p - Concentration of a pollutant whether it be gaseousor particulate (g/m3)
yppm - Volume concentration in parts per million (ppm),
Mp - Molecular weight of the pollutant
45.24
103ppmpp
yM
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The normal cubic meter is important if the emissiontemperature is greater than ambient as one mole of the
emission gas does not occupy 22.4 L.
At non standard temperatures and pressures, correctionshave to be made.
At STP ( 0C and 101.3 Kpa), 1 mole of an ideal gas
occupies 22.4 L.At non STP conditions,
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L
P
kPa101*
K273
T*22.4mole1
Scales of concentration
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Classification Air Pollutants
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Primary Pollutant (Directly emitted from source)- Ex. Particulatematter, inorganic gases and radioactive compounds.
Secondary Pollutant (Formed as a result of chemical andphotochemical reactions in the atmosphere)
Properties of Air Pollutants (particulate matter and gaseous pollutants)
The classification of various particulates may be made as follows:
Dust Particles of size ranging from 1 to 200m. These are formed by
natural disintegration of rock and soil or by mechanical processesof grinding and spraying.
Smoke Fine particles of size ranging from 0.01 to 1 m resultingwhich can be liquid or solid from combustion or other chemicalprocesses. Based on materials burnt it is of different colours. 7
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Fumes Particles of size ranging from 0.1 to 1m formed
by condensation, sublimation , or chemical reaction /
metallurgical processes.
Mist Liquid droplets generally smaller than 10m which are
formed by condensation in the atmosphere or released from
industrial operations.
Fog It is the mist in which the liquid is water and is sufficiently
dense to obscure vision.
Aerosol Air-borne suspensions either solid or liquid; these are
generally smaller than 1m. Dispersion of microscopic solid or liquid
particles in gaseous media.
Classification Air Pollutants
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Particles- 1-10m
Particles of size ranging from 0.1 to 1m have smaller settling velocities readilystirred by air movements. Those below 0.1 m, a submicroscopic size found in
urban air, undergo random Brownian motion resulting from collisions among
individual molecules.
Most particles of size ranging from 0.1 to 10m in urban air cause significant
damage to health.
Hydrocarbons which can coalesce into aerosol droplets that constitute one kind of
particulate matter.
Most harmful components of incomplete combustion are generally
grouped as particulate polycyclic organic matter (PPOM). PPOMs are
derivatives of benz--pyrene, a potent carcinogen.
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Sizes of Atmospheric particulate matter
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Gaseous PollutantsOxides of Sulphur (SOx, H2SO3)
SO2 is the most important pollutant emitted and is oxidized slowly in clean air to sulphurtrioxide. SO3 with moisture in atmosphere to form sulphuric acid. Both SO2 and SO3are relatively quickly washed out of the atmosphere by rain or settle out as aerosols.Ex. Large SO2 from roasting and treatment of non-ferrous sulphide minerals,principally lead, zinc and copper ores. Metallic and non metallic industries,Petroleum refining operations.
Oxides of Nitrogen (NOx = NO &NO2)
Among the seven oxides of nitrogen, N2O, NO and NO2 are formed in appreciablequantities in the atmosphere. NO2 major pollutant emitted by fuel combustion andnitric acid plants.
Carbon Monoxide (CO) and CO2CO -Single largest pollutant in urban atmosphere and has strong affinity towards
hemoglobin of blood stream and so dangerous asphyxiant. The rate of oxidation ofCO to CO2 is very slow. The main sources of CO in the urban air are smoke andexhaust fumes of burning gas, coal or oil.
Classification Air Pollutants
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Lighter Hydrocarbons (HCs)
Gaseous and volatile liquid hydrocarbons.
CH4 is the abundant hydrocarbon constituting 40-80% of total
HCs. It has very low photochemical activity and so non-methaneHC concentration is of interest.
Among the alkenes, ethylene and propenes are prominentpollutants. Ex: toluene and m-xylene (urban atmosphere)
Terpenes-volatile HCs (pine tar and wood sources)
These are responsible for the production of secondarypollutants in the presence of sunlight and nitrogen oxides formingphotochemical oxidants Ozone.
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Classification Air Pollutants
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Emission sources- Source type
NaturalThe pollutant emission from natural sources is much greater thanthat from anthropogenic sources. Fortunately, natural pollutantsare distributed throughout the world and reach a sink such asocean or the soil. The atmosphere can cleanse itself from thepollutants given sufficient time. Ex. wind blown dust, pollen, sea
salt nuclei, volcanic ash and gases, smoke and trace gases fromforest fire.
AnthropogenicThe pollutants are concentrated in specific locations and reachhigh levels in atmosphere. The emission of these pollutants is atsuch massive rates that they overwhelm the capacity of theenvironment to cleanse itself. Ex. Combustion of fossil fuels Ex.SO2, NO2, CO & fly ash, trace metal oxides, Ex. mercury, lead andcadmium. Chemical and metallurgical industries, food andagriculture etc.
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Classification of Anthropogenic Airpollution sources
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Classification of Anthropogenic Airpollution sources
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Classification of Anthropogenic Airpollution sources
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Behavior and Fate of Air Pollutants
Natural Pathways (scavenging processes) of exchange ofpollutants from atmosphere to earth surface
Particulates:
Wet removal by precipitation. Dry removal by sedimentation, impaction and diffusion.
Gases:
Wet removal by precipitation.
Chemical reaction in the atmosphere to produce aerosols and /or absorption on aerosols with subsequent removal.
Absorption or reaction at land and ocean surfaces.
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Wet PrecipitationWet precipitation has two distinct mechanisms rainout andwashout
The rainout includes various processes taking place insideclouds, where the contaminants serve as condensation nuclei on whichdroplets condense. Ex. Particles less than 0.1m . These particlescaptured by cloud droplets (30 m).
The washout mechanism refers to the removal of pollutants below the
cloud level by falling rain. Ex. Particles larger than 2 m .
The wet precipitation is very effective in removing acid droplets andsulphate particles formed after chemical reactions.
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Behavior and Fate of Air Pollutants
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Dry DepositionParticulate matter smaller than 0.1m often coagulates through mutual collisions and formslarger aggregates which are effectively removed by gravitational settling. Brownian motion isthe major mechanism of coagulation, although atmospheric turbulence also enhances thediffusive motion of particles.
Atmospheric turbulence is particularly effective for coagulating larger particles whose
Brownian motion is less pronounced.
The rate of settling of the particles depends on their settling
velocities according to Stokes Law:
Where
vt = terminal settling velocity; dp = particle diameter;
p and a = density of particle and air, respectively;
a = viscosity of air; P = air pressure; C = constant
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pd
Cgd
v papa
p
t
2
118
2
Behavior and Fate of Air Pollutants
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Interaction at the earths surface
Gaseous pollutants can be transported to the earth surface byatmospheric turbulence where they interact with the oceansurface, vegetation and upper layers of the soil and are removed
by absorption or chemical reaction.
SO2 and CO are the 2 major pollutants formed.
SO2
- Ocean, vegetation and upper layers of the soil
Co converts to CO2 or CH4- Biological action by the bacteria inthe soil acts as a sink.
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Behavior and Fate of Air Pollutants
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Chemical reactions in the atmosphere
Many of the gaseous pollutants undergo chemical reactions within theatmosphere and form new compounds or aerosols.
Oxides of the sulphur is removed from the atmosphere primarily by wet
precipitation.
Oxides of nitrogen are removed through their conversion process to formnitric acid.
CO is removed by the fast reaction with hydroxyl radicals present in theatmosphere. Another possible mechanism is the migration of CO into thestratosphere, where the oxidation to CO2 may subsequently take place bythe hydroxyl radicals. All these pollutants inter-reactby photochemicalprocesses in the phenomenon known as thephotochemical smog.
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Interaction at the Earths surfaceAbsorption
At the ocean surface SO2, first diffuses through the gas phase, crosses the
gas-liquid interface, and finally diffuses into the bulk of the ocean where
it is absorbed
NO2 also absorbed by ocean and other surface waters
ADSORPTION
SO2 first diffuses to the external surface of the solid, penetrates into the
pores of the solid,
and is subsequently adsorbed on the pore site
Behavior and Fate of Air Pollutants
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BIOLOGICAL ACTION IN SOIL
Soil contains certain bacteria which can make use ofCO in their metabolism, producing either CO2 or CH4.
OHCHHCO
COOCO
242
22
3
22
Behavior and Fate of Air Pollutants
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SO2 is oxidized to SO3 which combines with atmosphericmoisture to form H2SO4 mist(Slow process)
Metal salt particles serve as nucleation sites for droplet
formation and react with H2SO4 to produce sulphates,
which are also removed by wet precipitation
4232
322 22
SOHSOOH
SOOSO
HClSONaSOHNaCl 22 4242
Chemical reactions in atmosphere
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Direct conversion of NO2 to HNO3 in presence of moisture(slow process)
NOHNOOHNO 322 23
Chemical reactions in atmosphere
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Conditions for the formation of photochemical smog areAir
stagnation, sunlight, & high concentration of HCs & N oxide
in the atmosphere.
Smog arises from photochemical reactions in the loweratmosphere by the interaction of HCs & nitrogen oxidereleased by exhausts of automobiles & some stationarysources.
This interaction results in a series of complex reactionsproducing secondary pollutants like ozone, aldehydes,ketones, & PAN
Photochemical Smog
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smogNOHC atmloweratandhvx
)(PANsNitratesPeroxyacylKetones
Aldehydes
Ozone
Photochemical Reaction
Photochemical Smog
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Interaction at the Earths surface
ABSORPTION
At the ocean surface SO2, first diffuses through the gas phase,
crosses the gas-liquid interface, and finally diffuses into the bulk ofthe ocean where it is absorbed
NO2 also absorbed by ocean and other surface waters
ADSORPTION
SO2 first diffuses to the external surface of the solid, penetratesinto the pores of the solid,
and is subsequently adsorbed on the pore site
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Behavior and Fate of Air Pollutants
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Photochemical smogThe conditions for the formation of photochemical smog are air stagnation,
abundant sunlight, and high concentrations of hydrocarbon and nitrogen
oxides in the atmosphere.
Smog arises from photochemical reactions in the lower atmosphere by the
interaction of hydrocarbons and nitrogen oxide released by exhausts of
automobiles and some stationary sources.
This interaction results in a series of complex reactions producing secondary
pollutants such as ozone, aldehydes, ketones, and peroxyacyl nitrates.
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Behavior and Fate of Air Pollutants
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h d f A ll
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The starting mechanism is the absorption of ultraviolet lightfrom the Sun by NO2. This causes the nitrogen dioxide todecompose into nitric oxide and highly reactive atomicoxygen .
ONOhvNO 2
The atomic oxygen initiates oxidizing processes or quicklycombines with molecular oxygen to form ozone, whichitself is reactive and acts as an oxidant:
223
32
ONONOO
MOMOO
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B h i d F f Ai P ll
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M is an energy-absorbing molecule or particle is required tostabilize O3 or else it will rapidly decompose.
Under normal conditions, the ozone formed will be quicklyremoved by reaction with NO to provide NO2 and O2.
However, when hydrocarbons are present in the atmospherethis mechanism is partially eliminated as NO reacts with thehydrocarbon radical peroxyacyl (RCO.3) and as a result ozoneconcentration builds up to dangerous levels.
Hydrocarbons compete for free oxygen released by NO2decomposition to form oxygen-bearing free radicals such as theacyl radical.
( )H C O R C O a c y l r a d ic a l
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B h i d F f Ai P ll
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This radical takes part in a series of reactions involvingthe formation of still more reactive species, which in turnreact with O2, hydrocarbons and nitric oxide.
32.
23
22.
3.
2
3
32
)(
ORCOORCO
NORCONORCO
ketonesCOR
aldehydesRCHOHCRCOradicalperoxyacylRCOORCO
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B h i d F t f Ai P ll t t
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The typical smog episode occurs in hot, sunny weather
under low humidity conditions. The characteristics
symptoms of the smog are the brown haze in the
atmosphere, reduced visibility, eye irritation, respiratory
diseases and plant damage.
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Behavior and Fate of Air Pollutants
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E A
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Effects of Air Pollution
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Human healthAdverse effects may be divided into acute and chroniceffects.
Acute: High concentration for shorter duration.
Chronic: lower concentration for higher durations(prolonged periods).
Particular attention to six pollutants:Particulates, sulphur oxides, carbon monoxide, nitrogenoxides, hydrocarbons and photochemical oxidants.
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Eff f Ai P ll i
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Pollutants may Enter into body by 4 ways:
Ingestion: by means of swallow
Inhalation: by means of respiration inhaled intolungs
Absorption: by means of absorption in skin or eye
Injection: by means of external injection
Effects of Air Pollution
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Effects of Air Pollution
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Respiratory Effects:
Pollutants may enter the body by a number of ways but primarily
through respiration.
Causes skin irritation.
The major organs of the respiratory system are nose, pharynx, larynx,
trachea, bronchi and lungs. The first four of the above is called
as upper respiratory tract (URT) where as the last 2 are called
as Lower respiratory tract (LRT).
Particulate matter inhaled may be deposited in various regions of the
respiratory system depending on the particle size.
Effects of Air Pollution
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Particles above 10m are almost retained in the nose itselfand smaller than this may escape the entrapment and
passes through the URT.
Fine particle in the size range from 0.5 to 5m are
deposited in LRT.
This results in the damaging the respiratory organs.
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Effects of Air Pollution
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The Respiratory and the Alveoli
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The Respiratory and the Alveoli.
the pulmonary alveoli are the terminal ends of the respiratory tree, which outcropfrom either alveolar sacs or alveolar ducts, which are both sites of gas exchangewith theblood as well. Carbon dioxide rich blood is pumped from the rest of thebody into the alveolar blood vessels where it through diffusion releases its carbondioxide and absorbs oxygen.
Source: Wikipedia 38
Effects of Air Pollution
http://en.wikipedia.org/wiki/Respiratory_treehttp://en.wikipedia.org/wiki/Alveolar_ductshttp://en.wikipedia.org/wiki/Bloodhttp://en.wikipedia.org/wiki/Capillarieshttp://en.wikipedia.org/wiki/Diffusionhttp://upload.wikimedia.org/wikipedia/commons/9/9f/Illu_conducting_passages.svghttp://en.wikipedia.org/wiki/Diffusionhttp://en.wikipedia.org/wiki/Capillarieshttp://en.wikipedia.org/wiki/Bloodhttp://en.wikipedia.org/wiki/Alveolar_ductshttp://en.wikipedia.org/wiki/Respiratory_treehttp://en.wikipedia.org/wiki/File:Alveolus_diagram.svg -
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Particulate Matter:
Interference of inert particles with the clearing
mechanisms of the respiratory tract.
Particles act as carriers of adsorbed toxic gases
such as SO2 and produce synergetic effects.
Particles may be intrinsically toxic because of their
physical or chemical characteristics.
Effects of Air Pollution
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Lead
Lead is neurotoxin whose poisoning results in convulsions, delirium,coma,severe and irreversible brain damage and death.
Cadmium
Cigarette smoking constitutes a major source for cadmium accumulation in the
body. It inhibits the performance of certain enzymes thereby producinghypertension in humans. Also causes cardiovascular diseases when exposed tofumes or oxides of cadmium.
Mercury ( Hg present as gas due to high Vap pressure)
Effects of mercury poisoning include neurological damage, chromosomal
aberrations and even death. It penetrates through membranes separatingbloodstream from brain causing injury to cerebellum and cortex.
Higher levels of mercury can build up in the fetus without the mothershowing any signs of illness. The effects are congenital birth defects or thedeath of the fetus.
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Gaseous Pollutants
Sulphur Dioxide
Leads to broncho-constriction when exposed for a few minutes
to levels of 1.6 ppm. Chronic effects are the infection of the
respiratory system in children.Primary threat of SO2 is the formation of H2SO4 and sulphate aerosols.
Carbon Monoxide
When inhaled, passes through the lungs and diffuses directly
into the blood stream to form carboxyhemoglobin, because of itsaffinity, 210 times greater than that of oxygen. This results in
limiting the availability of hemoglobin to carry the oxygen
resulting in asphyxiation.
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Oxides of Nitrogen NO is not irritant and does not show any adverse health effects at the
concentrations generally occurs in the atmosphere. NO2 is relatively insoluble and upon inhalation causes damage to the lung tissues. It form HNO2 & HNO3 which are highly irritating & cause damage to the lungs
tissue Long-term exposure even with 1ppm may lead to health problem like biochemicalchange in blood
Hydro carbons and Photochemical Oxidants
At the concentrations usually found in the urban air, causes no adverse effects onhuman health. The oxidant produced in photochemical smog causes irritation tothe nose, throat and causes chest constriction.
Aromatics causes irritation on mucous membrane PAN & PBN causes irritation on eye, nose, throat & 5 min exposure
with 0.005ppm PBN may lead death
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Effects on VegetationLeaf structure damage is visible incase of vegetation.
The pollutants try to enter through stomata and diffuse to
the surface of the cells within the leaf causing damage topalisade and spongy mesophyll.
The damages are necrosis (dead areas), chlorosis (loss orreduction chlorophyll), epinasty (downward curvature of
the leaf).
Chemicals such as arsenic and fluorides when deposited onthe leaves can poison animals.
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Effect on materials
Particulates such as dust and fumes can damage the
exposed surfaces because of their abrasive nature
The most notorious pollutant responsible for metallic
corrosion is SO2.
Ozone is also very reactive substance and causes thecracking of synthetic rubbers at the levels of 0.01 to 0.02
ppm.
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Green house effect: Global warming
Out of total light energy 20% is absorbed by gases inatmosphere, 50% is absorbed by earth surface, 30% is reflected
back into the space by clouds, ice, snow, sand etc.
The warm earth emits radiation absorbed by it as infrared (heat) radiation
Gases like CO2, in the atmosphere absorbs this heat radiation
The gas molecule then re - emit the absorbed radiation in all directions
A part of this radiation is re diverted to the earth's surface. These processeskeep the earths surface and its atmosphere warm and is called Greenhouse effect.
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Major Air Pollution Disasters
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j
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Ozone HoleOzone layer or natural sunscreen is located in stratosphere
It filters ultraviolet rays of the sunlight, which is harmful tohumans and other forms of life.
Certain gases like Freons or chlorofluoro compounds(CFCs)used as fluids in refrigerators and also as propellants in spraycans of deodorants, perfumes etc is the main cause for theatmospheric ozone depletion.
Cl2CF
2+ h Cl. + ClCF2.
Cl. + 03 ClO + 0
2
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Properties of air pollutants
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p p
Carbon monoxides
Constitutes the single largest pollutant in the urbanatmosphere
Has a B.Pt of -192 0C
Affinities towards hemoglobin in blood stream & isdangerous asphyxiant Main sources of CO in urban air are smoke, exhaust fumes,
from devices burning coal, gas or oil
Hydrocarbons
Gaseous & volatile liquid hydrocarbons are particular airpollutants
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Air Pollution Laws
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To control, to reduce & to monitor
Oldest anti-pollution law Smoke nuisanceAct1920 for Bombay city
Central Air Act,1981 and empowered centralBoard formed for Prevention & Control of WaterPollution,1974
The State PCB are also authorized to close,prohibit/regulate any industry/operation forimproper implementation of acts
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Function of Central PCB
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Advise GOI about prevention, control & abatement ofair pollution acts
Coordination with state PCBs
Plan, arrange & execute training programs on Air PollutionPrevention & Control (APPC)
Sponsor research to mass media on APPC
Publish technical data, measuring devices, manuals, codes]and lay down standards
Recognize a laboratory for air quality analysis
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Air Pollution Standards
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BITS Pilani, K K Birla Goa Campus11th Jan. 2014 (Course Code: etzc 362)
In most country the Govt. set Legal Standards
Standards depends on: population density, meteorological& geographical features
In India, PCB classify state-land into 3 category: Industrial areas Residential & rural areas Sensitive areas (hill station, tourist resort, parks)
Indian Ambient Air Quality Standards (IAAQS) setspermissible limit of air pollutants
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Air Quality Standards
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BITS Pilani, K K Birla Goa Campus11th Jan. 2014 (Course Code: etzc 362)
In USA, the standards are set by United State Environment
Protection Agency
2 types of air quality standard US: Primary & Secondary
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Chapter-2 (Problems)
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BITS Pilani, K K Birla Goa Campus11th Jan. 2014 (Course Code: etzc 362)
Problem-1
Carbon monoxide (CO) is present in standardatmospheric air at a concentration of 50 ppm.Compute volume concentration, mass-volumeconcentration and mass concentration values forthe CO concentration in the atmosphere.
Given: air density at standard condition is 1.185kg/m3 and the molecular weight (MP) is 28.
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Solution
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BITS Pilani, K K Birla Goa Campus11th Jan. 2014 (Course Code: etzc 362)
Given data:Concentration of CO = 50 ppm
Volume concentration,yp =yppm x 10-6 = 50 x 10-6 = 5 x 10-5
Mass volume concentration, p
Mass concentration wp, can be calculated as follows:Divide mass concentration to volume concentration equation
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Solution
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BITS Pilani, K K Birla Goa Campus11th Jan. 2014 (Course Code: etzc 362)
But the term (ma+mp/va+vp) can be written as
Taking the density of air, a, as equal to ma/va, and densityof pollutant, p = (mP/vP)yp; we get
pa
pa
p
p
p
p
mm
vv
v
m
y
w
p
p
p
a
a
a
pa
pa)1( y
v
my
v
m
vv
mm
000048.01026.57)00005.01(185.1
1026.57
)1( 6
6
ppa
p
p
yw
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Chapter-2 (Problems)
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BITS Pilani, K K Birla Goa Campus11th Jan.2014 (CourseCode:etzc362)
Problem 3
The behavior of particulate pollution in the atmosphere is
influenced by their relative sizes. Explain how the size of
particulates makes a difference.
Particles larger than 10 m have high settling rates & has
short residence time in atm
Terminal`s velocity is related to particle`s density
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