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* Annual arithmetic mean of minimum 104 measurements in a year at a particular site taken twice a week
24 hourly at uniform intervals.
** 24 hourly or 8 hourly or 1 hourly monitored values, as applicable, shall be compiled with 98% of the
time in a year. 2% of the time, theymay exceed the limits but not on two consecutive days of monitoring.
Note - Whenever and wherever monitoring results on two consecutive days of monitoring exceed the
limits specified above for the respective category, it shall be considered adequate reason to institute
regular or continuous monitoring and further investigation.
Criteria Pollutants
Given the ongoing focus of the Clean Air Act, most of the monitoring of emissions, concentrations, and
effects of air pollution has been directed toward the six criteria pollutants: ground-level ozone (O3),
carbon monoxide (CO), sulfur dioxide (SO2), small particulates (PM10 and now PM2.5), nitrogen dioxide
(NO2), and lead (Pb). The original ambient air quality standards for these pollutants were based on
extensive documentation assembled and published by the EPA in a multivolume set of Air Quality-
Criteria documents, from which the name criteria pollutants originated.
Carbon Monoxide
Over two-thirds of the mass of all the pollutant emissions in the United States is the colorless, odorless,
tasteless, poisonous gas, carbon monoxide (CO). It is produced when carbonaceous fuels are burned
under less than ideal conditions. Incomplete combustion, yielding CO instead of CO2, results when any of
the following four variables are not kept sufficiently high: (1) oxygen supply, (2) combustion
temperature, (3) gas residence time at high temperature, and (4) combustion chamber turbulence.
These parameters are generally under much tighter control in stationary sources such as power plants
than in motor vehicles, and CO emissions are correspondingly less. For example, power plants, which are
designed and managed for maximum combustion-efficiency, produce less than 1 percent of all CO
emissions in spite of the fact that they consume about 30 percent of our fossil fuel.
Over 80 percent of total CO emissions are from the transportation sector, and almost all of the
CO in urban areas comes from motor vehicles. Hourly atmospheric concentrations of CO over our cities
often reflect city driving patterns: peaks occur on weekdays during the morning and late afternoon rush
hours, while on weekends there is typically but one lower peak in the late afternoon. Personal exposure
to CO is very much determined by the proximity of motor vehicle traffic, with some occupational groups
such as cab drivers, police, and parking lot attendants receiving far higher than average doses. Carbon
monoxide emissions from motor vehicles decreased by 41 percent in the past 20 years (1983-2002)
despite a doubling in vehicle-miles traveled. The impact of tightening emission controls, coupled with a
drop in the fraction of older, more polluting cars still on the road, is clearly evident.
At levels of CO that occur in urban air, there are apparently no detrimental effects on materials
or plants; those levels can, however, adversely affect human health. Carbon monoxide is an asphyxiant;
it interferes with the blood's ability to carry oxygen from the lungs to the body's organs and tissues.
When inhaled, it readily binds to hemoglobin in the bloodstream to form carboxyhemoglobin (COHb).
Hemoglobin, in fact, has a much greater affinity for carbon monoxide than it does for oxygen, so that
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even small amounts of CO can seriously reduce the amount of oxygen conveyed throughout the body.
With the bloodstream carrying less oxygen, brain function is affected and heart rate increases in an
attempt to offset the oxygen deficit. The usual way to express the amount of carboxyhemoglobin in the
blood is as a percentage of the saturation level, %COHb. The amount of COHb formed in the blood is
related to the CO concentration and the length of time exposed, as suggested in the following.
where
y = 0.402/hr
= 0.15%/ppm CO
Estimate the %COHb expected for a one-hour exposure to 35 ppm (the federal standard).
Physiological effects can be noted at small percentages of COHb, increasing in severity as the
concentration increases. The elderly, the fetus, and individuals who suffer from cardiovascular disease,
particularly those with angina pectoris (a heart condition characterized by chest pain) or peripheral
vascular disease, are the most sensitive to COHb since the heart must work harder in an attempt to
offset the reduction in oxygen. Studies of patients with angina have shown an earlier-than-usual onset
of pain during exercise when levels are as low as 2 percent COHb. In Example 7.3, it was calculated that
an individual breathing CO at the federal ambi-ent air quality standard of 35 ppm for one hour would be
likely to reach 1.7 percent COHb. That is very close to the level at which health effects have been noted,
and the federal standard has been criticized as a result. California's CO standard has been set lower (20
ppm) in an attempt to assure less than 2 percent COHb.
The reduction of oxygen in the bloodstream also affects the brain's ability to perceive and react.
At 2.5 percent COHb, studies have shown an impairment in time-interval discrimination. (Subjects were
less able to distinguish the duration of a tone signal.) Studies have also shown that at 5 percent,
psychomotor response times may be affected, and patients with heart disease experience increased
physiological stress. At 5 to 17 percent, manual dexterity, ability to learn, and performance in complex
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sensorimotor tasks such as driving are diminished. At 10 percent, headache is com-mon, and at 30
percent COHb, most people will experience dizziness, headache, fatigue, and impaired judgment.
Concentrations above 60 percent produce loss of consciousness and death if exposure continues.
Carbon monoxide concentrations near busy roadways frequently range from 5 to 50 ppm, and
measurements made on congested highways indicate that drivers can be exposed to CO concentrations
of 100 ppm. Carbon monoxide is an important pollutant in indoor air as well. Cigarette smoke contains
more than 400 ppm CO, and smokers frequently have COHb levels between 5 and 10 percent. Tobacco
smoke in bars and restaurants often raises indoor CO levels to 20 to 30 ppm, which is close to the one-hr
ambient standard (Wadden and Scheff, 1983). Fortunately, COHb is removed from the bloodstream
when clean air is breathed. Healthy sub-jects clear about half of the CO from their blood in three to four
hours, so adverse effects are usually temporary.
SO2 + OH HOSO2
HOSO2 + O2 SO3 + HO2
SO3 reacts with water vapour to form sulfuric acid, thus causing acid rain.
SO3 + H2O H2SO4
Natural rain has a pH between 5 and 5.6 and any rain containing water of pH value less is called acid
rain.
Sulfuric acid molecules become particles by either condensing on existing particles in the air or by
merging with water vapor to form H2O-H2SO4 aerosol droplets (known as sulfate aerosols).
Sulfate aerosols constitute a significant portion of the urban air particulate matters. Their size is
normally less than 2 m that allows penetration into the respiratory system. Most of the aerosols have
size in the range of 0.2 to 0.9 m comparable to wavelength of visible lights and thus they obstruct the
light and cause reduced visibility.
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Effect of SOx
Sulfur entrained in the form of aerosol can reach far deeper into lungs. The combination of particulates
and sulfur oxides can act synergistically, with the effect being much more detrimental.
SOx can damage tress. Acidification affects the plants ability to extract nutrients from the soil.
Nutrients are leached from soils more readily under acidic conditions.
They discolor plant, corrode metal, and cause organic fibres to weaken.
Prolonged exposure to sulfates causes serious damage to building marble, limestone, and
mortar.
The carbonates are replaced by sulfates.
Oxides of Nitrogen
There are 7 oxides of N2 that may occur, NO, NO2, NO3, N2O, N2O3, N2O4, and N2O5.
However the important ones are: nitric oxide (NO) and nitrogen dioxide (NO2).
Source: when fossil fuel is burnt at higher temperature (more than 7000C), nitrogen gets oxidized.
Thermal NOx: nitrogen and oxygen of the combustion air are heated sufficiently to oxidize N2.
Fuel NOx: results from the oxidation of nitrogen compounds that are chemically bound in the fuel
molecules. Natural gas has almost no N2, while coal may have up to 3% by weight.
The transport sector contributed 57% and stationary sources accounted for 37% of NOx emissions.
About 95% of the NOx emissions are in the form of NO. However it rapidly oxidized to NO2.
Also produced during blasting of explosives such as gelatin, dynamite due to incomplete detonation.
Physiological effcets
Highly poisonous. These are toxic gases with a biting and choking smell.
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NOx react with moisture to form nitrous and nitric acid. NOx may react with the moisture in the
lungs create acids and corrode the respiratory passage. Can irritate the lungs.
Cause bronchitis and pneumonia and lower resistance to respiratory infection.
NO2 combines with the hemoglobin of the blood about 300,000 times more readily than O2 to
form an extremely stable compound thereby quickly reducing the oxygen carrying capacity of the
blood.
Death from exposure to NOx may be very quick if the exposure level is very high.
It reacts with the volatile organic compounds (VOC) in the presence of sunlight to form
photochemical oxidants that have adverse health effects.
It reacts with the hydroxyl radicals (OH) in the atmosphere and forms acid causing acid rain.
Consists of volatile compounds that are emitted when solvents, fuels, and other organics evaporate along
with unburned and partially burned hydrocarbons emitted from tail pipes and smoke stacks of fossil fuel
combustion facility.
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VOC is important because of their role in formation of photochemical smog.
Transportation sector produces >50% of the anthropogenic VOCs. Rest by the industrial sector.
Properties: A colorless gas that is the major constituent of photochemical smog and has an electric-
discharge-type odor.
"Good" ozone occurs naturally in the stratosphere and forms a layer that protects life on earth from the
harmful sun's ultraviolet radiation. In the earth's lower atmosphere, or troposphere, ground-level ozone is
harmful for health of animals and plants.
Sources
At ground-level, ozone is formed as a result of chemical reactions caused by the presence of nitrogen
oxides (NOx) and volatile organic compounds (VOCs). These compounds react with oxygen in the air in
the presence of heat and strong sunlight to produce ground-level ozone, the primary ingredient of smog.
Physiological Effects of O3
Examples: Formaldehyde (HCHO), acetaldehyde (C2H4O), Acrolein (CH2=CHCHO), nitric acid (HNO3),
PAN, Peroxybenzyl nitrates.
Annoying respiratory effects such as coughing, shortness of breath, airway constriction,
headache, chest tightness, eye/ nose/ throat irritation. Both formal dehyde and acrolein are
irritating to eye.
Chest constriction
Irritation of the mucous membrane
Cracking of rubber products,
Damage to vegetation
The symptoms can be very severe for the asthma patients.
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Irritation of eye is caused by formaldehyde (HCHO), peroxybenzyl nitrate (PBzN), peroxy acetyl
nitrate (PAN).
CO
Properties
Colorless, TASTELESS, odorless, and non-irritating
Slightly heavy than air: density 1.250 kg/m3.
Mixes with air easily.
Tc and Tp - -140 0C, 34.6 atm
Slightly soluble, 100 vol. of water dissolves 2.3 vol. of gas at 20 0C.
Not a supporter of combustion, but burns in air at about 700 0c with a light-blue flame to form CO2.
Physiological Effects
Deadly poisonous.
High affinity for hemoglobin (oxygen carrier) of the blood; 200 to 300 times more than that of O2.
Forms a more stable compound than oxy-hemoglobin (Hb.O2) called Carboxy haemoglobin (Hb.CO) a bright pink
compound.
Once the Hb.CO is formed, the haemoglobin cannot combine with O2, thus reducing the O2 carrying capacity of the
blood depriving the brain and body tissue the same.
The rate at which CO combines with Hemoglobin depends on the exposure time, the CO concn, and the activity
being performed.
HbO2 + CO HbCO + O2
An individuals response will depend on his age, and general physical condition.
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Fig. 2 gives a chart showing physiological effects of CO on human beings. Shows the relationship between the CO
concn, time of exposure, % saturation of blood, and the health effect on a normal healthy human being.
Particulate Matters
PM consists of any dispersed matter, solid and liquid or their aggregates.
The size of the aggregates or particles may vary between 0.005 to 100 m.
They vary in size, chemical composition, and atmospheric concentrations.
The black smoke, or soot, emitted from diesel engines and smoke stacks consists mostly of solid particles
made up of vast numbers of carbon atoms fused together in benzene rings.
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A class of benzene like hydrocarbons called polynuclear (polycyclic) aromatic hydrocarbons (PAHs)
are of great concern. PAHs are formed when carbon containing material are not completely oxidized
during combustion. They are released as gases but quickly condense onto particles of soot.
Common sources of PAHs include: vehicle exhausts, smoke from wood and coal combustion.
PAHs consist of fused benzene rings. The simplest one is naphthalene.
Mist: Liquid particles or droplets formed by condensation of vapors. The size range is < 10 m.
If mist concentration is high enough to obscure visibility, the mist is called a fog.
Coarse particles tend to settle quickly, so their spatial impact is limited to areas near their source. Fine
particles have longer atmospheric lifetimes and travel vast distances.
Impacts of particulates
The upper respiratory system consists of the nasal cavity and the trachea. The lower respiratory system
consists of bronchial tubes and the lungs.
Large particles that enter the respiratory system can be trapped by the hairs, and lining of the nose.
Once captured, they can be driven out by cough or sneeze.
Smaller particles make into the trachea-bronchial system can be captured by mucus and carried back
to the throat by tiny hair like cilia and removed by spitting.
Still smaller particles reach the lungs without being captured on the mucus lining. Particles between 2
to 4 m are mostly deposited in the lungs.
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Effects of PM
Aggravate existing respiratory and cardiovascular disease
Damage lung tissues.
Some are carcinogenic in nature.
Ammonia
Ammonia (NH3) is one of the most commonly produced industrial chemicals. Ammonia is essential for many
biological processes and serves as a precursor for amino acid and nucleotide synthesis.
In the environment, ammonia is part of the nitrogen cycle and is produced in soil from bacterial processes. Ammonia
is also produced naturally from decomposition of organic matter, including plants, animals and animal wastes.
Some chemical/physical properties of ammonia are:
At room temperature, ammonia is a colorless, highly irritating gas with a pungent, suffocating odor.
In pure form, it is known as anhydrous ammonia and is hygroscopic (readily absorbs moisture).
Ammonia has alkaline properties and is corrosive.
Ammonia gas dissolves easily in water to form ammonium hydroxide, a caustic solution and weak base.
Ammonia gas is easily compressed and forms a clear liquid under pressure.
Ammonia is usually shipped as a compressed liquid in steel containers.
Ammonia is not highly flammable, but containers of ammonia may explode when exposed to high heat.
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Ammonia interacts immediately upon contact with available moisture in the skin, eyes, oral cavity, respiratory tract,
and particularly mucous surfaces to form the very caustic ammonium hydroxide.
Ammonium hydroxide causes the necrosis of tissues through disruption of cell membrane lipids (saponification)
leading to cellular destruction. As cell proteins break down, water is extracted, resulting in an inflammatory response
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Benzene
Benzene is highly volatile, and most exposure is through inhalation.
Benzene is degraded rapidly in the upper atmosphere. Because of its solubility in water, a minor amount
may be removed by rain to contaminate surface waters and soil.
Benzene occurs naturally in crude petroleum at levels up to 4 g/l. Emitted from industrial processes
including processing of petroleum products, coking of coal, production of petrol (gasoline) and heating
oils.
Automobile exhaust accounts for the largest source of benzene in the general environment.
Human exposure to benzene has been associated with a range of acute and long-term adverse health
effects and diseases, including cancer and aplastic anaemia.
Health effects
Acute effects
Acute occupational exposure to benzene may cause narcosis: headache, dizziness,
drowsiness, confusion, tremors and loss of consciousness. Use of alcohol enhances the
toxic effect.
Benzene is a moderate eye irritant and a skin irritant
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Particulate matter Settling Properties
Settling is the major natural self-cleaning process for removal of particulates from the atmosphere.
Settleable particles are larger and heavier and settle close to their sources. Greater than 10 m in size.
The terminal settling velocity of the settleable particulates using Stokes law.
Stokes law is generally applied to calculate the terminal settling velocity of particulates.
( ) 2
= (1)
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p is the density of the particle, g = gravitational constant, d is the particle diameter
Density of air can be neglected and the equation is reduced to Vt = g p d2/ 18 (2)
Particles smaller than 0.1 m often coagulates through mutual collisions and forms larger aggregates
which are removed by gravitational settling.
The rate of sedimentation is controlled by the particle size. Particles larger than 10 m have high settling
rates and, hence have short residence time in the atmosphere.
The terminal velocity is also related to the particle density, but only by a less sensitive linear dependence.
Deviations from the Stokes law occur due to the irregular particle shape, turbulence in the wake of large
particles.
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Fig. Gravitational Chamber
By assuming Stokes law applies, we can calculate the minimum diameter of a particle that will be
collected with 100% efficiency.
In a chamber of length L, and height H:
In order that a particle of settling velocity Vt is retained.
=
Where is the velocity of flow of the gas in horizontal direction.
Solving for Vt, yields, = (For 100 % theoretical removal efficiency)
Solving for d, for 100 % removal, the particle diameter can be given as:
/
=( ) (3)
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A more elaborate settling chamber is the Howard type. By inserting several trays, the collection efficiency
of the device is improved since the particle has a much shorter distance to fall before reaching the bottom
of the passage between trays.
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