CHE PE3 AIR POLLUTION CONTROL

Air Pollutants
We have defined air pollution as the presence in the outdoor atmosphere of one or more air contaminants ( dust, fumes,
gas, mist, odor, smoke, vapor) in sufficient quantities, of such characteristics, and of such duration as to be or to threaten to
be injurious to human, plant, or animal life or to property, or which reasonably interferes with the comfortable enjoyment
of life or property.
We call those substances present in air that can adversely affect ecosystems and the health of humans are called air
pollutants.

UNITS OF MEASUREMENT OF AIR POLLUTANTS

Air quality measurement are commonly reported in terms of:
• Micrograms per cubic meter - concentration
• Parts per million - concentration
• Micron/micrometer – particle size

Pollutants Units

Particulate fallout or dustfall mg/cm2 –time interval

Particulates million particles per cu. m. (106/m3)

Suspended particulates and Mass per unit volume

gaseous contaminants (i.e. µg/m3); ppm; ppb

Ppm is volume-to-volume ratio, which makes it independent of local temperature and pressure.
−6 )(MW) 3 L 106 μg
μg (ppm × 10 (10 3 ) ( )
m g
3
=
m V/mol
where the volume, V, is influence by the temperature and pressure of the gas.
According to Avogadro’s Law, one mole of any gas occupies the same volume as one mole of any other gas at the same
temperature and pressure.
At 273K and 1 atm pressure, standard conditions for many chemical reactions, this volume is 22.414 L/mol.
Most regulations for air quality determinations are referenced at 25ºC and 1 atm, while most source measurements are
referred at 21.1ºC and 1 atm.
To convert the volume per 1 mole of gas at these or other conditions, we can use the formula:
P1 V1 P2 V2
=
T1 T2
Example:

1. A one cubic meter sample of air was found to contain 80µg/m3 of SO2. The temperature and pressure were 25ºC
and 103.193 kPa when the air sample was taken. What was the SO 2 conc. in ppm?
Solution:
at 25ºC and 103.193 kPa
1atm
1atm(22.414𝐿/𝑚𝑜𝑙) 103.193kPa (101.325kPa) (𝑉)
=
273K 228K
V = 24.0237L/mol

concentration in ppm
μg 1mol 24.0237L 1m3 106 μL 1g μL
ppm = 80 3
( ) ( ) ( ) ( ) ( 6 ) = 0.03 = 0.03ppm
m 64g 1mol 1000L 1L 10 μg 1L
or
 μg 24.0237L
80 ( )
ppm = m3 1mol = 0.03ppm
64g 1000L
( 3 )
1mol 1m

2. Convert 1950µg/m3 of SO2 to ppm at 25ºC and 101.325 kPa pressure

Solution:
at 25ºC and 101.325 kPa
22.414𝐿
1atm ( ) 1atm(𝑉)
𝑚𝑜𝑙 =
273K 298K
𝑉 = 24.4666𝐿/𝑚𝑜𝑙
concentration in ppm
μg 1mol 24.4666L 1m3 106 μL 1g μL
ppm = 1950 3
( ) ( ) ( ) ( ) ( 6 ) = 0.75 = 0.75ppm
m 64g 1mol 1000L 1L 10 μg 1L
3. A sample of air analyzed at 0 OC and 1 atm pressure is reported to contain 9 ppm of CO. Determine the equivalent
CO concentration in micrograms per cubic meter and milligrams per cubic meter.
Solution:

𝑔 L 106 μg
μg (9ppm × 10−6 ) (28 ) (103 3 ) ( ) μg mg
𝑚𝑜𝑙 m g
= = 10,321.95 3 = 10.32 3
m3 24.414/mol m m

SOURCES OF AIR POLLUTANTS

All air contains natural contaminants such as:
- pollen
- fungi spores,
- salt spray and
- smoke and dust particles from forest fires and volcanic eruptions

It also contains
- naturally occurring CO from the breakdown of methane,
- hydrocarbons in the form of terpenes from pine trees,
- hydrogen sulfide and methane from the anaerobic decomposition of organic matter

Air pollutants of anthropogenic origin are due to:

- the use of fossil fuels for heating and cooling
- transport
- industrial use and for energy conversion
- incineration of various forms of industrial, municipal and private waste

Categories of Sources of Air Pollutants:

1. Mobile sources are any air pollution sources that can be moved from one location to another.
examples: motor vehicles, aircrafts, ships, handling and/or evaporation of gasoline
2. Stationary sources are any fixed emitter of air pollutants.
examples: residential, commercial, industrial power and heating including steam-powered power plants, sewage
treatment plants
3. Area sources are smaller sources of air pollution.
4. Industrial Processes
- Chemical
- Metallurgical
- pulp and paper industries
 - petroleum refineries
5. Solid-Waste Disposal
- household and commercial refuse
- coal refuse
- agricultural burning

CLASSIFICATION OF AIR POLLUTANTS

Air Pollutants can be also classified according to:

• ORIGIN
1. Primary Pollutants are emitted from a process/source directly in the atmosphere and found there in the form in
which they were emitted.
examples: ash from volcanic eruption
carbon monoxide gas from motor vehicle exhaust
sulfur dioxide released from factories
2. Secondary Pollutants are formed in the atmosphere when the primary pollutants and atmospheric constituents react
or interact. They are usually formed by a photochemical reaction or by hydrolysis or oxidation.
examples: ground level ozone
photochemical smog

• CHEMICAL COMPOSITION
1. Organic compounds are compounds which contain carbon and hydrogen and many also contain other elements
such as oxygen, nitrogen, phosphorus and sulfur. Organic compounds of concern include hydrocarbons, carboxylic
acids, alcohols, ethers, amine, and organic sulfur compounds.
a. Particulate organic compounds
b. Volatile organic compounds
2. Inorganic compounds found in contaminated atmosphere include CO, CO2, carbonates, SOx, NOx, O3, hydrogen
fluoride, hydrogen chloride.

• STATE OF MATTER
1) Particulate pollutants are any dispersed matter, finely divided solids and liquids, in which the individual aggregates
are larger than a single small molecule (about 0.002m in diameter) but smaller than 500 m. It includes dust, fumes,
smoke, fly ash, mist and spray, that will settle out of the atmosphere.
Particulate pollutants are inhalable and respirable. Particulates with a diameter less than 10 microns (PM10), including
fine particles less than 2.5 microns (PM2.5) pose the greatest risks to health as they are capable of penetrating
people’s lungs and entering their bloodstream.

Classification of Particulate Pollutants:

a. according to physical characteristics
• Size is one of the most important physical properties of particulates and is measured in m.
*Particles larger than 50 m can be seen by the naked eye and those smaller than 0.005 m may only be
observed through an electron microscope.
*Human hair ranges from 5m to 600 m in diameter.
*Particles smaller than 1 m do not tend to settle out rapidly.
• mode of formation
i. Dust – are small solid particles created by the breakup of larger masses through crushing, grinding, or
blasting
ii. Smoke – are fine solid particles resulting from the incomplete combustion of organic particles such as
coal, wood or tobacco. It mainly consists carbon and other combustible materials with diameters
ranging from 0.5 m to 1 m.
 iii. Fumes – are fine solid particles (often metallic oxides such as zinc and lead oxides) formed by the
condensation of vapors of solid materials. Its size ranges from 0.03 m to 0.3 m.
iv. Fly ash – consists of finely divided, noncombustible particles contained in flue gases arising from the
combustion of coal. Its size ranges from 1 – 1000 m.
v. Mist – consists of liquid particles or droplets formed by the condensation of vapor, the dispersion of
liquid or the enactment of a chemical reaction. Mists are usually less than 10 m in diameter. It’s
called a fog if the concentration is high enough to obscure visibility.
vi. Spray – consists of liquid particles formed by the atomization of parent liquids, such as pesticides and
herbicides. Spray particles range in size from 10 m - 1000 m.

• settling characteristics
Settling characteristics are one of the most important properties of particulates since settling is the major
natural self-cleansing process for the removal of particulates from the atmosphere.
i. Suspended particles – vary in size from less than 1 m to approximately 20 m. They remain suspended
in the atmosphere for a long period of time.
ii. Settleable particles – otherwise known as dustfall, are larger and heavier and tend to settle out close to
their sources. They are generally greater than 10 m in size.
• optical qualities
Reduction in visibility is one of the most obvious effects of air pollution, and the scattering of light by
particulate matter is primarily responsible for that reduction. Particles in the range of visible light (0.38 m
to 0.76m) are the most effective in visibility reduction.
b. according to chemical characteristics
Atmospheric particulates contain both organic and inorganic components. Some of the most common of the
organics found in particulates include phenols, organic acids and alcohols. Common inorganics found in
particulates include nitrates, sulfates and metals such as iron, lead, manganese, zinc and vanadium.
c. according to biological characteristics
Biological particulates in the atmosphere include protozoa, bacteria, viruses, fungi, spores, pollens and algae.
Microorganisms generally survive for only a short time in the atmosphere because of the lack of nutrients and
UV radiation of the sun.
2) Gaseous pollutants are formless fluids that completely occupy the space into which they are released, behave
much as air and do not settle out of the atmosphere.
a. Hydrocarbons - are organic compounds containing only carbon & hydrogen.
Most gasoline and other petroleum products are hydrocarbons which are divided into:
• aliphatic
i. alkanes – saturated hydrocarbons (i.e. methane) that are fairly inert and generally not active atmospheric
photochemical reactions
 ii. alkenes – often called olefins, are unsaturated and highly reactive in atmospheric photochemistry. The
reactivity of alkenes such as ethylene makes them much more important in the study of air pollution
than alkanes because, in the presence of sunlight, they react with NO2 at high concentrations to form
secondary pollutants such as PAN and O3
iii. alkynes – highly reactive but are relatively rare; not of major concern in air pollution studies
• aromatic - are biochemically and biologically active and some are potentially carcinogenic

Hydrocarbon present in the atmosphere are from natural sources though small amounts of these come from
geothermal areas, coal fields, natural gas from petroleum fields and natural fires.

Other hydrocarbon are the volatile terpenes and isoprene produced by plants and trees. The terpene molecules
combine to form aerosols that produce the “blue haze” over forested areas.

Sometimes, a blue haze lingers over

forests. This blue haze phenomenon is
caused by natural organic aerosols. These
airborne particles absorb, reflect and
scatter incoming solar radiation, thus
causing the bluish shimmer that can be
seen over forests on sunny days.

Mountains look blue from a distance

because of blue haze that blankets it.

In small amounts, hydrocarbon may be present in the atmosphere from anthropogenic sources like
transportation, fuel combustion in stationary sources, industrial processes, solid-waste disposal, forest fires,
agricultural burning and coal waste fires.
b. Carbon Monoxide - is a colorless, tasteless and odorless, chemically inert gas under normal conditions which is
a product of the incomplete oxidation of carbon. It has an estimated atmosphere mean life of about 2 ½ months,
non-irritating but is very poisonous and lethal at a concentration of 5000ppm.

Carbon monoxide in the atmosphere are both of natural and anthropogenic in origin. About 3.5 billion tons of
it are produced in nature yearly by the oxidation of methane gas from the decaying vegetation. It can also be
produced by human metabolism – the exhalation of a resting person contains approximately 1 ppm CO.
Anthropogenic sources of carbon monoxide include transportation, fuel combustion in stationary sources,
industries, solid waste and others.
c. Oxides of Sulfur
 Sulfur oxides are compounds of sulfur and oxygen molecules.
• The predominant form is sulfur dioxide found in the lower atmosphere. Sulfur dioxide is a colorless gas that
can be detected by taste and smell in the range of 1000 to 3000 micrograms per cubic meter. It is a
nonflammable and nonexplosive gas with a suffocating odor. It has a taste threshold of 784 µm/ m3 (0.3
ppm) and odor threshold of 1306 µm/ m3 (0.5 ppm). It is highly soluble in water and is twice as heavy as air.
At concentrations of 10,000 µg/m3, it has a pungent and unpleasant odor.
This gas readily dissolves in water present in the atmosphere to form sulfurous acid. It is estimated to remain
airborne at an average of 2-4 days during which time it may be transported as far as 1000 km, thus, the
problem of SO2 can become international.
• Sulfur trioxide is either emitted directly into the atmosphere or produced from sulfur dioxide and is rapidly
converted to sulfuric acid.

Sources of sulfur oxides in the atmosphere:

• The burning of solid and fossil fuel contributes more than 80 % of anthropogenic SO2 emissions
• Fuel combustion in stationary sources (primarily electric utilities) and industrial processes are the principal
contributors of Sox from human sources
• Transportation contributes little to the anthropogenic Sox in the atmosphere, because the sulfur content of
gasoline is low.
• Present concern about automotive catalytic converters oxidizing SO2 to SO3 is of small consequence when
compared to the potential dangers of CO and HC emissions. However, the SO3 can react with moisture in
the air to produce H2SO4 mist.
d. Oxides of Nitrogen
Nitrogen oxides are compounds of nitrogen and oxygen molecules. Two oxides of nitrogen that are significant
air pollutants are nitrogen monoxide and nitrogen dioxide. They are produced from the reaction of nitrogen
and oxygen gases in the air during combustion, especially at high temperatures. In areas of high motor vehicle
traffic, such as in large cities, the amount of nitrogen oxides emitted into the atmosphere as air pollution can
be significant.
They can also be produced in the atmosphere by lightning and forest fires and bacterial decomposition of
organic matter which produces approximately ten times as much nitrogen oxides as do anthropogenic sources.

Hydrocarbons react with oxides of nitrogen to produce photochemical smog consisting of air contaminants
(secondary pollutants) such as ozone, PAN, aldehydes, ketones, alkyl nitrates and CO.
e. Volatile Organic Compounds
These compounds are emitted as gases from certain solids or liquids. They include a variety of chemicals and
are released from burning fuel such as gasoline, wood coal or natural gas. They are also released from many
consumer products including cigarette, solvents, paints and thinners, adhesives, hobby and craft supplies, dry
cleaning fluids, glues, wood preservatives, cleaners and disinfectants, moth repellants, air fresheners, building
 materials and furnishings, copy machines and printers, and pesticides. Because of this, VOCs have a higher
concentration indoor than outdoor.
When VOCs combine with nitrogen oxides in the air, they form smog.
f. Photochemical Oxidants
Oxidants or total oxidants are two terms used to describe levels of photochemical oxidants. They generally
indicate the net oxidizing ability of ambient air.
• Ground Level Ozone is a photochemical oxidant that makes up approximately 90% of the oxidant pool. It is
a secondary pollutant, meaning that it is not directly emitted. Instead, it is produced when carbon monoxide
(CO), methane, or other volatile organic compounds (VOCs) are oxidized in the presence of nitrogen oxides
(NOx) and sunlight.

Other photochemical oxidants of concern in air pollution monitoring are:

• Nascent oxygen
• Excited molecular oxygen
• Peroxyacetyl nitrate (PAN) is a photochemical oxidant that is more stable than ground level ozone, hence it
is more capable of long-range transport. It serves as a carrier for NOx into rural regions and causes ozone
formation in the troposphere.
• Peroxy-butyl nitrate
• Nitrogen dioxide
• Hydrogen peroxide
• Alkyl nitrates
A photochemical smog is a mixture of pollutants that are formed when nitrogen oxides and volatile organic
compounds react to sunlight, creating a brown haze above cities. It is most prominent during the morning and
afternoon, especially in densely populated areas. It tends to occur more in the summer because that is when we
have sunlight.