Et ZC362-L2

Environmental Pollution Control
(ETZC362)
Dr. Jegatha Nambi Krishnan
Department of Chemical Engineering
11
th
Jan. 2014
1 etzc362
BITS Pilani, K K Birla Goa Campus 11
th
Jan. 2014 (Course Code: etzc 362)
Air Pollution
2

Air pollution:
any atmospheric condition in which certain substances are present in
such concentrations that they can produce undesirable effects on man
and 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 on
humans, animals, plants or property.

Ex. Sulphur dioxide - > 2 x 10
-4
ppm

BITS Pilani, K K Birla Goa Campus
1. Mass concentration, , defined as the ratio of the mass of
pollutant to the mass of air plus mass of pollutant

Where m
p
is the mass of pollutant and m
a
is the mass
of 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
p a
p
p
m m
m
w
+
=
p a
p
p
v v
v
y
+
=
3
3. Volume concentration in parts per million (ppm), y
ppm

4. Mass-Volume concentration,
p
(g of pollutant per cubic
metre 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 are
usually formed in the atmosphere

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th
6
10 =
p ppm
y y
p a
p
p
v v
m
+
=
4
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The relation between
p
and y
ppm
:

p -
Concentration of a pollutant whether it be gaseous
or particulate (g/m
3
)

y
ppm
- Volume concentration in parts per million (ppm),

M
p
- Molecular weight of the pollutant

( )
45 . 24
10
3
ppm
p
p
y M
=
5
The normal cubic meter is important if the emission
temperature is greater than ambient as one mole of the
emission gas does not occupy 22.4 L.

At non standard temperatures and pressures, corrections
have 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
kPa 101
*
K 273
T
* 22.4 mole 1 =
6
Classification Air Pollutants
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Primary Pollutant (Directly emitted from source)- Ex. Particulate
matter, inorganic gases and radioactive compounds.
Secondary Pollutant (Formed as a result of chemical and
photochemical 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 200 m. These are formed by
natural disintegration of rock and soil or by mechanical processes
of grinding and spraying.
Smoke Fine particles of size ranging from 0.01 to 1 m resulting
which can be liquid or solid from combustion or other chemical
processes. Based on materials burnt it is of different colours.

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th
Fumes Particles of size ranging from 0.1 to 1 m formed
by condensation, sublimation , or chemical reaction /
metallurgical processes.
Mist Liquid droplets generally smaller than 10 m 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 1 m. Dispersion of microscopic solid or liquid
particles in gaseous media.
8
Particles- 1-10m
Particles of size ranging from 0.1 to 1 m have smaller settling velocities readily
stirred 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 10 m 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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9
th
Sizes of Atmospheric particulate matter
10
Gaseous Pollutants
Oxides of Sulphur (SO
x,
H
2
SO
3
)
SO
2
is the most important pollutant emitted and is oxidized slowly in clean air to sulphur
trioxide. SO
3
with moisture in atmosphere to form sulphuric acid. Both SO
2
and SO
3

are 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 (NO
x
= NO &NO
2
)
Among the seven oxides of nitrogen, N
2
O, NO and NO
2
are formed in appreciable
quantities in the atmosphere. NO
2
major pollutant emitted by fuel combustion and
nitric acid plants.

Carbon Monoxide (CO) and CO
2
CO -Single largest pollutant in urban atmosphere and has strong affinity towards
hemoglobin of blood stream and so dangerous asphyxiant. The rate of oxidation of
CO to CO
2
is very slow. The main sources of CO in the urban air are smoke and
exhaust fumes of burning gas, coal or oil.
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11
Lighter Hydrocarbons (HCs)

Gaseous and volatile liquid hydrocarbons.

CH
4
is the abundant hydrocarbon constituting 40-80% of total
HCs. It has very low photochemical activity and so non-methane
HC concentration is of interest.

Among the alkenes, ethylene and propenes are prominent
pollutants. Ex: toluene and m-xylene (urban atmosphere)

Terpenes-volatile HCs (pine tar and wood sources)

These are responsible for the production of secondary
pollutants in the presence of sunlight and nitrogen oxides forming
photochemical oxidants Ozone.

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12
Emission sources- Source type
Natural
The pollutant emission from natural sources is much greater than
that from anthropogenic sources. Fortunately, natural pollutants
are distributed throughout the world and reach a sink such as
ocean or the soil. The atmosphere can cleanse itself from the
pollutants given sufficient time. Ex. wind blown dust, pollen, sea
salt nuclei, volcanic ash and gases, smoke and trace gases from
forest fire.

Anthropogenic
The pollutants are concentrated in specific locations and reach
high levels in atmosphere. The emission of these pollutants is at
such massive rates that they overwhelm the capacity of the
environment to cleanse itself. Ex. Combustion of fossil fuels Ex.
SO2, NO2, CO & fly ash, trace metal oxides, Ex. mercury, lead and
cadmium. Chemical and metallurgical industries, food and
agriculture etc.

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th
13
th
Classification of Anthropogenic Air
pollution sources
14
th
pollution sources
15
th
pollution sources
16
Behavior and Fate of Air Pollutants
Natural Pathways (scavenging processes) of exchange of
pollutants 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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th
17
Wet Precipitation

Wet precipitation has two distinct mechanisms rainout and
washout

The rainout includes various processes taking place inside
clouds, where the contaminants serve as condensation nuclei on which
droplets condense. Ex. Particles less than 0.1 m . These particles
captured 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 and
sulphate particles formed after chemical reactions.

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18

Dry Deposition
Particulate matter smaller than 0.1m often coagulates through mutual collisions and forms
larger aggregates which are effectively removed by gravitational settling. Brownian motion is
the major mechanism of coagulation, although atmospheric turbulence also enhances the
diffusive 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
v
t
= terminal settling velocity; d
p
= particle diameter;

p
and
a
= density of particle and air, respectively;

a
= viscosity of air; P = air pressure; C = constant

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th
( )
|
|
.
|
\
|
+ =
p d
C
gd
v
p
a p
a
p
t
2
1
18
2


19
Interaction at the earths surface

Gaseous pollutants can be transported to the earth surface by
atmospheric turbulence where they interact with the ocean
surface, vegetation and upper layers of the soil and are removed
by absorption or chemical reaction.

SO
2
and CO are the 2 major pollutants formed.

SO
2
- Ocean, vegetation and upper layers of the soil

Co converts to CO
2
or CH
4
- Biological action by the bacteria in
the soil acts as a sink.
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20
Chemical reactions in the atmosphere

Many of the gaseous pollutants undergo chemical reactions within the
atmosphere 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 form
nitric acid.

CO is removed by the fast reaction with hydroxyl radicals present in the
atmosphere. Another possible mechanism is the migration of CO into the
stratosphere, where the oxidation to CO
2
may subsequently take place by
the hydroxyl radicals. All these pollutants inter-react by photochemical
processes in the phenomenon known as the photochemical smog.

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21
th
Interaction at the Earths surface
Absorption
At the ocean surface SO
2,
first diffuses through the gas phase, crosses the
gas-liquid interface, and finally diffuses into the bulk of the ocean where
it is absorbed
NO
2
also absorbed by ocean and other surface waters
ADSORPTION
SO
2
first diffuses to the external surface of the solid, penetrates into the
pores of the solid,
and is subsequently adsorbed on the pore site

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th
BIOLOGICAL ACTION IN SOIL

Soil contains certain bacteria which can make use of
CO in their metabolism, producing either CO2 or CH4.

O H CH H CO
CO O CO
2 4 2
2 2
3
2 2
+ +
+
23
th
SO
2
is oxidized to SO
3
which combines with atmospheric
moisture to form H
2
SO
4
mist(Slow process)

Metal salt particles serve as nucleation sites for droplet
formation and react with H
2
SO
4
to produce sulphates,
which are also removed by wet precipitation

4 2 3 2
3 2 2
2 2
SO H SO O H
SO O SO
+
+
HCl SO Na SO H NaCl 2 2
4 2 4 2
+ +
Chemical reactions in atmosphere
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th
Direct conversion of NO
2
to HNO
3
in presence of moisture
(slow process)

NO HNO O H NO + +
3 2 2
2 3
Chemical reactions in atmosphere
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th

Conditions for the formation of photochemical smog are Air
stagnation, sunlight, & high concentration of HCs & N oxide
in the atmosphere.

Smog arises from photochemical reactions in the lower
atmosphere by the interaction of HCs & nitrogen oxide
released by exhausts of automobiles & some stationary
sources.

This interaction results in a series of complex reactions
producing secondary pollutants like ozone, aldehydes,
ketones, & PAN

Photochemical Smog
26
th
smog NO HC
atm lower at and hv
x
+

) (PANs Nitrates Peroxyacyl

Ketones
Aldehydes
Ozone
Photochemical Reaction

Photochemical Smog
27
Interaction at the Earths surface

ABSORPTION

At the ocean surface SO
2,
first diffuses through the gas phase,
crosses the gas-liquid interface, and finally diffuses into the bulk of
the ocean where it is absorbed
NO
2
also absorbed by ocean and other surface waters

ADSORPTION

SO
2
first diffuses to the external surface of the solid, penetrates
into the pores of the solid,
and is subsequently adsorbed on the pore site

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28
Photochemical smog

The 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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29
The starting mechanism is the absorption of ultraviolet light
from the Sun by NO
2
. This causes the nitrogen dioxide to
decompose into nitric oxide and highly reactive atomic
oxygen .
O NO hv NO + +
2
The atomic oxygen initiates oxidizing processes or quickly
combines with molecular oxygen to form ozone, which
itself is reactive and acts as an oxidant:
2 2 3
3 2
O NO NO O
M O M O O
+ +
+ + +
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30
M is an energy-absorbing molecule or particle is required to
stabilize O
3
or else it will rapidly decompose.
Under normal conditions, the ozone formed will be quickly
removed by reaction with NO to provide NO
2
and O
2.
However, when hydrocarbons are present in the atmosphere
this mechanism is partially eliminated as NO reacts with the
hydrocarbon radical peroxyacyl (RCO
.
3
) and as a result ozone
concentration builds up to dangerous levels.
Hydrocarbons compete for free oxygen released by NO
2

decomposition to form oxygen-bearing free radicals such as the
acyl radical.
( ) HC O RCO acyl radical
+
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31
This radical takes part in a series of reactions involving
the formation of still more reactive species, which in turn
react with O
2
, hydrocarbons and nitric oxide.
( )
( )
3
2
.
2
3
2
2
.
3
.
2
3
3
2
) (
O RCO O RCO
NO RCO NO RCO
ketones CO R
aldehydes RCHO HC RCO
radical peroxyacyl RCO O RCO
+ +
+ +
+
+

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32
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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33
Effects of Air Pollution
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Human health
Adverse effects may be divided into acute and chronic
effects.

Acute: High concentration for shorter duration.

Chronic: lower concentration for higher durations
(prolonged periods).

Particular attention to six pollutants:
Particulates, sulphur oxides, carbon monoxide, nitrogen
oxides, hydrocarbons and photochemical oxidants.
34
th

Pollutants may Enter into body by 4 ways:

Ingestion: by means of swallow
Inhalation: by means of respiration inhaled into
lungs
Absorption: by means of absorption in skin or eye
Injection: by means of external injection

35
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.
36
Particles above 10 m are almost retained in the nose itself
and smaller than this may escape the entrapment and
passes through the URT.

Fine particle in the size range from 0.5 to 5 m are
deposited in LRT.

This results in the damaging the respiratory organs.

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37
th
The Respiratory and the Alveoli.
the pulmonary alveoli are the terminal ends of the respiratory tree, which outcrop
from either alveolar sacs or alveolar ducts, which are both sites of gas exchange
with the blood as well. Carbon dioxide rich blood is pumped from the rest of the
body into the alveolar blood vessels where it through diffusion releases its carbon
dioxide and absorbs oxygen.
Source: Wikipedia
38
Particulate Matter:

Interference of inert particles with the clearing
mechanisms of the respiratory tract.

Particles act as carriers of adsorbed toxic gases
such as SO
2
and produce synergetic effects.

Particles may be intrinsically toxic because of their
physical or chemical characteristics.
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39
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 producing
hypertension in humans. Also causes cardiovascular diseases when exposed to
fumes 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 separating
bloodstream from brain causing injury to cerebellum and cortex.

Higher levels of mercury can build up in the fetus without the mother
showing any signs of illness. The effects are congenital birth defects or the
death of the fetus.

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40
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 SO
2
is the formation of H
2
SO
4
and sulphate aerosols.

Carbon Monoxide
When inhaled, passes through the lungs and diffuses directly
into the blood stream to form carboxyhemoglobin, because of its
affinity, 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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41
th

Oxides of Nitrogen

NO is not irritant and does not show any adverse health effects at the
concentrations generally occurs in the atmosphere.
NO
2
is relatively insoluble and upon inhalation causes damage to the lung tissues.
It form HNO
2
& HNO
3
which are highly irritating & cause damage to the lungs
tissue
Long-term exposure even with 1ppm may lead to health problem like biochemical
change in blood

Hydro carbons and Photochemical Oxidants

At the concentrations usually found in the urban air, causes no adverse effects on
human health. The oxidant produced in photochemical smog causes irritation to
the 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

42
Effects on Vegetation

Leaf 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 to
palisade and spongy mesophyll.

The damages are necrosis (dead areas), chlorosis (loss or
reduction chlorophyll), epinasty (downward curvature of
the leaf).

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

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43
th
44
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 SO
2
.

Ozone is also very reactive substance and causes the
cracking of synthetic rubbers at the levels of 0.01 to 0.02
ppm.
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45
Green house effect: Global warming
Out of total light energy 20% is absorbed by gases in
atmosphere, 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 CO
2
, 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 processes
keep the earths surface and its atmosphere warm and is called Green
house effect.
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46
th
47
th

Major Air Pollution Disasters
48
Ozone Hole
Ozone layer or natural sunscreen is located in stratosphere
It filters ultraviolet rays of the sunlight, which is harmful to
humans and other forms of life.
Certain gases like Freons or chlorofluoro compounds(CFCs)
used as fluids in refrigerators and also as propellants in spray
cans of deodorants, perfumes etc is the main cause for the
atmospheric ozone depletion.
Cl
2
CF
2
+ h Cl. + ClCF2.
Cl. + 0
3
ClO + 0
2
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49
th
Properties of air pollutants
Carbon monoxides

Constitutes the single largest pollutant in the urban
atmosphere
Has a B.Pt of -192
0
C
Affinities towards hemoglobin in blood stream & is
dangerous 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 air
pollutants

50
th

Air Pollution Laws

To control, to reduce & to monitor

Oldest anti-pollution law Smoke nuisance
Act1920 for Bombay city

Central Air Act,1981 and empowered central
Board formed for Prevention & Control of Water
Pollution,1974

The State PCB are also authorized to close,
prohibit/regulate any industry/operation for
improper implementation of acts

51
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Function of Central PCB

Advise GOI about prevention, control & abatement of
air pollution acts

Coordination with state PCBs

Plan, arrange & execute training programs on Air Pollution
Prevention & 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

52
th

Air Pollution Standards

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) sets
permissible limit of air pollutants

53
th

Air Quality Standards

In USA, the standards are set by United State Environment
Protection Agency

2 types of air quality standard US: Primary & Secondary

54
th
Chapter-2 (Problems)
Problem-1

Carbon monoxide (CO) is present in standard
atmospheric air at a concentration of 50 ppm.
Compute volume concentration, mass-volume
concentration and mass concentration values for
the CO concentration in the atmosphere.

Given: air density at standard condition is 1.185
kg/m3 and the molecular weight (MP) is 28.

55
th
Given data:
Concentration of CO = 50 ppm
Volume concentration, y
p
= y
ppm
x 10
-6
= 50 x 10
-6
= 5 x 10
-5

Mass volume concentration,
p

Mass concentration w
p
, can be calculated as follows:
Divide mass concentration to volume concentration equation

Solution
56
th

But the term (m
a
+m
p
/v
a
+v
p
) can be written as

Taking the density of air,
a
, as equal to m
a
/v
a
, and density
of pollutant,
p
= (m
P
/v
P
)y
p
; we get

|
|
.
|
\
|
+
+
=
p a
p a
p
p
p
p
m m
v v
v
m
y
w
p
p
p
a
a
a
p a
p a
) 1 ( y
v
m
y
v
m
v v
m m
+ =
+
+
000048 . 0
10 26 . 57 ) 00005 . 0 1 ( 185 . 1
10 26 . 57
) 1 (
6
6
p p a
p
p
=
+

=
+
=

y
w
Solution
57
th
Problem 2

A 1 m
3
sample of air was found to contain 80 g/m
3

of
SO
2
. The temperature and pressure were 25
o
C and
103.193 kPa when the air sample was taken.
What was the SO
2
concentration in ppm.

M.wt of SO
2
= 64.07
Convert to ppm; using equation in page 6.

2
3 3
3
SO of ppm 03 . 0
07 . 64 1000 m 1
193 . 103
325 . 101
273
298
414 . 22
80
ppm =

=
m L
m
g
( )
45 . 24
10
3
ppm
p
p
y M
=
58
th
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

59

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Environmental Pollution Control

Behavior and Fate of Air Pollutants

) (PANs Nitrates Peroxyacyl

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