CH 262 Environmental Chemistry Slides

CH 262
ANALYTICAL
AND
ENVIRONMENTAL
CHEMISTRY
1
ENVIRONMENTAL CHEMISTRY
Content
1. Introduction
2. Atmospheric Chemistry (Composition of the
atmosphere, Atmospheric pollution, Tropospheric
chemistry and Stratospheric chemistry)
3. Water and Soil Pollution
4. Major Pollutants (Pesticides, Heavy Metals,
Persistent Organic Pollutants-POPs, Solid and
Hazardous Wastes)
5. Effects of Water and Soil Pollution
6. Water Quality Parameters
7. Management of Water and Soil Pollution; Water
Treatment, Water Disinfection and Wastewater
INTRODUCTION TO
ENVIRONMENTAL CHEMISTRY
Environmental chemistry is the study of the

sources, transport, reactions, effects, and fates
of chemical species in the environment.
 Environmental chemistry is about

environmental issues and the chemistry
behind them (chemistry of the environment).
 It aims to apply knowledge of chemistry to

understand environmental issues.
Environmental Pollution
Environmental pollution: Contamination of the
natural environment with substances that adversely
affect the health, survival, or activities of humans or
other living organisms.
 Pollutants are substances that have harmful effects
on the health, survival, or activities of humans or
other living organisms. They are substances that
under excessive quantity in a wrong place and a
wrong time will cause impurity to the living
environment. Simply put, they are the things that
cause pollution.
 Examples of pollutants: Nitrogen oxides, sulfur

oxides, particulate matter, ground level ozone,
volatile organic compounds, heavy metals.
 In the process of environmental pollution, pollutants

ATMOSPHERIC CHEMISTRY
 Atmospheric chemistry is the study of the
composition, and chemical transformations
occurring in the atmosphere.
 The atmosphere is a thin layer of gases that

envelops the earth.
 Atmospheric chemists are interested in

understanding chemical composition of the natural
atmosphere, the way gases, liquids, and solids in
the atmosphere interact with each other and with
the Earth's surface, and how human activities may
be changing the chemical and physical
characteristics of the atmosphere.
5
Composition of the Atmosphere
N2 = 78.08%
O2 = 20.95%
Ar = 0.93%
CO2 = 0.03%,
Water vapor (Variable). In addition, air contains a large
variety of trace level gases at levels below 0.002%,
including neon, helium, methane, krypton, nitrous
oxide, hydrogen, xenon, sulfur dioxide, ozone, nitrogen
Composition of the Atmosphere…
 These trace components are where the interesting

atmospheric chemistry occurs.
The atmosphere: reservoir of gases, moderates

Earth’s temperature and absorbs damaging
ultraviolet (UV) radiation from the sun.
7
Expressing the amount of substances
in the atmosphere
The concentration of a gas in the environment is

expressed as: μg/m3, mg/m3, mol/m3, “parts per …..”
(parts per million, parts per billion and parts per trillion)
 The “parts per …..” units express the number of

molecules of a pollutant that are present in one million
or billion or trillion molecules of air
 Example, a concentration of 100 molecules of a gas
such as CO2 dispersed in one million (106) molecules of
air would be expressed as
 “100 parts per million,” i.e. “100 ppm.”
 Similarly, “ppb” and “ppt” stand for “parts per
billion” (109) and “parts per trillion” (1012)
respectively.
8
Regions of the Atmosphere
 The atmosphere extends from the earth’s

surface to hundreds of kilometers into space.
 Functions of the atmosphere include:

reservoir of gases, moderates Earth’s
temperature and absorbs energy and
damaging ultraviolet (UV) radiation from the
sun.
With increasing distances from the earth’s
surface, properties such as density, pressure
and temperature of the atmosphere gradually
change.
Regions of the Atmosphere…
 The atmosphere
is divided into
five layers on
bases of altitude
and temperature
variation.
 Boundaries between
these regions are:
tropopause,
stratopause,
mesopause, and
thermopause
The most significant
respectively.
are the troposphere
and stratosphere.
Troposphere
 Lowest layer of Earth's atmosphere. It extends
from the Earth's surface to an average height of
about 12 km.
 The troposphere contains air and clouds. Nearly

all atmospheric water vapor or moisture is found
in the troposphere, so it is the layer where most
of Earth's weather takes place. Most of our
weather (e.g. rain, snow, and wind) occurs in
this layer.
 We live our entire lives within the troposphere.
 The troposphere is denser than the other layers

11
Troposphere…
 Temperature in the
troposphere generally
decreases with increasing
altitude, reaching a
minimum of about –58 °C
at its upper boundary.
 This is because the
troposphere is mostly
heated through energy
transfer from the earth’s
surface.
 Thus, the lowest part of
the troposphere is
typically the warmest
Stratosphere
 The stratosphere is the second-lowest layer of
Earth's atmosphere.
 It is the layer above the troposphere, separated

from it by the tropopause. It extends to about 50
km.
 The stratosphere contains the ozone layer; It is the

part of the atmosphere that contains relatively high
concentrations of ozone. Ozone absorbs ultraviolet
(UV) radiation from the sun. By doing so, ozone
converts the radiation’s energy to heat and is
responsible for the temperature maximum
encountered at the boundary between the
stratosphere O 3 + the
and hv mesosphere
O2 + O • at an altitude 13of
Stratosphere
 The absorption of the solar radiation causes the
rise in temperature with altitude in this layer;
temperature increases with altitude, reaching a
maximum of nearly -2°C at the stratopause.
 The presence of ozone in the stratosphere helps

to shield the Earth’s surface from the sun’s
harmful ultraviolet (UV) radiation.
The lower atmosphere
 The troposphere and the stratosphere

together are called the lower atmosphere.
 The lower atmosphere is the domain of

main interest from the environmental
perspective:
Ozone depletion (stratosphere)
Air pollution (troposphere)

15
Mesosphere
 Beyond the stratosphere lies the mesosphere;
below the thermosphere (third-highest layer of
Earth's atmosphere).
 The mesosphere extends from the top of the
stratopause to about 80 km.
 In the mesosphere, temperature decreases with

altitude because there is little ozone in the air to
absorb solar radiation (due to the absence of
high levels of radiation-absorbing species). The
atmosphere reaches its coldest temperatures
(about -90°C) at the top layer of the
mesosphere.
Thermosphere
 This is the layer above the mesosphere
(second-highest layer of Earth's atmosphere).
 It extends from the mesopause to the

thermopause (exobase), at an altitude range of
500–1000 km.
 In the thermosphere, temperature rises with

altitude, caused by the absorption of intense
solar
 radiation by atmospheric gases,
Molecules of oxygen gas absorbs much of the
principally O2.
high-energy UV radiation and photodissociate to
produce atomic oxygen.
O2 + high-energy UV → 2O
Thermosphere…
 Molecular nitrogen and oxygen, as well as atomic
oxygen, undergo photoionization in the upper
atmosphere. Photoionization is a process in which
highly energetic radiation is absorbed by removing
electrons from atoms, resulting in the formation of
ions. Ions and electrons are most abundant.
 High-energy radiations from the sun are absorbed in

the thermosphere, raising its temperature to
hundreds or at times thousands of degrees.
Thermosphere…
 The temperature of the thermosphere gradually increases

with height.
 The ionosphere is a region of the atmosphere that is

ionized by solar radiation.
 Since most of this harmful radiation is absorbed during

photodissociation and photoionization, no UV light having
wavelengths shorter than 220 nm reaches the Earth's
surface. This screening protects our skin and eyes, and in
fact protects all biological life from extensive damage by
this part of the Sun's output.
Exosphere
Final?
he outermost layer of the atmosphere is the exosph
 Extending from the top of the thermosphere

outward; the exosphere marks the transition
from Earth’s atmosphere to outer space.
Eventually, there are so few molecules that,
for all practical purposes, Earth’s atmosphere
has ended.
There are simply fewer and fewer molecules

of gas at increasingly higher altitudes.
Atmospheric Regions (on the basis of air
T)
21
Atmospheric (Air) Pollution
 Air pollution can be

defined as the addition of
harmful substances to
the atmosphere,
resulting in damage to
the environment, human
health, and quality of life.
 It is an indication of
disturbances to the
composition of
compounds in the
atmosphere. 22
Classification of Air Pollutants
 Based on the way they reach the atmosphere,
air pollutants are classified as primary and
secondary pollutants.
 Primary pollutants: Released directly from
sources.
Examples: sulfur dioxide, nitrogen oxides (NO,
NO2), carbon oxides (CO, CO2).
 Secondary pollutants: Formed through

chemical reactions of the primary pollutants and
the constituents of the unpolluted atmosphere in
the air. They are not emitted directly from a
source.
23
Gaseous Inorganic Air Pollutants
 A number of gaseous inorganic pollutants
enter the atmosphere due to human activities.
 Those added in high amount are:
 CO
 SO2
 NOx (NO, and NO2)
Others are: NH3, N2O, H2S, Cl2, HCl, and HF.

24
Carbon Monoxide, CO
 Carbon monoxide (CO) is a colorless, odorless,

tasteless gas.
 One of the most serious air pollutants;
unnoticed poison of the 21st century; silent
Sources:
killer.
Anthropogenic Sources
 The major amount of CO contamination in the
atmosphere is contributed by anthropogenic
sources.
 Automobile emissions: The incomplete
combustion process that occurs in an engine
can result in the emission of carbon monoxide
Anthropogenic Sources…
 Industries using various carbon-based fuels

as a source of energy.
 Residential sources: E.g. firewood, charcoal,

coal and other fuels burning in stoves.
 Incineration of solid wastes
 Cigarette smoking
 Biomass burning: Agricultural clearing

Natural Sources
Volcanic eruption
Incomplete burning of biomass:

Forest/bushfires, building fires
Fate of atmospheric CO
 CO is removed from the atmosphere by
reaction with hydroxyl radical, HO•
CO + HO• → CO2 + H•
 The reaction produces hydroperoxy radical
O2 + H• + M → HOO• + M
where M is a third body, such as a molecule

of N2, which absorbs excess energy from 28
 HO• is regenerated from HOO• by
HOO• + NO → HO• + NO2
HOO• + HOO• → H2O2 + O2
Followed by:
H2O2 + hv → 2HO•
Health effects of CO
 CO enters the blood stream and binds
preferentially to hemoglobin, thereby
replacing oxygen. Causes headaches,
dizziness, nausea, brain damage, collapse,
Control of CO Emission
Control: Since the internal combustion engine is the primary source of
carbon monoxide emissions, control measures have been concentrated on
automobiles.
 Adjustment of air-fuel ratio: The air-fuel ratio acts as a significant role

in the combustion process. When the air-fuel ratio is too low, there is
no enough oxygen to convert all CO present in a fuel into CO 2. Carbon
monoxide emissions may be lowered by employing a leaner air-fuel
mixture, that is, one in which the weight ratio of air to fuel is relatively
high.
 Application of catalytic converter: A catalytic converter is an

automobile emissions control device that converts more contaminated
pollutants present in the exhaust gases to the lower poisonous
pollutants such as CO2 and N2 by a catalyzing redox reaction. The
basic reactions of CO in the exhaust are oxidation while the NOx
reaction is a reduction with preferred product of N 2.
Sulphur Dioxide
Sources
 Oxides of sulphur enter the atmosphere mostly through
human activities, primarily as SO2 from the combustion
of coal. Can also be produced in the process of
producing sulphuric acid and in metallurgical processes
involving ores that contain sulphur.
 Non-anthropogenic sulphur enters the atmosphere

largely as SO2, H2S from:
 Volcanoes
 Decay of organic matter.

31
SO2 sources…
 Any H2S that does get into the atmosphere is converted rapidly to
SO2 by the following process;
• H2S reacts with hydroxyl radical:
H2S + HO• → SH• + H2O

Sulfanyl radical
• Followed by the following two reactions to give SO2
SH• + O2 → HO• + SO
SO + O2 → SO2 + O 32
Sulphur dioxide reactions in the
atmosphere
• Sulphur dioxide reacts to form particulate matter
which then settles or is scavenged from the
atmosphere by rainfall or other processes.
• Much of the SO2 in the atmosphere ultimately is

oxidized to
– Sulphuric acid
• HO• + SO2 → HOSO2• hydroxysulfonyl radical
• HOSO2• + O2 → HO2• + SO3
• SO3 + H2O → H2SO4
– Sulphate salts
• Ammonium sulphate 2NH3 + H2SO4 →
(NH4)2SO4 33
Effects of atmospheric sulphur
dioxide
• Affect the respiratory tract, producing irritation and increasing
airway resistance, especially to people with respiratory
weaknesses.
• Mucus secretion is also stimulated by exposure to air
contaminated by sulfur dioxide.
• Harmful to plants, it kills leaf tissue.
• It is converted to sulphuric acid, causing acid rain.
• Deterioration of building materials. It attacks limestone, marble
and dolomite (MgCO3·CaCO3) forming products which are either
water-soluble or in the form of poorly adherent solid crusts on
the rock’s surface, adversely affecting the structure and life of
the building.
CaCO3 + SO2 + 2O2 + 6H+ → CaSO4 · 2H2O + CO2 + H2O
34
Removal of Sulphur Dioxide (Control)
 Most of the methods concentrate on coal since it is the
major source of sulphur oxides pollution.
 Many processes have been proposed for the removal of

SO2 from stack of gas:
1. Lime slurry scrubbing
• Ca(OH)2 + SO2 → CaSO3 + H2O
 A scrubber or scrubber system is a system that is used to remove

harmful materials from industrial exhaust gases before they are
released into the environment.
35
Control of Sulphur Dioxide
Removal of sulphur dioxide (Cont..)
2. Limestone slurry scrubbing
CaCO3 + SO2 → CaSO3 + CO2
3. Magnesium oxide scrubbing

Mg(OH)2 + SO2 → MgSO3 + H2O
4. Sodium base scrubbing

Na2SO3 + H2O + SO2 → 2NaHSO3
5. Double alkali scrubbing

2NaOH + SO2 → Na2SO3 + H2O
Ca(OH)2 + Na2SO3 → CaSO3 + 2NaOH
37
(regeneration of NaOH)
Nitrogen oxides in the Atmosphere
 There are three oxides of nitrogen normally
encountered in the atmosphere; nitrous oxide (N2O),
nitric oxide (NO), and nitrogen dioxide (NO2)
 N2O is released into the atmosphere by both natural

and human-generated sources, and is a component of
the unpolluted atmosphere.
 Natural sources of N2O: Microbial activity in soils and

in the ocean; the gas is a by-product of the biological
denitrification and nitrification processes.
38
N2O…
 Human production of nitrous oxide is primarily due to combustion of
fossil fuels, biomass burning, industrial production of nitric acid.
 The major sink for atmospheric N2O is destruction in the

stratosphere where the majority undergoes photolysis to N 2 and O.
N2O + hv → N2 + O
 Its concentration decreases rapidly with altitude in the stratosphere.
 The remaining N2O reacts with O to produce NO, which can enter
into a stratospheric ozone-depleting reaction cycle.
N2O + O → 2NO
 N2O is a greenhouse gas and is an ozone-depleting substance.

Nitrogen oxides in the atmosphere...
 Colorless, odorless nitric oxide (NO), and pungent red-brown
nitrogen dioxide (NO2), collectively designated NOx, enter the
atmosphere from both natural and anthropogenic sources.
 Natural sources: Volcanic action, decay of organic matter,

lightning.
N2 + O2 → 2NO
2NO + O2 → 2NO2
 Stratospheric intrusion: minimal amounts of NOX are formed

from stratospheric intrusion. Nitrous oxide in the stratosphere
is oxidized and dissociated by solar radiation. The newly
formed NOX compounds descend to the troposphere. 40
Nitrogen oxides in the atmosphere...
Anthropogenic sources:
 Fossil fuel combustion in power plants and automobiles and

burning of biomass.
 Fuel NOx: Formed by the reaction of nitrogen bound in the fuel

with oxygen in the combustion air.
 Thermal NOx: Formed when nitrogen and oxygen in the

combustion air combine at high temperatures.
 High-temperature oxidation of the molecular nitrogen in the air
used for combustion. Formation of thermal NOx depends on
the combustion temperature.
N2 + O2 → 2NO
2NO + O2 → 2NO2
Atmospheric reactions of NOx
• The principal reactive nitrogen oxide species in the
troposphere are NO, NO2 and HNO3. These species
cycle among each other. Although NO is the primary
form in which NOx is released to the atmosphere, the
conversion of NO to NO2 is relatively rapid in the
troposphere.
• NO2 is very reactive. It absorbs light throughout the

ultraviolet and visible spectrum penetrating the
troposphere:
NO2 + hv → NO + O
42
Atmospheric reactions of NOx…
The photodissociation of nitrogen dioxide can give
rise to the following significant inorganic reactions in
addition to a host of atmospheric reactions involving
organic species:
NO2 + hv → NO + O
O + O2 + M → O 3 + M
NO + O3 → NO2 + O2
HO2• + NO → NO2 + HO•
RO2• + NO → NO2 + RO•

NO + O + M → NO2 + M
NO + NO3 → 2NO2
O + NO2 + M → NO3 + M
O + NO2 → NO + O2
NO2 + O3 → NO3 + O2
NO2 + NO3 → N2O5

Interconversion of NO and NO2
NO2 + hv → NO + O (1)
O + O2 + M → O 3 + M (2)
NO + O3 → NO2 + O2 (3) No net O3 formation
NO2 + hv → NO + O (1)
O + O2 + M → O 3 + M (2)
HO2• + NO → NO2 + OH• (3)
RO2• + NO → NO2 + RO• (4) O3 formed
45
Atmospheric reactions of NOx…
In the stratosphere, nitrogen dioxide reacts with
hydroxyl radicals to produce nitric acid:
NO2 + HO• → HNO3
Also HNO3:
N2O5 + H2O → 2HNO3
• HNO3 can be destroyed by hydroxyl radicals,
OH• + HNO3 → NO3 + H2O
• Or by a photochemical reaction,
HNO3 + hv → HO• + NO2

Nitric acid produced from NO2 is removed as

precipitation or reacts with bases (Ammonia, particulate
lime) to produce particulate nitrates.
HNO3 + NH3 → NH4NO3
2HNO3 + Ca(OH)2 → Ca(NO3)2 + 2H2O
47
Harmful effects of nitrogen oxides:
NO, NO2 and N2O
NO may be incorporated into hemoglobin in the blood to interfere with
the transport of oxygen around the body.
Short-term exposure to NO causes inflammation of lung tissue. Death
may result from exposure to high concentration.
Irritate the lungs, damage the respiratory tract.
Formation of acid precipitation and photochemical smog.
N2O and the greenhouse effect.
NOx catalyze the partial destruction of the stratospheric ozone layer that
absorbs damaging ultraviolet radiation.
NO2 causes “silo-filler’s disease”. Death can result from the inhalation
of NO2
 silo-filler’s disease: respiratory illness produced by exposure to silo gas
released from fermenting organic matter in freshly filled, poorly
ventilated farm silos. 48
Control of nitrogen oxides
 Less excess air (LEA): Excess air flow for combustion has been
correlated to the amount of NOx generated. Limiting the net excess
air flow can strongly limit NOx content of flue gas.
 Catalytic converters: Catalytic converters in automobiles can

remove a large amount of NOx.
 Flue gas recirculation (FGR): Recirculation of cooled flue gas into

the combustion chamber reduces peak flame temperature and lowers
the percentage of oxygen in the combustion air/flue gas mixture,
thereby reducing thermal NOx formation.
 Low NOx burners (LNBs)  Reduced air preheat and reduced firing rate
 Reburning  Selective non-catalytic reduction (SNCR)
taged combustion (off-stoichiometric combustion)
 Water or steam injection
Selective catalytic reduction (SCR)
Ammonia in the Atmosphere
 Sources of atmospheric ammonia are: Agricultural sources
(livestock wastes, artificial fertilizer application); ammonia
manufacture; combustion of biomass; coke manufacture; and
leakage from ammonia-based refrigeration systems.
 NH3 is removed from the atmosphere by its affinity for water and
by its action as a base.
 Ammonia reacts with these acidic aerosols to form ammonium
salts:
NH3 + HNO3 → NH4NO3
NH3 + H2SO4 → NH4HSO4
 It is a key species in the formation of nitrate and sulphate

aerosols in polluted atmosphere. 51
Health Effects of
Ammonia
Exposure to high concentrations of ammonia in
the environment can cause irritation to the eyes,
nose and throat as well as skin.
 Long-term health concerns related to ammonia

exposure include:
• severe cardiovascular and respiratory effects
• decreased lung function
• asthma aggravation
Organic Air Pollutants
• Organic substances comprise a potentially large group
of air pollutants, particularly in urban environments.
• Organic compounds are released when fuels or organic

waste materials are burned.
• Organic compounds are also emitted by consumer

products such as aerosol sprays and by paints, inks,
solvents and gasoline when they evaporate, and
cigarette smoke.
• Organic compounds react with oxides of nitrogen in the

presence of sunlight to produce photochemical smog.
53
Hydrocarbons
• Hydrocarbons are organic compounds containing only hydrogen
and carbon.
• Classes of hydrocarbons: alkanes, alkenes, alkynes and aromatic

compounds. Because of their widespread use in fuels,
hydrocarbons predominate among organic atmospheric
pollutants.
Sources of hydrocarbons in the atmosphere
• Anthropogenic Sources: Petroleum products, primarily

gasoline, are the source of most of the anthropogenic pollutant
hydrocarbons found in the atmosphere. Others: paints and dry
cleaning solvents. Hydrocarbons enter the atmosphere either
directly or as by-products of the partial combustion of other
hydrocarbons.
• Natural Sources: Decomposition of organic matter, forest fires, 54

Hydrocarbons, Carbonyl compounds and Alcohols
• Aromatic hydrocarbons: The common aromatic hydrocarbons are
benzene, toluene, and xylene. Single-ring aromatic compounds are
important constituents of lead-free gasoline, which has largely
replaced leaded gasoline. Aromatic solvents are widely used in
industries. Aromatic hydrocarbons are raw materials for the
manufacture of monomers and plasticizers in polymers. Many
aromatic hydrocarbons have been detected primarily as ingredients
of tobacco smoke. Because of these applications, plus production of
these compounds as combustion by-products, aromatic compounds
are common atmospheric pollutants.
• Carbonyl compounds (aldehydes and ketones): These are often
the first species formed in the photochemical oxidation of
atmospheric hydrocarbons. The most widely produced carbonyl
compound is formaldehyde.
• Alcohols: Because of their volatility, the lower alcohols, especially
methanol and ethanol, predominate as atmospheric pollutants.
 Combustion of fuels (eg bioethanol), industrial solvents use, biomass
55
combustion.
Environmental effects of organic compounds
• Methane is an extremely efficient greenhouse gas.
• Other hydrocarbons (VOCs) play a significant role in

creating ozone in the atmosphere.
• Many organic compounds cause health effects, such as

cancer and reproductive problems. For example, the
aromatic compounds benzene, toluene and xylene are
suspected carcinogens and may lead to leukemia through
prolonged exposure.
 Carcinogens are substances that can cause or promote the

development of cancer.
56
Loss of Organic Compounds from the Atmosphere
Gaseous organic compounds in the atmosphere interact
with oxidants such as ozone, hydroxyl and nitrate
radicals which provide an important sink.
The attack of parent hydrocarbons (RH) by tropospheric

hydroxyl radicals (HO) proceeds through the following
key reactions:
57
Where R· is an alkyl radical, and RO•2 and RO· are its

alkylperoxy and alkoxy counterparts, respectively.
• Unlike alkanes, alkenes are highly reactive in the
atmosphere, especially in the presence of NOx and
sunlight.
• Hydroxyl radical reacts with alkenes either by
– abstracting a hydrogen atom or
– by adding to the double bond.
• If hydroxyl radical adds to the double bond in
propylene, for example, the product is;
• Addition of molecular O2 to this radical result in the

formation of a peroxy radical:
59
TROPOSPHERIC CHEMISTRY
• Tropospheric chemistry refers to the chemical processes
occurring in the troposphere by which trace substances
released into the atmosphere are oxidized.
• The reactions form stable compounds, i.e. CO2 and H2O, or

more soluble compounds, such as peroxides or acids,
which are rained out or deposited from the atmosphere.
• Photochemical reactions initiated by hydroxyl (OH) radicals,

oxidize most gases to products which are easily removed.
60
The oxidizing capacity of the Troposphere
 The atmosphere avoids any substantial accumulation of
pollutants. It has a remarkable natural ability to cleanse
itself.
 A number of free radicals and other oxidants have been
recognized as the detergents of the atmosphere:
 The hydroxyl radical, OH•

 The nitrate radical, NO3
 The oxygen atom, O
 Hydroperoxy and peroxy radicals, HO2• & ROO•
 Hydrogen peroxide H2O2

61
The Importance of OH radicals and other Oxidants
as the Detergents of the Atmosphere
In descending order of importance:
1. The hydroxyl radical, HO•: Hydroxyl is the most effective
scavenger in the troposphere. It is the main oxidant for CO, CH 4
and higher hydrocarbons, H2S (hydrogen sulfide) and SO2 (sulfur
dioxide).
• It is formed by several reactions. Primary reactions that
generate hydroxyl radicals:
O3 + hv → O• + O2
O• + H2O → 2HO•
• Photolysis of nitrous acid (HONO):

HNO2 + hv → HO• + NO
• Photolysis of hydrogen peroxide (H2O2):

62
H O + hv → 2HO•
The Importance of OH radicals and other
Oxidants as the Detergents of the Atmosphere
2. The nitrate radical, NO3: At night, this radical takes

over from hydroxyl as the dominant oxidant in the
atmosphere: hydroxyl is formed by photolysis and its
concentration peaks during daytime while NO 3 does
not survive sunlight.
3. The oxygen atom O: The oxygen atom has the

ability to oxidize unsaturated hydrocarbons and
other gases containing a double bond such as CS 2
in the upper troposphere.
63
Oxidizing Capacity of the Troposphere (Cont…)
4. Peroxy and hydroperoxy radicals HO2 and RO2 (where

R is an alkyl). HO2 and RO2 are very much intertwined with
hydroxyl in the oxidation cycle. HO2 react with themselves
to form H2O2.
5. Hydrogen peroxide H2O2. Oxidizes a number of trace

gases, in particular sulfur dioxide.
• Together, these oxidants determine the lifetime and the

abundance of trace species, acting as atmospheric
regulators. The reverse is also true: the abundance of trace
species regulate the oxidizing capacity of the atmosphere
since an increase in the emission of a given pollutant
reduces the abundance of its principal oxidant. 64
Principles of Reactivity in the Troposphere
Most gases in the troposphere are gradually oxidized by a
sequence of reactions involving free radicals. For a given
gas, the sequence can be predicted using the following
principles.
 The usual initial step in the oxidation of an atmospheric
gas is its reaction with the OH•.
 With molecules that contain a multiple bond, OH usually
reacts by adding itself to the molecule at the position of
multiple bond.
For example, for propylene (CH2=CHCH3), the product is;
65
Principles of Reactivity in the Troposphere…
 Generally, OH does not add to multiple bonds

in any fully oxidized species such as CO2, SO3,
N2O5 since such processes are endothermic
and therefore are very slow to occur at
atmospheric temperatures.
 Similarly, N2 does not react with OH. because
the component of the nitrogen-to nitrogen
bond that would be destroyed is stronger
than the N-O bond that would be formed.
 OH addition does not occur to CO double
bonds since they are very strong relative to
the single O-O or C-O bond which would be
produced.
Principles of Reactivity in the Troposphere…
 However, OH addition does occur to the carbon atom in
carbon monoxide, CO, since the triple bond is thereby
converted to the very stable double bond and a new single
bond is also formed.
-
CΞO+ + OH• → HO—C• ═ O
 For molecules that do not have a reactive multiple bond but
do contain hydrogen, OH• reacts with them by the
abstraction of a hydrogen atom to form a water molecule
and a new reactive free radical. For CH4, NH3, H2S, and
CH3CI, for instance, the reactions are:
CH4 + OH • → CH3• + H2O
NH3 + OH • → NH2• + H2O
H2S + OH • → SH• + H2O
CH3Cl + OH • → CH2Cl• + H2O
 Some gases emitted into the atmosphere can absorb UV

or Visible sunlight and produce two free radicals.
• For example, atmospheric formaldehyde gas, H2CO,

reacts by photochemical decomposition after absorption of
UV-A from sunlight.
H2CO + UV (λ < 338 nm) → H• + HCO•
 The predominant fate in tropospheric air for most simple

radicals is reaction with diatomic oxygen, often by addition
process.
• For instance,
CH3• + O2 → CH3OO• 68
 The common fate of peroxy radicals is reaction with nitric

oxide, NO forming NO2 and a radical which has one
oxygen atom.
HOO• + NO → OH• + NO2
CH3OO• + NO → CH3O• + NO2
• It is by this type of reaction that most atmospheric NO is

oxidized to NO2.
69
 For radicals that contain non-peroxy oxygen, the reaction
with O2 involves the abstraction of a H atom. As a result, a
single bond involving oxygen is converted to a double one,
and a double bond is converted to a triple one.
• For example;
CH3—O• + O2 → H2C═O + HOO•
HO—C•═O + O2 → O═C═O + HOO•
H—C•═O + O2 → -C≡O+ + HOO•
70
Oxidation reactions involving OH
• OH is extremely reactive and able to oxidise most of the

chemicals found in the troposphere. It is, therefore, known
as the 'detergent of the atmosphere'.
• The chief substrates for reaction with OH in the unpolluted

troposphere are methane and carbon monoxide.
• The most common reaction of the hydroxyl radical is called

"hydrogen abstraction“, in which hydrogen atom from
another substance is added to the OH, converting the OH
to H2O and simultaneously generating a new radical on the
substance, which lost the hydrogen atom.
71
Oxidation reactions involving OH
1. Oxidation of Methane
• The first step in the reaction of hydroxyl radical with
methane is an example of a hydrogen abstraction reaction.
The methyl radical, CH3•, formed at the same time reacts
with oxygen forming a methylperoxy radical, CH3O2•. This
will react with nitric oxide, NO, to form a methoxy radical
that in turn reacts with oxygen to form formaldehyde,
HCHO.
CH4 + HO• → CH3• + H2O

CH3• + O2 → CH3O2•
CH3O2• + NO → NO2 + CH3O•
CH3O• + O2 → HCHO + HO2•
72
2. Oxidation of formaldehyde
• Like CH4, the formaldehyde molecule itself may be
oxidised by OH in a similar sequence of reactions to
form CO or CO2 and water.
HCHO + HO● → H2O + HCO●

HCO● + O2 → CO + HO2●
HO● + CO → CO2 + H●
H● + O2 + M → HO2● + M
• The hydroperoxy radical, HO2●, oxidises NO to NO2 and

regenerates an OH radical:
73
HO + NO → OH + NO
● ●
3. Oxidation of carbon monoxide
• The atmospheric oxidation by OH which is the only
known gas phase tropospheric sink for carbon
monoxide is:
HO• + CO → CO2 + H•
H• + O2 + M → HO
+ M2
•
HO2• + NO → •OH + NO2
74
Tropospheric Ozone
 Ozone is found in two primary areas of our
atmosphere.
 Tropospheric ozone is referred to as the ground
level or ‘bad’ ozone.
 In the upper stratosphere, ozone (stratospheric
ozone) is a beneficial molecule that absorbs
harmful UV radiation from the sun before it
reaches the Earth’s surface;-typically regarded
as ‘good’ ozone.
 On the surface of the Earth in the troposphere,
ozone is a hazardous air pollutant. It is one of
the constituents of photochemical smog.
• It is an air pollutant that damages human
Formation of Tropospheric Ozone
Ozone from NO2
 The formation of ozone in the lower atmosphere stems from

only one reaction: the addition of oxygen atoms to-oxygen
molecules in the presence of a third body:
O + O 2 + M → O3 + M
 The oxygen atoms are known to stem principally from the

photolysis of nitrogen dioxide (NO2);
 Sunlight provides the energy to initiate ozone formation.
NO2 + hv → NO + O
O + O2 + M → O 3 + M
76
NO + O → NO + O
Tropospheric ozone
NO2 + hv → NO + O
O + O2 + M → O3 +
M
NO + O3 → NO2 +
 Whereas nitrogen
O2 dioxide (NO2)
participates in the formation of ozone,
nitrogen oxide (NO) destroys ozone to form
oxygen (O2) and nitrogen dioxide (NO2).
• For this reason, ozone levels are not as

high in urban areas (where high levels of
NO are emitted from vehicles) as in rural
Ozone from Methane, CH4
CH4 + .OH + O2  CH3OO. + H2O

VOC CH3OO. + NO  CH3O. + NO2
CH3O. + O2  HCHO + HO2.
HO2. + NO  .OH + NO2
NO2 + hn  NO + O
O + O 2 + M  O3 + M
Net: CH4 + 4 O2  HCHO + H
Sunlight 2O + 2 O 3
78
Ozone from carbon monoxide
HO• + CO → CO2 + H•
H• + O2 + M → HO
+ M2
•
HO2• + NO → •OH +
NO2
NO2 + hv → NO + O
O + O2 + M → O 3 + M
79
Ozone from formaldehyde
HCHO + HO● → H2O + HCO●

HCO● + O2 → CO + HO2●
HO● + CO → CO2 + H●
H● + O2 → HO2●
HO2● + NO → ●OH + NO2
NO2 + hv → NO + O
O + O2 + M → O 3 + M
Negative impacts of tropospheric ozone
• Causes eye irritation, air passages irritation causing breathing
difficulties, chest pain, coughing, nausea, headaches and chest
congestion and discomfort.
• It may increase susceptibility to infection and creates more

frequent attacks for individuals with asthma.
• It damages forests and crops; and injures or destroys living

tissue. High concentrations of ozone cause plants to close their
stomata; this slows down photosynthesis and plant growth.
• Destroys nylon, rubber, and other materials;-textile dyes, fibers,

and certain paints may be weakened or damaged by exposure
to ozone. Some elastic materials can become brittle and crack,
while paints and fabric dyes may fade more quickly.
81
Acid Rain
 Natural rain, including precipitation in
relatively clean or unpolluted regions, is
naturally acidic, with a pH in the range of
5.0 to 6.0. This natural acidity is due to the
presence of dissolved atmospheric carbon
dioxide in it.
 Acid rain in the pollution sense is produced

by the conversion of the primary pollutants
sulfur dioxide (SO2) and nitrogen oxides (NO
and NO2) to sulfuric acid (H2SO4) and nitric
acid (HNO3), respectively, to generate an
 Precipitation
acid solution with
witha a
pH pH
lower than
less 5. 5.0 is
than
designated acid rain.
Acid Rain…
Sulphur and nitrogen oxides are converted to sulphuric
and nitric acids respectively. The presence of sulphuric
acid and nitric acid in precipitation causes acid rain.
SO2 + H2O  H2SO3

H2SO3 + 1/2O2  H2SO4
NO + 1/2O2  NO2
2NO2 + H2O  HNO2 + HNO3
NO2 + OH  HNO3
83
Effects of Acid Rain
i. Effects of acid rain in aquatic systems
 Acidification of surface water
(e.g. lakes, rivers) and
subsequent damage to aquatic
ecosystem.
o Kills aquatic plants, fish and
microorganisms in lakes and
 The lower pH levels in the
streams.
water have a direct and primary
effect on many of the various
creatures that live within the
o lake ecosystem.
For example, a pH of 5 will kill
fish eggs, and lower levels will
kill adult fish.
 Also affects the lives of
terrestrial species and birds
that feed on aquatic life.
Effects of Acid Rain…
ii. Damage of materials and structures e.g. Building
materials (cement, plastics, limestone and marble),
metals, cars (automobile) coatings. Materials constructed
from limestone, iron or steel are easily attacked by acids.
E.g. CaCO3 + H2SO4 → CaSO4 + CO2 + H2O
CaSO4 is more soluble than CaCO3
 Paint on cars can react with acid deposition causing

fading.
Effects of Acid Rain
iii. Changes the pH of the soil and water
to damage plants. Leaching of plant
nutrients
 Ca2+, Mg2+, Na+ and K+ are some of the
important nutrients for plants growth. H+
in acid rain displaces positive cations
from soil particles, which causes free
cations to be mobilized. An increase in the
acidity of the soil therefore results in the
leaching of several important plant
nutrients.
 Many important soil organisms cannot

survive in soils below a pH of about 6.0.
The death of these organisms can inhibit
decomposition and nutrient cycling.
 Damage to forests, vegetation and reduction
of crop productivity. 86
Effects of acid rain
iv. Harm to human beings: Irritation to eyes, aggravate brain
disorders, inflammation of lung tissue and respiratory illness.
v. Acid deposition influences the economic livelihoods of some

people.
Examples: reduced fish numbers, crop productions and material
destruction.
87
PHOTOCHEMICAL SMOG
Smog derives from the words smoke and fog.

Smoke: Smoke generally refers to a visible mixture of
products given off by the incomplete combustion of
organic substances such as wood and fuel oil.
Fog - droplets of water vapor suspended in the air.
Particulates: microscopic particles of solid or liquid 88
matter suspended in the air. Include fog, mists, dust and
Photochemical Smog…
 Photochemical smog is a reddish brown haze that is caused by the

action of solar ultraviolet radiation on the atmosphere polluted with
hydrocarbons and oxides of nitrogen.
 A mixture of pollutants that are formed by the reactions of nitrogen oxides

and volatile organic compounds (VOCs) in the presence of sunlight,
creating a reddish brown haze.
 Photochemical smog is one of the most dangerous effects of pollution on

atmosphere.
Photochemical smog…
• The primary pollutants of smog are nitrogen oxides and
volatile organic compounds (VOCs e.g. hydrocarbons).
• These primary pollutants, in the presence of sunlight and

high temperatures (>18 oC), convert rapidly to secondary
pollutants such as:
˗ Ozone,
˗ Organic nitrates,
˗ Oxidized hydrocarbons
which constitute photochemical smog.
Mechanism of Photochemical Smog Formation
 The photodecomposition of nitrogen dioxide initiates the formation of
photochemical smog.
 NO, the predominant form of NOx emissions, reacts with O2 to form NO2.
NO + 1/2O2  NO2
 This small amount of NO2 triggers subsequent reactions through its

decomposition, forming NO2 photolytic cycle.
Eq. 1 NO2 + hv NO + O.
Eq. 2 O. + O2 + M O3 + M
Eq. 3 NO + O3 NO2 + O2
 These reactions constitute a null cycle, whereby there is no net

91
buildup of ozone or oxidation of NO to NO 2 by this mechanism.
Mechanism of Photochemical Smog Formation…
 The release of large amounts of NOx with CO, carbonyl

compounds and hydrocarbons by anthropogenic
sources disrupts the photolytic cycle.
 The oxygen atoms react with water to form hydroxyl
radicals.
Eq. 4 O. + H2O 2HO.
 The hydroxyl radicals then react with hydrocarbons

according to equations 5 through 8 to form
peroxyacylnitrates (or PAN).
92
Mechanism of Photochemical Smog formation
Eq. 5 RH + HO. H2 O + R.
R. + O2 RO2. very fast
Eq. 6 RO2. + NO NO2 + RO.

RO. + O2 R'CHO + HO2. very fast
Eq. 7 R'CHO + HO. R'CO. + H2O Acyl radical
RCO. + O2 R'C(O)O2. very fast Acylperoxy

radical
Eq. 8 R'C(O)O2. + NO2 R'C(O)O2NO2 Acylperoxy

nitrate
93
Mechanism of Photochemical Smog formation
94
Causes of Photochemical Smog
 Photochemical smog is a condition that is developed
when primary pollutants, i.e., NOx and VOCs, interact
under sunlight to produce a mixture of hazardous
secondary pollutants.
 A variety of conditions are necessary for the formation of

photochemical smog:
1. Emission rates of the sources of NOx and VOCs;

2. Time of the day;
3. Meteorological factors;
4. Topography.
Causes of photochemical smog
1. A source of nitrogen oxides and VOCs is a primary
factor for the formation of photochemical smog.
– High concentrations of these two substances are
associated with industrialization and transportation.
– They create pollutants in the atmosphere through
fossil fuel combustion.
96
Causes of photochemical smog…
2. Time of the day: the concentration of nitrogen oxides, VOCs and
the progress of the reactions producing ozone depend on time;
– Early morning traffic increases nitrogen oxides and VOCs as

people drive to work. Later in the morning, traffic dies down,
nitrogen oxide and VOCs begin to react forming nitrogen
dioxide, thereby increasing its concentration.
– As sunlight becomes more intense later in a day, nitrogen

dioxide is broken down increasing the concentration of ozone.
At the same time, nitrogen oxides can react with the VOCs to
produce toxic chemicals such as Peroxylacetylnitrate (PAN).
As sun disappears, the production of ozone is halted. The
ozone that remains is then consumed by different reactions
and the concentration goes down.
97
Causes of photochemical smog…
3. Meteorological factors
– precipitation-washes pollutants out of the atmosphere
with the rainfall,
– winds- blow smog away,
– temperature-can enhance the severity of a smog
episode.
4. Topography - valleys are more susceptible to smog as

hills and mountains surrounding them tend to reduce the
airflow.
98
The effects of photochemical smog
• Reduces visibility.
• Photochemical smog is involved in global climate change
(tropospheric ozone is a greenhouse gas).
• Affects human health: Tropospheric ozone irritates eyes,
nose and throat. As smog increases can cause asthma,
bronchitis, coughing, chest pain, and decreased lung
function.
• Damages plants:
– Tropospheric ozone degrades chlorophyll causing
leaves to turn yellow;
– Reduces productivity and reproduction.
GREENHOUSE GASES
Greenhouse gas: any gas that has the property of absorbing
infrared radiation emitted from the Earth’s surface and re-
radiating it back to the Earth’s surface, thus contributing to the
greenhouse effect.
 Light from the sun penetrates the atmosphere and warms

the Earth’s surface.
 Longer wavelength infrared radiation is radiated from the

earth’s surface.
 A considerable amount of the outgoing IR radiation is

absorbed by gases in the atmosphere and re-radiated back
to earth, warming the earths surface.
100
Greenhouse gases…
 What makes a gas greenhouse gas?
• Able to absorb infrared light: Must have molecular
vibration(s).
Molecular vibration is a periodic motion of the atoms of a molecule
relative to each other such that the centre of mass of the molecule
remains unchanged.
 The molecular vibrations help determine if a gas can absorb
infrared radiation.
 A molecular vibration will only occur in a molecule if infrared
radiation of a particular frequency or wavelength is absorbed.
 A vibration in a molecule is any change in shape of the molecule.
This excludes monoatomic gases as greenhouse gases (that is

why argon, the third most abundant atmospheric constituents is
transparent to infrared radiation).
101
Greenhouse gases…
 The molecular vibrations must result in a change in dipole
moment (A molecule can only absorb infrared radiation
when it experiences a change in dipole moment during a
vibration), i.e. infrared active. Homonuclear diatomic
molecules are IR inactive; N2, O2 are not greenhouse
gases.
 The primary greenhouse gases in Earth's atmosphere are:
 Water vapour
 Carbon dioxide
 Methane
 Nitrous oxide
 Ozone
 Chlorofluorocarbons (CFCs), and SF6 102
Carbon Dioxide (CO2)
• Sources:
– Manmade: Fossil fuel combustion in industrial
processes and transportation, deforestation-removes
the carbon sinks.
– Natural: Respiration of plants and animals.
• Sinks
– Photosynthesis.
– Oceans
• The oceans are a vast reservoir of CO 2.

103
Methane (CH4)
Sources
 Natural: End product of the metabolism from anaerobic
bacteria, herbaceous digestion in termites, natural wetlands,
enteric fermentation (wild animals and domestic grazing
animals-herbaceous digestion).
Enteric fermentation: Is a natural part of the digestive process in
ruminants such as cows, sheep, goats and buffalo.
 Manmade: Rice/paddies cultivation (anaerobic conditions
due to flooding), coal mining, decomposition of organic
wastes in municipal solid waste landfills, biomass burning.
 Sinks
HO• + CH4 → CH3• + H2O

104
Nitrous Oxide (N2O)
• Sources
– Natural: Denitrification and Nitrification

processes.
– Manmade: Fertilizer use, Biomass burning,

Fossil fuel combustion.
• Sink
Photolysis in the stratosphere.
N2O + hv → N2 + O
105
Tropospheric Ozone & CFCs
Tropospheric Ozone
• Source: created as a by-product of human created
photochemical smog.
• Sink: Photolysis
CFCs
• Sources: CFCs are synthetic chemicals used in electronic
appliances: used as coolants in a.c. and refrigerators,
sterilants for hospital equipment, propellants in
aerosol/spray cans, cleaner for electronics.
• Sink: Photolysis in the stratosphere.

106
Greenhouse Effect
• The greenhouse effect is a naturally occurring process that

aids in heating the Earth's surface and atmosphere.
• The greenhouse effect is important. Without the greenhouse

effect, the Earth would not be warm enough for humans to live.
• But if the greenhouse effect becomes stronger, it could make

the Earth warmer than usual. Even a little extra warming may
cause problems for humans, plants, and animals.
• You might hear people talking about the greenhouse effect as if
it is a bad thing. It is not a bad thing, but people are concerned
because the Earth’s greenhouse is warming up very rapidly.
• This is happening because we are currently adding more
greenhouse gases to our atmosphere, causing an increased
greenhouse effect.
107
Greenhouse effect…
• Too many greenhouse gases can cause the
temperature to increase out of control.
• The increased greenhouse effect is causing changes

in our planet that can affect our lives.
108
Global warming
• Global Warming: Increase in the earth’s surface
temperature due to an anthropogenic enhancement of
the greenhouse effect.
• Greenhouse gases cause the average global

temperature to increase, significantly affecting the
climate.
• Recent years have been the warmest over the entire

period.
109
Global warming…
Effects of global warming
– Increase in average temperature
– Melting of glaciers, less snowpack, shrinking sea ice
– Rising sea levels

• Warmer temperatures increase melting of mountain
glaciers and ice caps and cause ocean water to
expand.
– Droughts
– Changes in the distribution of disease-bearing

organisms. As temperatures rise, disease-carrying
mosquitoes and rodents move into new areas, infecting
people. 110
Slowing Global Warming
• Cut fossil fuel use and develop nonpolluting energy sources e.g.
solar and wind energy: This will reduce millions of tons of
carbon dioxide and other pollution into the atmosphere every
year.
• Reduce deforestation and plant trees: By planting trees (plants
use carbondioxide), preserving forests, it is possible to increase
the size of carbon sinks.
• Slow human population growth
• Improve energy efficiency: Cars and light trucks, home
appliances and power plants could be made much more
efficient by simply installing the best current technology.
• Kyoto Protocol-1997: An international agreement to reduce
greenhouse gases. Countries that ratify this protocol commit to
reduce their emissions of greenhouse gases.
111
Indoor Air Pollution
Air pollution can also occur indoors (in buildings).
Sources of indoor air pollution: Cigarettes smoke, cooking and
heating appliances, and building materials (paints, furniture, etc).
Cigarette smoke contains about 4000 chemicals generated during
burning and smoking of tobacco including:
Irritants and systemic toxicants e.g. hydrogen cyanide and
sulfur dioxide;
Mutagens and carcinogens e.g. at least 50 compounds,
including Polycyclic aromatic hydrocarbons (e.g. benzo(a)pyrene),
formaldehyde, arsenic, acetaldehyde, benzene, beryllium, 1,3-
butadiene, cadmium, ethylene oxide, hydrazine, furan,
heterocyclic amines, lead, polonium-210, O-toluidine, vinyl
chloride; and
Reproductive toxicants e.g. nicotine, cadmium, and carbon
112
monoxide.
Indoor Air Pollutants
• Combustion products
Some of the indoor pollutants are formed by combustion: e.g.
– CO2: Sources include space heaters, gas cooking ranges,

and respiration.
– CO: Sources include space heaters, woodstoves, tobacco

smoke, and fumes from garages.
– NOX: Sources include gas cooking ranges and space

heaters.
– Particulate matter: Sources include woodstoves and

113
tobacco smoke.
Indoor Air Pollutants…
• Lead: Old lead-based paint is the most significant source of
lead exposure today. Harmful exposures to lead can be
created when lead-based paint is improperly removed from
surfaces by dry scraping, sanding, or open-flame burning.
• Volatile organic compounds (VOCs)

These are chemical substances that are volatile at room
temperature. They are given off by most paints and paint
strippers, wood preservatives, aerosol sprays, glues,
cleansers and disinfectants, pesticides, air fresheners, and
stored fuels and automotive products.
114
Potential Health Effects of Indoor Air Pollutants
• Carbon monoxide: Headache, nausea, impaired vision

and mental functioning, fatal at high concentrations.
• Nitrogen oxides: Eye, nose and throat irritation,
increased respiratory infections in children.
• Organic chemicals: Eye, nose and throat irritation;

headaches; loss of coordination; damage to liver, kidney
and brain; and various types of cancer. Formaldehyde:
Eye, nose and throat irritation; headache; allergic
reactions; and cancer.
• Lead: Nerve and brain damage, particularly in children,

anemia, kidney damage and growth retardation.
115
Control of Indoor Air Pollutants
• Restrict smoking: cigarette smoke contains many toxic
pollutants.
• Use products safely: Products such as cleaning agents,
paints, and glues should be used outdoors whenever possible.
Use gas appliances, wood stoves, and fireplaces only as
intended. Gas stoves should never be used to heat the house
since high pollutant levels can result.
• Provide adequate ventilation: Increase ventilation by opening
windows and doors, particularly when using products or
engaging in activities that may generate pollutants.
• Practice good housekeeping e.g. proper storage of solvents
and frequent housecleaning.
• Select building materials and furniture carefully.
116
STRATOSPHERIC CHEMISTRY
• Stratospheric Chemistry is mainly the chemistry of the
ozone layer.
• Ozone layer is a region of the atmosphere that filters out
harmful ultraviolet (UV) rays from sunlight.
Location of the Ozone Layer
• Ozone is mainly found in two regions of the atmosphere:
– Stratosphere known as “ozone layer” or “good ozone”.
Stratospheric ozone shields us from ultraviolet
radiation;
– Troposphere; known as “ground level ozone” or “bad
ozone”.
117
The Formation and Destruction of Ozone
 Ozone is created in the stratosphere when solar

radiation strikes molecules of oxygen and causes the
two oxygen atoms to split apart.
 If a freed atom bumps into another O2, it joins up,

forming ozone.
O2 + O • + M → O 3 + M
118
The Formation and Destruction of Ozone…
 Ozone is also naturally broken down in the stratosphere

by sunlight and by chemical reactions with various
compounds containing nitrogen, hydrogen and chlorine.
 In an unpolluted atmosphere there is a balance between

the amount of ozone being produced and the amount of
ozone being destroyed.
Chapman Mechanism
• In 1930, S. Chapman, a
British scientist, proposed
a theory of the formation of
ozone in the stratosphere.
• Chapman mechanism
• Four steps: Formation and

destruction
120
Major Steps of Chapman Mechanism:
1. O2 absorbs solar radiation (wavelength < 242 nm)

and photodissociates:
O2 + hv → O• + O•
2. O reacts rapidly with O2 in the presence of a third

body, denoted M (M is usually another O 2 or N2
required to absorb heat energy due to collision
between O and O2 ), to form ozone:
O2 + O• + M → O 3 + M
Chapman Mechanism…
3. Ozone absorbs solar radiation (in the wavelength range
of 240 to 320 nm) and decomposes back to O2 and O•:
O3 + hv  O2 + O•
4. Additionally, ozone can be destroyed by reacting with

atomic oxygen to regenerate two molecules of O2:
O3 + O •  O 2 + O 2
Or, by collision of ozone molecules:

O3 + O3  3O2 122
Chapman Mechanism…
a) O2+ hv (<242 nm)  2O•

Formatio
b) O + O2 + M  O3+ M
•
n
c) O3 + hv (<320 nm)  O• + O2
Destructio
d) O• + O3  2O2 n
Where M is a random air molecule (O2
or N2)
 Chapman theory describes how sunlight converts

the various forms of oxygen from one to another.
123
2. Catalytic ozone destruction
• Apart from the non-catalytic ozone destruction described
above, there exist a number of atomic and molecular
species, designated in general as X, that react efficiently
with ozone by abstracting (removing) an oxygen atom
from it.
X + O3  XO + O2
• Where the atomic oxygen concentration is appreciable,

the XO molecules react subsequently with oxygen atoms
to produce O2 and to re-form X.
XO + O  X + O2
• X is regenerated in the process. It acts as a catalyst. The

chain reaction continues until X is removed by some side
reaction.
Catalytic Ozone destruction…
• The overall reaction corresponding to this reaction

mechanism is given below.
X + O3 XO + O2
XO + O X + O2
O3 + O 2O2
• Thus the species X are catalysts for ozone destruction in

the stratosphere since they speed up a reaction (here,
between O3 and O), but they are eventually re-formed
intact and are able to begin the cycle again and again.
Catalytic ozone destruction…
 Chemically, all the catalysts X are free radicals. Ozone can
be destroyed by a number of free radical catalysts, these
include:
 Hydroxyl radical (OH•),

 Nitric oxide radical (NO•),
 Atomic chlorine (Cl•) and bromine (Br•)
 All of these have both natural and anthropogenic sources.

Most of the OH• and NO• in the stratosphere is of natural
origin, but human activity has dramatically increased the
chlorine and bromine.
126
Catalysts for stratospheric O3 destruction
Hydroxyl radical (OH)
OH + O3  HO2. + O2
.
HO2. + O  .OH + O2
Net: O. + O3  2 O2
Sources
 OH radical in the stratosphere originates from the reaction of
oxygen atoms with water or methane.
O3 + hv  O2 + O• .
O• + H2O  2 •OH (major)
O• + CH4  •OH + CH3• (minor)
Termination reaction: •OH + NO2  HNO3 127
Hydroxyl radical (OH)…
• Water vapor in the stratosphere has two main sources.

(i) Transport of water vapor from the troposphere which
occurs mainly as air rises in the tropics.
(ii) Oxidation of methane which occurs mostly in the
upper stratosphere.
• The methane originates with emissions from the Earth's

surface, a small fraction of which survives sufficiently long
to migrate up to the stratosphere.
Catalysts for stratospheric O3 destruction…
Nitric oxide (NO)
NO + O3  NO2 + O2
NO2 + O.  NO + O2
Net: O. + O3  2 O2
Sources
 NO is produced abundantly in the troposphere, but all of it is
converted into NO2  HNO3
 NO in the stratosphere is produced from nitrous oxide (N2O).
NO is produced when molecules of nitrous oxide, N2O, rise
from the troposphere to the stratosphere, where they may
eventually collide with oxygen atoms produced by
photochemical decomposition of ozone.
N2O + O•  2 NO
Nitric oxide, NO…
Removal processes
• NO may be converted into catalytically inactive forms that

prevent the NO catalyst from destroying ozone.
• There are two inactive forms in which NO exists; the NO2

will react with stratospheric hydroxyl radical, OH, to form
nitric acid, HNO3.
NO2 + .OH HNO3
Or
• NO2 reacts with hypochlorite, ClO. to form inactive chlorine
nitrate:
ClO. + NO2 ClONO2
Catalysts for stratospheric O3 destruction…
Chlorine and Bromine (Cl and Br)
Chlorine
Cl. + O3  ClO. + O2
ClO. + O.  Cl. + O2
Net: O. + O3  2 O2
Bromine
Br. + O3  BrO. + O2
BrO. + O.  Br + O2
Net: O. + O3  2 O2
Sources of Chlorine and Bromine in the Stratosphere
Chlorine
 Large amounts of chlorine in the stratosphere are produced
from synthetic chlorine-containing gaseous compounds that
are released into the air during their production or use.
 Most of these substances are chlorofluorocarbons (CFCs).
• CFCs is the abbreviated form of ChloroFluoroCarbons, a

collective name given to a series of compounds containing
chlorine, fluorine and carbon atoms. Also called freons.
• Some of the common ones are CCl 3F (Freon 11 or CFC - 11),

CCl2F2 (Freon 12 or CFC - 12), CClF 3 (Freon 13 or CFC-13)
C2Cl3F3, (Freon 113, CFC-113).
Chlorofluorocarbons (CFCs) in the Atmosphere
• CFCs are used in refrigerators, displacing the highly toxic

and odorous gases SO2 and NH3.
• Most of the CFCs produced for commercial and industrial

use are eventually discharged into the atmosphere.
• Due to inertness, the CFCs slowly diffuse up to the

stratosphere, where UV radiation causes them to
decompose to produce atomic chlorine, Cl•.
E.g. CCl3F + hv (185-210 nm)  CFCl2• + Cl•

Ozone layer destruction by CFCs
• Step 1: Photolysis of CFCs in the stratosphere, e.g.
CF2Cl2 + UV light  CF2Cl• + Cl•
• Step 2: Catalytic destruction of ozone
Cl• + O3  ClO• + O2
ClO• + O  Cl• + O2
Termination reactions for Cl•
Cl• + CH4  CH3. + HCl
• HCl is stable in the stratosphere. Removed from air by
precipitation when it migrates to the troposphere.
• A single chlorine atom removes about 100,000 ozone molecules

134
before it is taken out of operation by other substances.
Chlorine radical…
 Despite the catalytic action of chlorine to ozone, the
majority of stratospheric Cl exist in a form that is not a free
radical and that is inactive as a catalyst for ozone
destruction.
 The two main catalytically inactive (or reservoir) molecules

containing chlorine in the stratosphere are hydrogen chloride
gas, HCl, and chlorine nitrate gas, ClONO2.
 The chlorine nitrate is formed by the combination of chlorine

monoxide and nitrogen dioxide;
ClO + NO2 ClONO2

sunlight
Atomic Chlorine as Catalyst
ClO. + NO2 + M  ClONO2 + M
Reservoir species: Relatively unreactive but can

regenerate reactive species upon suitable conditions
ClONO2 + hv  ClO + NO2
ClONO2 + hv  Cl• + NO3
136
Sources of Chlorine and Bromine in the
Stratosphere…
• Methyl chloride gas, CH3Cl produced at the Earth's surface
mainly in the oceans as a result of the interaction of
chloride ion with decaying vegetation, also its use as a
fumigant and biomass burning, slowly migrates upward to
the stratosphere.
CH3Cl + hv (UV-C)  Cl• + CH3•
 Large quantities of methyl bromide, CH3Br, are also

produced naturally, and in the stratosphere, CH3Br is
decomposed photochemically to yield atomic bromine.
CH3Br + hv  Br• + CH3•

The important catalysts for stratospheric O3
destruction
 Hydroxyl radical (OH)
OH + O3  HO2. + O2
.
HO2. + O  .OH + O2 HO cycle

Net: O. + O3  2 O2
 Chlorine and bromine (Cl and Br)
Cl. + O3  ClO. + O2 ClO cycle
ClO. + O.  Cl. + O2
Net: O. + O3  2 O2
 Nitric oxide (NO)
NO cycle
NO + O3  NO2 + O2
NO2 + O.  NO + O2
.
The two sided-effect of NO
• NO provide a catalytic chain mechanism for O3 destruction.
• NO inhibit the HO and ClO cycles for O3 destruction by

removing radical species in the two cycles.
NO2 + .OH HNO3
ClO. + NO2 ClONO2
139
Ozone abundance
• Total column ozone is the total amount of ozone

integrated from the surface to the top of the atmosphere.
• Dobson units (DU) is used to express the total column

ozone; named after G.M.B. Dobson, a scientist who
conducted pioneering measurements of the stratosphere
in the 1930s.
• One Dobson unit is equivalent to a 0.01-mm (0.001-cm)

thickness of pure ozone at the density it would occupy at
standard temperature and pressure (273 K and 1 atm).
Consequences of Ozone layer depletion
• Ozone layer depletion is expected to increase

surface UV levels leading to the increase in:
– Skin cancer.
– Crop and marine life damage.
– Cataracts (clouding of the normally clear lens of
the eye) and sunburning.
– Suppression of immune systems in organisms.
141
Global efforts to protect the ozone layer
The Montreal protocol

In 1987, an international treaty, The Montreal protocol, was signed
by most industrialized nations; in which it sets targets for cutbacks
in CFCs production and the complete elimination of these
substances.
CFC replacement
• CFCs are not soluble in water; they are not rained out of rain and
have no tropospheric sink.
• They are not attacked by the OH radical or any other atmospheric
gases. There are efforts to find substitutes that are not harmful to
the ozone layer. One of them are hydrochlorofluorocarbons
(HCFCs, called soft CFCs) e.g. HCFC-123 (CF 3CHCl2). The
presence of the hydrogen atom makes the compound more
susceptible to oxidation in the lower atmosphere, so that it never
142
Air Pollution Control
• Catalytic converters in cars used to reduce emissions

of NOx, hydrocarbons, and CO.
• Develop nonpolluting energy sources like solar
energy, wind power, and hydropower.
• Development of hydrogen powered or electric
vehicles to reduce emissions of pollutants.
• Use of filters to stop particles.
• Reduce indoor pollution e.g. by proper ventilation.
• Avoid the creation of the pollutants.
• Encourage mass transit.
143
WATER AND SOIL POLLUTION
WATER POLLUTION
 Water pollution is contamination of water by foreign matter that
deteriorates the quality of the water. Water pollution covers
pollutions in liquid forms like oceans and rivers, streams, and
underground water. Water has been contaminated by chemicals
for decades.
 The water contaminants include:
– Inorganic e.g. fertilizers from farms, heavy metals.
– Organic: chlorinated solvents, hydrocarbons such as
benzene, and their derivatives, e.g., toluene, C 6H5CH3,
Organic pesticides and drug residues. Sources of organic
pollutants: leaking chemical waste dumps, leaking
underground gasoline storage tanks, leaking municipal land
fills and accidental spills of chemicals on land, pesticides
application, industrial effluents, sewage and municipal
144
Sources of Water Pollution
 The sources of water pollution can be considered as point
sources of pollution, and non-point sources of pollution.
 Point source: is a single, identifiable source of pollution.
 E.g. factories and other industrial and commercial installations

that release toxic substances into the water.
 These toxic chemicals include Cd, Cr, Hg, Pb, cyanide, and
several chlorinated and nonchlorinated organic compounds.
145
Sources of Water Pollution…
Non-point sources: are diffuse pollution sources (i.e. without a
single point of origin or not introduced into a receiving stream from a
specific outlet).
 The pollutants are generally carried off the land by storm water
run-off. They include:
 Agricultural runoff, which carry excess nutrients, pesticides,

silts etc into streams and groundwater.
 Urban runoff, which can carry toxic metals and organics

through storm drains into sewage treatment plants or directly
into rivers and lakes.
 Emissions from transport vehicles.

146
SOIL POLLUTION
 Soil pollution: Contamination of the soil by different pollutants.
 It is the presence of man-made chemicals or other alteration of

the natural soil environment.
 This type of contamination typically arises from the rupture of
underground storage tanks, application of chemical fertilizers
and pesticides, leaching of wastes from landfills or sewage
sludge and direct discharge of industrial wastes to the soil.
Sewage sludge: the residue resulting from the treatment of wastewater.
 The most common chemicals involved are petroleum
hydrocarbons, solvents, sulfur dioxide, chemical fertilizers (e.g.
nitrates), pesticides, and heavy metals.
 The concern over soil contamination stems primarily from health
risks, both of direct contact and from secondary contamination
147
of water supplies.
MAJOR POLLUTANTS
PESTICIDES
 Pesticides are substances used to manage, control or kill
pests.
 Pests are organisms such as insects, rodents, weeds, and
fungi, that are considered to have undesirable effects.
 The ideal pesticides kill only the target pest, have no health
effects on non-target organisms, can be broken down into
harmless chemicals in a fairly short time, prevent the
development of genetic resistance in pests, and save money
compared with making no effort to control pest species.
Pesticide Names
 Pesticides can be named in three ways: by trade or brand
name, by common name or active ingredient, and by chemical
(IUPAC) name. 148
Classification of Pesticides
1. Pesticides can be classified according to targeted pests; E.g.

insecticides (for insects), herbicides (for weeds), fungicides (for
fungi), bactericides (for bacteria), rodenticides (for rodents).
2. Classification depending on their mode of action:
 Sterilants-are used to manage pests by rendering them incapable
of normal reproduction.
 Contacts pesticides-kill pests by coming into contact with them.
 Systemics pesticides are absorbed by one part of the animal or
plant and distributed internally to other parts of the plant or animal.
 Fumigants-produce a vapour that kills organisms.
 Selective pesticides-chemicals that kill only a specific pest or
group of pests.
 Broad spectrum pesticides-chemicals that kill a wide range of
pests.
149
Classification and chemistry of pesticides
3. Chemical Classification depending on active ingredient:
 Pesticides can be grouped according to chemical structure.
 Pesticide active ingredients are either inorganic or organic
pesticides.
 Examples of inorganic pesticides include copper sulphate,
ferrous sulphate, copper and sulphur.
 Organic pesticides contain carbon in their chemical
structures. Most organic compounds are created from various
compounds, but a few are extracted from plant materials and
are called 'botanicals'.
 Commonly used organic pesticide chemical classes include
the organochlorines, organophosphorous pesticides,
carbamates, pyrethroids, phenoxy acids, triazines and urea
herbicides.
(a) Organochlorine pesticides
• Organochlorine pesticides contain C, H and Cl atoms.
They are insecticides, which readily penetrate the waxy
coating of insects.
• Examples of the organochlorine insecticides include DDT

(dichlorodiphenyltrichloroethane), endosulfan, aldrin,
dieldrin, hexachlorocyclohexane (HCH), chlordane,
heptachlor, mirex, and dicofol.
Cl
Cl Cl
Cl Cl
Cl
DDT HCH Chlordane 151
Examples of organochlorines…
Cl Cl
Cl Cl
Cl Cl
Cl
Cl Cl
Cl Cl
Cl
Cl Cl
Cl Cl Cl
Aldrin Heptachlor Cl Cl
Mirex
Cl Cl
Cl Cl
Cl
Cl
Cl
O Cl
O
Cl Cl Cl S O
O
Cl
Dieldrin Endosulfan Dicofol

152
Organochlorine pesticides…
• They are chemically stable and degrade slowly; they are

persistent in the environment.
• They have low volatility.
• Have low solubility in water but high lipid solubility.
• They undergo bioaccumulation in food chains and
cause chronic health effects.
153
Classification depending on active ingredient…
(b) Organophosphorus pesticides

 Commonly called organophosphates. They are insecticidal
organic compounds containing phosphorus.
 Consist of a central, pentavalent phosphorus atom to which are
connected:
 an oxygen or sulfur atom doubly bonded to the P atom,
 two methoxy (-OCH3) or ethoxy (-OCH2CH3) groups singly

bonded to the P atom, and
 a longer, more complicated, characteristic R group singly

bonded to phosphorus, usually through an oxygen or sulfur
atom, that differentiates one organophosphate insecticide from
154
another.
Organophosphorus Pesticides…
Classification depending on active ingredient
Parathion
Malathion
Dichlorvos
Chlorpyrifos
156
They are toxic to insects because they inhibit enzymes in the

nervous system; they function as nerve poisons. They act by
inhibiting acetylcholinesterase, AChE (an enzyme that
hydrolyzes acetylcholine which is generated in the transmission
of nerve impulses) causing accumulation of acetylcholine and
interfere with the coordination of muscle response and eventually
death.
AChE
157
 Most organophosphate insecticides decompose in the

environment by hydrolysis reactions:
 They are non-persistent; they break down rapidly into

harmless and water soluble products, once released
into the environment.
 Organophosphates do not bioaccumulate.

158
The organophosphorus pesticides affect and
damage the nervous system and can cause
cancer. They also cause reproductive and
endocrinal damage.
Parathion described as extremely hazardous.

Nonspecific to insects; toxic to bees, fish, birds,
and other forms of wildlife.
Banned in most countries.

(c) Carbamates
• Pesticidal organic derivatives of carbamic acid
(H2NCOOH).
• Introduced as insecticides in 1951.
R = organic group
The general formula of

a carbamate insecticide
O NH
CH3
160
Carbaryl aldicarb
Carbamates…
• Carbamates are anticholinesterase compounds that inhibit the
removal or breakdown of acetylcholine.
• Carbamates undergo hydrolysis reactions and decompose to

simple, nontoxic products. Short-lived in the environment.
 Low level of persistence in the environment.
 Skin exposure: Minor rash; Long term exposure; weakness,

disturbance of renal, hepatic, neurological and reproductive
systems.
161

(d) Pyrethroids
 Pyrethroids are synthetic versions of naturally occurring

pyrethrins. The most commonly used pyrethroids include
permethrin and deltamethrin.
Cl2C CH CH CH C O CH2
C
O
H3C CH3 O
Permethrin
CN
Br2C CH CH CH C O CH
C
O
H3C CH3 O
162
Deltamethrin
 Pyrethroids are insoluble in water, immobile in soil and sorb
strongly to particles such as wood and soil. This means that once
applied, they will stick to the material and will not tend to transfer.
 They are broken down by sunlight and microorganisms such as

bacteria and are therefore generally not very persistent in the
environment.
 Some pyrethroids are toxic to the nervous system causing

neurotoxic effects including tremors, incoordination, increased
aggressive behaviour, and disruption of learning behaviour. They
also cause coughing, shortness of breath, runny or stuffy nose,
chest pain, difficulty breathing, skin rash, and itching, or blisters.
• Long term effects include liver damage, development of breast

cancer, disruption of the endocrine system.
163
(e) Phenoxy Herbicides

 Phenoxy herbicides are selective herbicides that induce similar
physiological responses to endogenous plant hormones, such as
auxins, and cytokinins, and may act as competitors or antagonists
of these natural plant growth regulators. By mimicking the natural
auxin, 3-indoleacetic acid, they produce lethally abnormal growth.
 The phenoxy herbicides are often described as the “hormone”
weed killers.
 Examples of common phenoxy acids are 2,4-D (2,4-
Dichlorophenoxy acetic acid) and 2,4,5-T (2,4,5-Trichlorophenoxy
acetic acid).
Cl
Cl OCH2COOH
Cl OCH2COOH
Cl
Cl
2,4-D 2,4,5-T 164

Phenoxy Herbicides…
 Phenoxy herbicides undergo a hydrolysis reaction in the

environment, degrading the compound to a phenol.
E.g.: Hydrolysis of 2,4-D
 Persistence in the environment is relatively low.

Classification and chemistry of pesticides…
(f) Triazines
 Triazine herbicides are cyclic compounds, containing a ring
system composed of three carbon and three nitrogen
atoms.
 Triazine herbicides inhibit photosynthesis.
 Example: atrazine.
(CH3)2CHNH N Cl
N N
NHCH2CH3
The general formula of triazines

Atrazine
In triazines that are useful as herbicides, R1= CI and R2
and R3 = amino groups 166
 While in soil, atrazine is degraded by microbes.

(g) Urea Herbicides are substituted ureas (H2NCONH2),

having their hydrogen atoms replaced by various carbon
chains and rings. They are usually applied to the soil as
pre-emergence or post-emergence materials.
• They are strongly absorbed by the soil, then absorbed by
roots.
• Their mechanism of action is inhibition of photosynthesis.
• e.g., linuron and isoproturon,
CH3 H3C
Cl NH C N CH3
CH NH C N
OCH3
O H3C CH3
Cl O
linuron Isoproturon
167
4. Classification depending on formulation
• A pesticide formulation is a mixture of the active and other

ingredients (previously called inert/inactive ingredients); a mixture of
chemicals which effectively controls a pest.
• The pesticide active ingredient (a.i.) is mixed with other compounds

to improve its effectiveness, safety, handling and storage. The other
compounds can include solvents, mineral clays, wetting agents,
spreaders, or other adjuvants (materials added to increase the
effectiveness or change the properties of the pesticide in the spray
mix). Examples of pesticide formulations are liquids, powders,
granules, baits/attractants, dusts, solutions.
• Pesticides come in many different formulations due to variations in

the active ingredient's solubility, ability to control the pest, and ease
of handling and transport.
• The amount of active ingredient and the kind of formulation are listed
on the pesticide label. For example, a 50W contains 50% by weight 168
5. WHO classification according to toxicity: Class Ia/Ib =
Extremely/Highly hazardous, Class II = Moderately
hazardous, Class III = Slightly hazardous and Class IV =
Product unlikely to present acute hazard in normal use.
• The classification is based primarily on the acute oral and

dermal toxicity to rats since these determinations are
standard procedures in toxicology.
LD50: The dose required to kill half the members of a tested population after a specified
169
Degradation/Transformation of Pesticides
• Chemical degradation of pesticides e.g. hydrolysis of
organophosphates and carbamates, oxidation and
reduction reactions such as of DDT to DDE and DDD etc.
• Photochemical reactions; chemical reactions brought

about by the absorption of light , frequently, isomers of the
pesticides are formed as products.
– Biodegradation; Biological degradation, either complete

mineralisation or partial decay to form metabolites,
brought about by microorganisms e.g. bacteria, fungi and
algae. Also by insects, earthworms, and plants.
170
Degradation/Transformation of Pesticides: Examples
Cl Cl
C
Microorganisms CCl3 Microorganisms CHCl2
C
Cl CH Cl Cl CH Cl
Aerobic Anaerobic
DDT DDD
Cl DDE Cl
Dichlorodiphenyldichloroethylene Dichlorodiphenyltrichloroethane Dichlorodiphenyldichloroethane
Cl Cl
Cl Cl
Cl Cl Cl
Cl Cl
Oxygenation Hydrolysis
Oxidation Cl
Cl
Cl Cl OH
O Cl
Cl Cl OH
Cl
Dieldrin
Cl Aldrin-diol
Aldrin
Cl Cl Cl Cl Cl Cl
Cl Cl Cl
Cl Oxidation Cl Hydrolysis Cl
O O OH
Cl SO2 Cl S O
O O Cl
Cl Cl Cl OH
Endosulfan sulphate Endosulfan Endosulfan diol
171
Degradation/Transformation of Pesticides: Examples
sis
roly
Hyd HO
HO NO2 + 2CH3CH2OH + P OH
CH3CH2O HO
S
P O NO2
CH3CH2O
S Parathion
HO
HO NO2 + 2CH3CH2OH + P OH
CH3CH2O HO
O
P O NO2
CH3CH2O
O Paraoxon
O
OH O
C H
O N C H
H2 O + HO N
CH3
bacteria, fungi CH3
Carbaryl 1-naphthol Methyl carbamic acid
Cl2C CH CH CH C O CH2
C O
H3C CH3 Permethrin O
Hydrolysis
Cl2C CH CH CH C OH HO CH2
C O
H3C CH3 3-phenoxyphenylmethanol O
dichlorovinyldimethyl cyclopropanoic acid
172
PERSISTENT ORGANIC POLLUTANTS (POPs)
• POPs are chemical substances that persist in the

environment, bioaccumulate through food web, and pose a
risk of causing adverse effects to human health and the
environment.
• Sources: Most POPs are man-made; some are
unintentionally produced combustion substances.
• POPs include:
(a) Organochlorine pesticides (e.g. DDT, aldrin, dieldrin,
endrin, chlordane, heptachlor, toxaphene, mirex alpha-
hexachlorocyclohexane, beta-hexachlorocyclohexane,
lindane or gamma-HCH, chlordecone, endosulfan,
hexachlorobenzene and pentachlorobenzene).
173
PERSISTENT ORGANIC POLLUTANTS (POPS)
(b) Industrial chemicals
(i) Polychlorinated biphenyls (PCBs): organic chlorine compounds with the

formula C12H10−xClx.
PCBs (R = Cl and H) There are 209 possible PCBs
 Uses: Coolants and insulating fluids (transformer oil) for transformers and
capacitors, as de-inking solvents for recycling newsprint, flame retardants, and as
waterproofing agents.
 Because of their stability and extensive usage, together with careless disposal
174
practices, PCBs became widespread and persistent environmental contaminants.
PERSISTENT ORGANIC POLLUTANTS…
(ii) Perfluorooctanesulphonic Acid (PFOS) and its salts
(Perfluorooctanesulphonates)
PFOS
 Hydrophobic (water-repelling) and oleophobic (oil-repelling).
 This substance was used to make the 3M (Minnesota Mining

and Manufacturing company) product Scotchgard, a fabric
protector that, because of the characteristics of the perfluoro
chain, repelled both water and oily spills and potential stains.
175
• Other compounds based upon PFOS were used in fire-fighting foams,

pesticide formulations, cosmetics, lubricants, grease-resistant coatings
for paper products, adhesives, and paints and polishes.
• The 3M company voluntarily phased out the production of PFOS in 2000

because it persists long enough in the environment to eventually be
detected in human blood samples. Its concentration in some wildlife had
reached levels of concern to some scientists.
• Main toxic effects of PFOS include hepatotoxicity, neurotoxicity,

reproductive toxicity, immunotoxicity, thyroid disruption, and
cardiovascular toxicity.
176
.
(iii) Polybrominated diphenyl ethers (PBDE): are a class of
organobromine compounds that are used as flame retardants.
• Used in a wide array of products, including building materials,

electronics, furnishings, motor vehicles, airplanes, plastics and textiles.
e.g. Tetrabromodiphenyl ether, pentabromodiphenyl ether,

hexabromodiphenyl ether and heptabromodiphenyl ether.
• Like PCBs, they are persistent and lipophilic, they bioaccumulate, and
are toxic.
177
(c) Unintentionally produced combustion substances Examples

include:
 Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD and

PCDF or Dioxins and Furans),
O O Clx
Cly Clx Cly
Chlorinated Dioxins Chlorinated Furans
E.g.
Cl O Cl Cl Cl
Cl O Cl Cl O Cl
2,3,7,8-Tetrachlorodibenzo-p-dioxin 2,3,7,8-Tetrachlorodibenzo-p-furan
178
Unintentionally produced combustion substances…
 PCDDs and PCDFs: Emitted from the incineration of hospital, municipal
and hazardous waste, car emissions, and the incineration of substances
such as coal and wood.
 Formed as trace amounts of undesired impurities in the manufacture of
other chemicals, such as chlorinated phenols and their derivatives,
chlorinated diphenyl ethers and polychlorinated biphenyls (PCBs).
 Polycyclic Aromatic Hydrocarbons (PAHs)
PAHs are products of combustion from automobiles, airplanes etc.
Benzo(a)pyrene Phenanthrene PAHs E.g.
179
The Science of POPs
POPs possess the following properties:
1. Persistence: POPs are very resistant to chemical and
biological breakdown in the environment because most of
them contain carbon-halogen bonds e.g. C-Cl, which are very
stable and others have stable aromatic rings.
2. POPs undergo bioaccumulation and biomagnification
because they are lipophilic: Bioaccumulation = storage of
stable substances in living tissues resulting in a much higher
concentration there than in the environment. Biomagnification
= increase in the concentration of a substance through a food
chain.
3. Toxicity: The lipophilicity of these compounds means that
they bioaccumulate and persist and thus, achieve
toxicologically relevant concentrations.
180
The Science of POPs
 POPs have been associated with chronic effects such as
teratogenicity (cause structural or functional birth defects e.g.
reproductive failure, reproductive impairment, birth and
developmental abnormalities), mutagenicity (cause mutations),
carcinogenicity (cause cancer), cause reduced immunological
function leading to reduced resistance to infections, disrupt the
endocrine system.
 POPs also cause some acute effects e.g. nausea, lung irritation,
skin rash, vomiting, and dizziness.
4. Migration over long distances from their source: POPs are semi-
volatile, thus are transported long distances by air in multiple cycles
of evaporation and condensation (grasshopper effect).
5. POPs tend to concentrate in colder climates: The ability of most

POPs to remain in the atmosphere decreases whenever the
atmosphere becomes colder, when they condense back to the
181
Earth’s surface.
Why are POPs a problem?
POPs are persistent in the environment and migrate over long
distances from their source.
They move through the food chain to humans.
They cause significant adverse effects to human health and wildlife.
 POPs have toxic effects on the nervous, endocrine and immune

systems; some are carcinogenic, teratogenic or mutagenic
 They clearly pose a hazard on wildlife populations, e.g. DDT

causes the eggshells of birds to become so thin they break during
incubation.
 They are passed on from mother to child across the placenta, and
through breast milk.
182
The Grasshopper Effect
• The grasshopper effect (global distillation) is the process by which
certain chemicals, most notably persistent organic pollutants
(POPs), are transported from warmer to colder regions of the Earth,
particularly the poles and mountain tops.
• When these chemicals are released into the environment, some

evaporate when ambient temperatures are warm, blows around on
winds until temperatures are cooler, and then condensation occurs.
Drops in temperature large enough to result in deposition can occur
when chemicals are blown from warmer to cooler climates, or when
seasons change. Since global distillation is a relatively slow process
that relies on successive evaporation/condensation cycles, it is only
effective for semi-volatile chemicals that break down very slowly in
the environment, like POPs.
• Global distillation explains why relatively high concentrations of

POPs have been found in the Arctic environment and in the bodies
of animals and people who live there, even though most of the
chemicals have not been used in the region in appreciable amounts.
Transformation/Degradation of POPs
• Some POPs may be converted to
metabolites/transformation products, which in some
cases are more persistent and toxic than the parent
compounds. Processes involved are: microbial, photo,
and chemical transformations.
• E.g.1: Conversion of DDT (1,1,1-Trichloro-2,2-bis(4-
chlorophenyl)ethane) to DDE (1,1-bis-(4-chlorophenyl)-
2,2-dichloroethene) and DDD (1,1-bis-(4-chlorophenyl)-
2,2-dichloroethane).
• E.g.2: Rapid metabolic conversion of aldrin to its
extremely environmentally persistent metabolite dieldrin
 Refer Transformation of Pesticides.
184
International Actions on POPs
• The uses of some POPs were banned in most countries especially in

developed countries in Europe and US during the 1970s to 1990s.
• The Stockholm Convention on POPs was signed in May 2001, to
reduce or eliminate 12 toxic substances known as the ‘dirty dozen’ i.e.
Organochlorine pesticides (DDT, aldrin, dieldrin, endrin, chlordane,
heptachlor, hexachlorobenzene, mirex, and toxaphene, PCBs,
Dioxins and Furans.
• The convention was amended (e.g. in May 2009; modifications came
into force in 2010) and the following compounds were added for
elimination: α-hexachlorocyclohexane, β-hexachlorocyclohexane,
lindane (gamma-HCH), endosulfan, pentachlorobenzene, chlordecone,
hexabromobiphenyl, tetrabromodiphenyl ether, pentabromodiphenyl
ether, hexabromodiphenyl ether, and heptabromodiphenyl ether.
• The production and use of DDT is eliminated except for few Parties
where it is under restriction for production or use for disease vector
control in accordance with the WHO guidelines.
185
HEAVY METALS
• Heavy metals are metals with a specific gravity greater
than about 5.
• Heavy metals consist of both biological essential (e.g.

copper nickel, iron, and zinc), and non-biological essential
metals (lead, mercury and cadmium).
• Heavy metals readily accumulate through food webs from

producers to consumers.
• As they exceed the maximum health standard levels, they

can be immediately poisonous or result in long-term health
problems.
186
Heavy metals - Mercury
 Occurrence: Mercury occurs naturally in the environment and exists in

several forms, such as metallic Hg (elemental Hg), inorganic mercury
(e.g. HgS and HgCl2), and organic mercury (e.g. methylmercury).
Microorganisms and natural processes can change the mercury in the
environment from one form to another. The most common organic Hg
compound generated from other forms is methylmercury.
 Sources of pollution: broken thermometers, barometers, batteries, and

lamps, dental amalgams, combustion of fossil fuels such as coal and
petroleum, household waste, medical and industrial wastes, pesticides
e.g. fungicides, volatilization from the ocean, mining industries,
volcanoes, and atmospheric deposition.
 Effects: kidney and central nervous system (CNS) damage, ulcers, death
if in the form of methyl mercury, carcinogenic, mutagenic, causes
blindness, Minamata disease, and damaging to aquatic life. 187
Heavy metals - Mercury
 Effects (ctd):
• Methylmercury is of particular concern because it can build up or biomagnify in edible

fish and marine mammals to levels that are many times greater than levels in the
surrounding water.
• Minamata disease is a neurological syndrome caused by severe mercury poisoning.

Symptoms include numbness in hands and feet, ataxia (lack of muscle control during
voluntary movements), general muscle weakness, loss of vision, and damage to
hearing and speech. In extreme cases, causes insanity, paralysis, coma, and death.
A congenital form of the disease can also affect fetuses in the womb.
• Minamata disease was first discovered in Minamata city in Kumamoto prefecture,

Japan, in 1956. It was caused by the release of methylmercury in the industrial
wastewater from the Chisso Corporation's chemical factory. The chemical reaction
used to produce acetaldehyde in the factory used mercury sulfate as a catalyst. A
side reaction of this catalytic cycle led to the production of an organic mercury
compound (methylmercury). This highly toxic compound was released into Minamata
Bay. The highly toxic chemical bioaccumulated in fish, which, when eaten by the local
populace, resulted in mercury poisoning. 188
Heavy metals - Lead
 Occurrence and Use: Metallic lead does occur in nature, but it is
rare. Lead is usually found in ore with zinc, silver and copper. The
main lead mineral is PbS. Other common varieties are PbCO3 and
PbSO4. Lead is used in building construction, lead-acid batteries,
bullets and shots, weights, as part of solders, fusible alloys and as a
radiation shield.
 Sources: automobile exhaust-combustion of leaded gasoline,
paintworks-using lead-based paints, mining industries, batteries,
incinerator ash- combustion of solid waste, tap water from lead pipes,
atmospheric deposition, combustion of coal and oils, and tobacco
smoke.
 Effects: kidney damage, central and peripheral nervous system
toxicity, anaemia, irritability, mental retardation in children, severe
depression of sperm count, exhibit weakness, general disability,
nervous disorders and eventual death.
 Pollutes soils and surface waters, accumulates in bodies of
organisms thus disturbs their body functions. Soil functions 189 and
organisms are disturbed by lead poisoning. Birth defects in animals.
Heavy metals – Cadmium
• Cadmium occurs as a component in most zinc ores and therefore is a
byproduct of zinc production.
• It is used as a pigment and for corrosion resistant plating on steel while

cadmium compounds were used to stabilize plastic and in nickel-
cadmium batteries and cadmium telluride solar panels.
• Sources of pollution include: burning of fossil fuels such as coal or oil

and the incineration of municipal waste, sewage effluent, cigarette
smoking, manufacture pigments and batteries, plastics industry and
mining industry.
Effects of Cd: Renal disease, lung irritation and risk of lung cancer.
190
Arsenic
Sources of Arsenic: mining industry, herbicides, wood preservatives,
volcanoes, semiconductor manufacture.
Effects of Arsenic: hyperpigmentation, skin lesions and tumors, carcinogenic

(skin and lung cancer), damage to gastrointestinal tract and liver,
gastrointestinal effects (diarrhoea, abdominal pain); birth defects, nervous
system disorders.
SOLID AND HAZARDOUS WASTES
Municipal Solid Wastes (MSW)
• The term Municipal Solid Wastes (MSW) is generally used
to describe most of the non-hazardous solid waste from a city,
town or village that requires routine collection and transport to
a processing or disposal site.
• Sources of MSW include private homes, commercial
establishments and institutions, construction, as well as
industrial facilities. They are genarated by households, stores,
offices, restaurants, schools, airports, hospitals, industries etc.
• Municipal solid wastes contain a wide variety of materials. It
can contain food waste (like vegetable and meat material,
leftover food, eggshells, etc), which is classified as wet
garbage as well as paper, plastic, newspaper, glass bottles,
cardboard boxes, aluminium foil, metal items, wood pieces,
etc, which is classified as dry garbage.
192
SOLID AND HAZARDOUS WASTES
Hazardous Wastes
• Hazardous wastes are wastes that pose a risk to human health
or the environment and require special disposal techniques to
make them harmless or less dangerous.
• Hazardous wastes exhibit any of four primary characteristics:
toxicity, reactivity, ignitability and corrosivity. In addition to this,
waste products that are radioactive are also classified as
hazardous.
• Toxic wastes: are those substances that are poisonous even in
very small or trace amounts. Some may have acute or
immediate effect on humans or animals, causing death or violent
illness. Others may have chronic or long-term effects.
• Reactive wastes are those that have a tendency to react
vigorously with air or water, are unstable to shock or heat,
generate toxic gases, or explode during routine management,
e.g. gunpowder.
193
Hazardous Wastes - ctd
 Ignitable wastes are those that burn at relatively
low temperatures (less than 60 oC) and are capable
of spontaneous combustion during storage, transport
or disposal e.g. gasoline, paint thinners, and alcohol.
 Corrosive wastes are those that destroy materials
and living tissues by chemical reaction e.g. acids
and bases.
 Radioactive waste is basically the output from
nuclear power plants and can persist in the
environment for thousands of years before it decays
appreciably.
• Radioactive material: Any material containing unstable
atoms that emit ionizing radiation as it decays.
194
Management of Municipal Solid Wastes
• Management and disposal of municipal solid wastes involves
sending to landfills (garbage dumps/sanitary landfills),
incineration (burning), or recycling/recovery.
• The problems with landfills are usually associated with ground-
water pollution. Pollutants seeping out from the bottom of a
sanitary landfill (leachates) very often percolate down to the
groundwater aquifer. The risks of incineration involve air-quality
problems and toxicity and disposal of the ash produced. Heavy
metals, which are harmful, may be present in incinerator ash.
• New directions in municipal solid waste management: 4R’s i.e.
reduce, reuse, recycle and recover
• Reduce amount of waste going to disposal, produce less waste
at the source of production.
• Reuse - repeated use of an item e.g. refillable bottles
• Recycling-use material to make a new product e.g. plastics,
aluminium, steel, metal, paper, glass etc. 195
• Recover: Transforming waste into resources. E.g. composting
Management and Disposal of Hazardous Wastes
• Destroy or detoxify wastes, then dispose them securely.
• Ultimate treatment methods i.e. permanent disposal methods,
include:
– incineration - burning at high temperature,
– solidification - making a liquid or sludge into a solid mass,
 cement technologies - dry solid wastes are immobilized in
concrete making,
 vitrification - the process converts liquid radioactive and
chemical waste into a solid, stable glass, eliminating
environmental risks.
• A suggested hierarchy (from best to worst) for disposal of
hazardous wastes is:
(i) On-site reuse or recycling, (ii) Waste exchange,
(iii) Chemical treatment, (iv) Incineration, (v) Disposal in a
196
permitted landfill, and (vi) Discarded into the environment.
Effects of Water and Soil Pollution
 The effects of water and soil pollution are myriad. Examples of the effects
are:
 Water and soil pollution can be lethal, killing organisms such as fish, plants,
birds and other animals.
 Eutrophication: lack of oxygen in a water body caused by excessive algae
growths because of enrichment of nutrients especially phosphates and
nitrates.
 Almost every type of contamination found in water has a detrimental effect
on humans.
 Many of the toxins found in polluted water and soil are carcinogenic, which
means they can cause cancer. Some substances can even affect
generations to come by changing the body’s chromosomal makeup. Others
have teratogenic effects etc.
 Diseases e.g. blood diseases, heart disease and nervous system disorders
are commonly linked to the effects of water/ soil pollution.
 Less severe effects of water pollution can include diarrhea, skin lesions,
and vomiting.
 Water pollution causes human deaths worldwide. 197
MANAGEMENT OF WATER AND SOIL POLLUTION
 Reduce agricultural waste.
 Reduce industrial waste.
 Reduce domestic waste.
 Promoting the sustainable system of agriculture which encourages
use of as less chemicals as possible in agricultural operations. Control
of pests by eco-friendly approaches like Integrated Pest Management
(IPM) System - where in biological methods are integrated with
chemical control.
 Ban pesticides like DDT, HCH etc - which are persistent, non-
biodegradable and bio-accumulative.
 Recycling and composting city wastes.
 Water treatment of drinking water, industrial water/ effluents, sewage
or wastewater.
 Wastewater reclamation-Reuse of treated water. 198
WATER QUALITY
 Water quality refers to the physical, chemical and biological
characteristics of water usually with respect to its suitability for a
particular purpose. It is a measure of the condition of water
relative to the requirements of one or more biotic species and or
to any human need or purpose.
 Water quality measurements include chemical, physical and
biological parameters. The parameters are determined by the
intended use. The following is a list of indicators often
measured by situational category:
 Drinking water: Colour, pH, taste and odor, alkalinity, dissolved
metals and salts (E.g. Na, K, Ca, Mn, Mg, chlorides),
microorganisms such as faecal coliform bacteria (Escherichia
coli), dissolved organics: colored dissolved organic matter,
dissolved organic carbon; radon, heavy metals,
pharmaceuticals.
199
Water Quality Parameters
Environmental
Environmental water quality relates to water bodies such as lakes, rivers,
and oceans.
 Physical assessment: Temperature, total suspended solids (TSS),

total dissolved solids (TDS), turbidity.
 Chemical assessment: pH, dissolved oxygen (DO), chemical

oxygen demand (COD), biochemical oxygen demand (BOD), total
hardness (TH), nitrogen compounds (nitrate, nitrite, ammonia),
phosphorus (orthophosphates, total phosphorus) etc.
 Biological assessment: faecal coliform bacteria, presence and

abundance of insects, benthic macroinvertebrates indicator (Benthic
refers to the bottom of a waterway).
200
Water Quality Parameters
Electrical Conductivity
 The electrical conductivity of water is a measure of how well water
can pass an electric current. The ability of water to pass an electric
current is directly related to the concentration of ions in the water.
These conductive ions come from inorganic dissolved solids such
as chlorides, sulfates, phosphates and carbonate compounds.
 Electrical conductivity is an indirect measure of the presence of

inorganic dissolved solids (e.g. chloride, nitrate, sulfate, phosphate,
Na, Mg, Ca, Fe and Al). The presence of these substances
increases the conductivity of water. The more ions that are
present, the higher the conductivity of water. Likewise, the fewer
the ions that are in the water, the less conductive it is.
 Inorganic dissolved solids are essential ingredients for aquatic life;

e.g. they regulate the flow of water in and out of organisms’ cells.
 A high concentration of dissolved solids, however, can cause
various problems for aquatic organisms such as a decrease in the 201
Electrical Conductivity…
 Typical conductivity of water is as follows:
 Ultra-pure water: 5.5 × 10−6 S/m;
 Drinking water: 0.005–0.05 S/m;
 Seawater: 5 S/m.
Turbidity
 Turbidity is the measure of relative clarity of a liquid.
 It is a measure of the amount of particulate matter that is suspended in

water. Water that has high turbidity appears cloudy or opaque.
 Cloudiness is caused by suspended solids (e.g. clay, silt, very tiny
organic matter, algae, plankton).
 Low levels of turbidity may indicate a healthy, well-functioning ecosystem.
 High turbidity causes increased water temperatures because
suspended particles absorb more heat and can also block out the light,
thus reduce the amount of light penetrating the water, which is needed by
submerged aquatic vegetation. Turbid waters may also be low203in
Turbidity…
 Suspended soil particles may carry pollutants (e.g. nutrients, and
pesticides) throughout a water system.
 Turbidity is measured by an instrument called nephelometer/ turbidity

meter which expresses turbidity in terms of NTU (Nephelometric
Turbidity Units) or TU.
 Turbidity more than 5 NTU can be visible to the average person

while turbidity in muddy water, exceeds 100 NTU.
Total Solids
 Total solids is a measure of the suspended and dissolved solids

in a body of water. Thus, it is related to both conductivity and
turbidity.
Total solids (TS) = Total dissolved solids (TDS) + Total suspended solids (TSS)
 To measure total suspended and dissolved solids, a sample of

water is placed in a drying oven to evaporate the water, leaving
the solids.
 To measure dissolved solids, the sample is filtered before it is
dried and weighed.
 To calculate the suspended solids, the weight of the dissolved

solids is subtracted from the total solids.
205
Secchi Depth
 Secchi depth is the depth to which one can see into a water body
and is an indication of water clarity. This measurement is obtained
by lowering a black and white disk into the water and recording the
depth at which it is no longer visible.
 If you could lower a Secchi disk into absolutely pure water, the
theoretical maximum value would be between 70-80 meters (230-262
ft). 206
Temperature
 Water temperature is one of the most important parameters for
aquatic organisms.
 It governs the kinds of aquatic life, influences the rate of
chemical and biological reactions and affects other measured
parameters.
 It controls the rate of metabolic activities, reproductive activities
and therefore, life cycles. If stream temperatures increase,
decrease or fluctuate too widely, metabolic activities may speed
up, slow down, malfunction, or stop altogether.
 Temperature affects the concentration of dissolved oxygen in a

water body; oxygen is more easily dissolved in cold water; as
temperature increases, the maximum amount of dissolved
oxygen decreases.
 Affects the rate of photosynthesis by aquatic plants. 207
pH
 pH is a term used to indicate the alkalinity or acidity of a
substance. Aquatic organisms differ as to the range of pH in
which they flourish. If the water is too acidic or basic, the H +
or OH- ion activity may disrupt aquatic organisms’
biochemical reactions by either harming or killing the stream
organisms.
208
Acidity
 Acidity of water is its quantitative capacity to react with a strong
base to a designated pH.
 Acidity in water is usually due to carbon dioxide, mineral acids,
and hydrolyzed salts such as ferric and aluminum sulfates.
 The level of acidity is determined by titration with standard basic
solution using selective indicators.
Alkalinity
 Alkalinity is a measure of the capacity of water sample to
neutralize acids.
 Alkalinity measures the amount of alkaline compounds in the
water, such as carbonates, bicarbonates and hydroxides.
 Alkalinity is determined by titration with a standard acid solution
using selective indicators (methyl orange or phenolphthalein). 209
Dissolved Oxygen (DO)
 Dissolved oxygen (DO) is the amount of oxygen that is
present in water. It is measured in milligrams per liter
(mg/L).
 DO is considered an important measure of water quality as
it is a direct indicator of a water body's ability to support
aquatic life.
 One of the most widely used methods of measuring the
concentration of dissolved oxygen in water samples is
known as the Winkler titration. The method uses iodine to
indirectly determine the amount of dissolved oxygen.
210
Dissolved Oxygen…
 Dissolved oxygen levels can be measured using a dissolved
oxygen meter.
 DO levels less than 3 mg/L are stressful to most aquatic organisms.

Most fish die at 1-2 mg/L. Water with low DO from 2 – 0.5 mg/L are
considered hypoxic; waters with less than 0.5 mg/L are anoxic.
 Hypoxic-absence of enough oxygen; anoxic- greatly deficient in oxygen.
Biochemical Oxygen Demand (BOD)
 Biochemical Oxygen Demand (BOD) is the amount of oxygen
consumed by microorganisms in the decomposition of organic
material.
 BOD is the measure of the level of pollution caused by organic

biodegradable material. Low value of BOD indicates that water
contains less organic matter.
 Sources of biochemical oxygen demand include leaves and

woody debris; animal manure; food-processing plants, and urban
stormwater runoff.
 It is most commonly expressed in milligrams of oxygen

consumed per liter of sample during 5 days (BOD5) of incubation
at 20 °C.
212
BOD…
BOD is determined by measuring the dissolved oxygen level in a
freshly collected sample and comparing it to the dissolved oxygen
level in a sample that was collected at the same time but incubated
under specific conditions for a certain number of days.
The difference in the oxygen readings between the two samples in

the BOD is recorded in units of mg/L.
The greater the value, the more rapidly oxygen is depleted in

the water body. This means less oxygen is available to higher
forms of aquatic life. Consequences of high BOD: aquatic
organisms become stressed, suffocate, and die.
 Unpolluted, natural waters should have a BOD of 5 mg/L or less.

Hardness
 Hardness is frequently used as an assessment of the
quality of water supplies.
 The hardness of a water is mainly governed by the content
of hydrogencarbonates of calcium and magnesium
(temporary hardness), sulphates or chlorides of calcium or
magnesium (permanent hardness).
 Hardness is normally determined by titration with ethylene
diaminetetraacidic acid (EDTA) and Eriochrome Black T
indicator.
214
Metals
 Metals, especially heavy metals (e.g. Cu, Fe, Cd, Zn, Hg, and Pb
are the most toxic to aquatic organisms. High levels of these
metals cause water quality problems and toxicity to organisms.
 Atomic absorption spectrophotometer (AAS).
Nitrogen Compounds
 Nitrogen occurs in natural waters in various forms including NO 3,
NO2, and NH3. Nitrate is the most common form tested. Test
results are usually expressed as nitrate-nitrogen (NO 3-N), which
simply means nitrogen in the form of nitrate. High nitrate
concentrations cause eutrophication.
 Nitrate is determined by cadmium reduction with colour
comparator or spectrophotometer.
215
Nitrates
 The cadmium reduction method involves contact of the nitrate
in the sample with cadmium particles, which cause nitrates to
be converted to nitrites.
 The nitrites then react with another reagent to give a red color
whose intensity is proportional to the original amount of nitrate.
 The red color is then measured either by comparison to a color
wheel with a scale in milligrams per liter that increases with the
increase in color hue, or by use of an electronic
spectrophotometer that measures the amount of light absorbed
by the treated sample. The absorbance value is then converted
to the equivalent concentration of nitrate by using a standard
curve.
 Measuring nitrite in the sample without the cadmium reduction
step is required to correct the nitrate results for any pre-existing
nitrite.
Phosphorus
 Phosphorus usually occurs in nature as phosphate. Phosphate
bound to plant or animal tissue is known as organic phosphate.
Phosphate associated with inorganic material is known as inorganic
phosphate. Inorganic phosphate is often referred to as
orthophosphate or reactive phosphorous.
 Phosphorus, in addition to nitrogen, is a nutrient which can result in
eutrophication of receiving water bodies. The parameters are total
orthophosphate, total phosphorus (test measures all the forms of
phosphorus in the sample i.e. orthophosphate, and organic
phosphate) and dissolved phosphorus.
 Total orthophosphate is determined by ascorbic acid method with
colour comparator or spectrophotometer. In this method, a combined
liquid consisting of sulphuric acid, potassium antimonyl tartrate,
ammonium molybdate, and ascorbic acid, is added to either 50 mL or
25 mL of the water sample. This colours the sample blue in direct
proportion to the amount of orthophosphate in the sample. 217
WATER TREATMENT
 Water treatment is any process that improves the quality of
water to make it appropriate for a specific end-use.
 The treatment of water may be divided into three major

categories:
• Purification for domestic use
• Treatment for specialized industrial applications
• Treatment of wastewater to make it acceptable for
release or reuse.
 The type and degree of treatment are dependent upon the

source and intended use of the water.
218
Municipal Water Treatment
Municipal water is treated to make sure that it is clean and healthy
enough to be delivered to rural, and urban populations.
1. Aeration: The process by which air is circulated through, mixed

with, or dissolved in water.
 During aeration, some soluble gases (volatile solutes) such as
carbon dioxide and hydrogen sulphide, and volatile odorous
substances such as methane thiol (CH3SH) are removed.
Contact with oxygen also aids iron removal by oxidizing soluble
iron(II) to insoluble iron(III).
2. Softening: Treatment of water with lime, Ca(OH)2 results in the

formation of precipitates containing the hardness ions Ca 2+, and
Mg2+. Ca2+ is precipitated as CaCO3, and Mg2+ as Mg(OH)2. These
precipitates settle in the primary basin.
Ca2+ + 2HCO3- + Ca(OH)2  2CaCO3(s) + 2H2O
219
Municipal Water Treatment…
3. Coagulation and flocculation
 Much of the solid material remains in suspension and requires the
addition of certain chemicals to settle the colloidal particles.
Coagulation: a step in which chemicals (coagulants) are added
to cause small particles suspended in the water to clump together.
 The coagulants commonly used in the treatment of water are

aluminium sulphate and ferric chloride (which form gelatinous
metal hydroxides) to settle the colloidal particles.
 Flocculation follows, which mixes the water with large paddles so

that coagulated particles can be brought together into larger
clumps (or “floc”) that slowly settle on the bottom of the tank or
basin.
 Sludge from both the primary and secondary basins is pumped to

a sludge lagoon.
4. Sedimentation: After the majority of the suspended particles
have settled, water exits the flocculation basin and then enters a
sedimentation basin. Sedimentation basins move treated waters
along through the purification process while allowing remaining
particles to settle. Sludge forms that appear on the floor of the
tank are removed and treated.
5. Filtration: From the sedimentation basin, water is moved to the

next step, filtration which removes the remaining suspended
particles and unsettled floc in addition to many
microorganisms.
6. Disinfection: The water is disinfected to eliminate any remaining

pathogenic micro-organisms. The most commonly used
disinfectant (the chemical used for disinfection) is chlorine, in the
form of a liquid (such as sodium hypochlorite, NaOCl) or a gas.
 Following disinfection the treated water is pumped into the

distribution system. Supplementary treatments??
Sewage Treatment
 Sewage: wastewater that flows through sewers,

released from various sources including residences,
industries and public institutions.
 Sewage contain oxygen-demanding materials,

sediments, grease, oil, scum, pathogenic bacteria,
viruses, salts, algal nutrients, pesticides, heavy
metals etc.
 Characteristics used to describe sewage include:

turbidity, suspended solids, total dissolved solids,
acidity, dissolved oxygen, BOD.
222
Why Wastewater Treatment?
 To remove undesirable components so the water can be
safely released to the environment.
 Biomass must be removed so dissolved oxygen is not
depleted from surface water.
 Nitrogen and phosphorous must be removed to prevent
excessive algae growth, which can accelerate the
eutrophication process and cause water pollution.
 Heavy metals and pathogenic bacteria need to be
removed from wastewater to reduce the health risk for
organisms that will come into contact with the water.
 Excess salts are often removed because they would
make the water unsuitable for many industrial or
agricultural uses.
223
Sewage Treatment…
 Processes for the treatment of wastewater may be divided
into three main categories of primary treatment,
secondary treatment, and tertiary treatment.
Primary Waste Treatment

 Primary treatment of wastewater consists of the removal of
insoluble matter-material that will either float or readily
settle out by gravity (e.g. grit (sand, coffee grounds etc),
grease, and scum from water)
 It includes the physical processes of screening,

comminution, grit removal, and sedimentation.
224
Sewage Treatment…
 Screens are made of long, closely spaced, narrow metal bars.
 Screens block floating debris such as wood, rags, and other

bulky objects that could clog pipes or pumps.
 In modern plants the screens are cleaned mechanically, and the
material is promptly disposed of by burial on the plant grounds.
 A comminutor may be used to grind and shred debris that

passes through the screens. The shredded material is removed
later by sedimentation.
Example of a comminutor
 Grit chambers are long narrow tanks that are designed to slow
down the flow so that solids such as sand, coffee grounds, and
eggshells will settle out of the water.
• Grit causes excessive wear and tear on pumps and other plant
equipment. Its removal is particularly important in cities with
combined sewer systems, which carry a good deal of silt, sand,
and gravel that wash off streets or land during a storm.
Sedimentation
 Suspended solids that pass through screens and grit chambers
are removed from the sewage in sedimentation tanks. These
tanks, also called primary clarifiers, provide about two hours of
detention time for gravity settling to take place. As the sewage
flows through them slowly, the solids gradually sink to the bottom.
The settled solids-known as raw or primary sludge-are moved
along the tank bottom by mechanical scrapers. Sludge is
collected in a hopper, where it is pumped out for removal.
Mechanical surface-skimming devices remove grease and other
floating materials.
Secondary Waste Treatment
 Secondary treatment removes biodegradable organic matter.
Secondary wastewater treatment is designed to remove Biochemical
Oxygen Demand (BOD) usually by taking advantage of the same kind
of biological processes that would otherwise consume oxygen in the
water receiving the wastewater.
 Microorganisms provided with added oxygen are allowed to degrade

organic material in solution or in suspension until the BOD of the waste
has been reduced to acceptable levels. Removal of soluble organic
matter at the treatment plant helps to protect the dissolved oxygen
balance of a receiving stream, river, or lake.
 Removal is usually accomplished by biological processes in which

microbes consume the organic impurities as food, converting them into
carbon dioxide, water, and energy for their own growth and
reproduction.
 The sewage treatment plant provides a suitable environment-of steel

and concrete, for this natural biological process.
Secondary Waste Treatment…
 There are three basic biological treatment methods: the trickling filter,
the activated sludge process, and the rotating biological
contactor.
 A trickling filter consists of a fixed bed of rocks or other solid support

material (e.g. coke, gravel, ceramic, or plastic media) over which
sewage flows downward and causes a layer of microbial slime (biofilm)
to grow, covering the bed of media.
 A conventional trickling filter distributed
system is made in such a way that
wastewater is sprayed through a rotary
distributor arm that consists of a series
of nozzles so that the liquid spreads
evenly over the surface of the filter
media. The structure of the trickling
filter is such that contact of the
wastewater with air is allowed and
degradation of organic matter occurs
by the action of the microorganisms.
Secondary Waste Treatment…
 The activated sludge treatment system consists of an aeration
tank followed by a secondary clarifier. Compressed air is injected
into the aeration tank containing the sewage. As it bubbles to the
surface, the diffused air provides oxygen and a rapid mixing
action.
• Microorganisms in the aeration tank convert organic material in

wastewater to microbial biomass and CO2. Organic N is
converted to NH4+ or NO3-. Organic phosphorus is converted to
orthophosphate.
• The mixture then flows from the aeration tank into the secondary
clarifier, where activated sludge settles out by gravity. Clear
water is skimmed from the surface of the clarifier, disinfected,
and discharged as secondary effluent.
Secondary Waste Treatment by Biological Processes
 Rotating biological reactors: In this treatment system, a series
of large plastic disks mounted on a horizontal shaft are partially
submerged in primary effluent. As the shaft rotates, the disks are
exposed alternately to air and wastewater, allowing a layer of
bacteria to grow on the disks and to metabolize the organics in
the wastewater.
After the secondary treatment, the water can be disinfected, and

discharged as secondary effluent, OR- tertiary treatment. 232
Tertiary Waste Treatment
 Tertiary waste treatment involves removal of pathogenic
organisms and toxic substances (to further reduce organics,
turbidity, nitrogen, phosphorus, metals, and pathogens).
Sometimes called advanced waste treatment.
 The goal of this treatment is reuse of waste water or to meet
effluent guidelines.
 Categories of contaminants removed by tertiary waste treatment:

(1) suspended solids
(2) dissolved organic compounds-potentially toxic
(3) dissolved inorganic materials-algal nutrients, toxic metals.
(4) disease-causing microorganisms, requiring disinfection
 Most processes involve some type of physicochemical treatment

such as coagulation, filtration, activated carbon adsorption of
organics, reverse osmosis, and additional disinfection. 233
Industrial Wastewater Treatment
 Industrial wastewater treatment describes the processes used for
treating wastewater that is produced by industries. The treated
industrial wastewater may be reused or released to a sanitary sewer
or to a surface water in the environment.
 Wastewater can be treated by several physical processes

including: sedimentation, filtration, distillation, and membrane
processes (e.g. reverse osmosis, microfiltration, and ultrafiltration).
 Wastewater can be treated by a variety of chemical processes

including: acid-base neutralization, precipitation and
oxidation/reduction.
 Biological treatment by an activated sludge process to remove

organic wastes.
 Organic wastes can also be removed by sorption of toxic

234
substances by activated carbon.
Removal of Solids
 Relatively large solid particles are removed from water by simple
settling and filtration.
 A special type of filtration procedure known as microstraining is

especially effective in the removal of the very small particles.
These filters (microstrainers) consist of a finely woven stainless-
steel wire so fine that it is barely visible. This enables preparation
of filters with openings only 60-70 μm across.
Removal of Solids…
 Coagulation removes colloidal solids from the water:
The coagulants commonly used are aluminium sulphate
and ferric chloride which form gelatinous metal hydroxides
which carry suspended materials as they settle.
 Coagulation: a step in which chemicals (coagulants) are added
to cause small particles suspended in the water to clump
together.
 Coagulation-filtration: much more effective procedure

than filtration alone for the removal of suspended material
from water.
addition of coagulants ==> formation of large particles
followed by filtration. Filtration performed on a medium e.g.
sand, anthracite coal. Example: rapid sand filter.
236
Removal of Ca and other Metals
 Ca and Mg bicarbonates and sulphates cause water hardness.
 Several processes are used for softening water including:
 The lime-soda process: treatment of water with lime, Ca(OH)2, and

soda ash, Na2CO3. Ca2+ precipitated as CaCO3, and Mg2+ as Mg(OH)2.
When the calcium is present primarily as “bicarbonate hardness,” it
can be removed by the addition of Ca(OH)2 alone:
Ca2+ + 2HCO3- + Ca(OH)2  2CaCO3(s) + 2H2O
 Calcium present as the chloride can be removed from water by the

addition of soda ash:
Ca2+ + 2Cl- + 2Na+ + CO32-  CaCO3(s) + 2Cl- + 2Na+
CaSO4(aq) + Na2CO3(aq) CaCO3(s) + Na2SO4(aq)

237
Removal of Ca and other Metals…
 Chelation (sequestration): a complexing agent is added e.g.

chelating calcium ion with excess EDTA anion.
 Calcium may be removed from water very efficiently by the addition

of orthophosphate:
5Ca2+ + 3PO43- + OH-  Ca5OH(PO4)3(s)

Hydroxylapatite
Removal of Other Metals
 Oxidation to higher insoluble oxidation states through aeration.
E.g. Iron, Manganese
 Lime treatment removes metals as insoluble hydroxides, basic
salts, or coprecipitated with calcium carbonate or ferric hydroxide
 Electrodeposition: deposition of material on conducting surfaces
using electric current from a solution containing ionic species.
 Reduction of metal ions to metal by electrons at an electrode
 Cementation: a metal deposits by reaction of its ion with a more
readily oxidized metal,
e.g. Cu2+ + FeFe2+ + Cu
 Activated carbon adsorption

 Reverse osmosis
 Biological waste treatment-metals accumulate in the sludge
from biological treatment 239
Removal of Dissolved Organics
 Dissolved organics include: water disinfection by-products (e.g.
chlorinated organics, aldehydes, carboxylic acids), humic
substances, etherextractable materials, carbohydrates, proteins,
detergents, tannins, and lignins.
 Methods for the removal of dissolved organics:

 Adsorption on activated carbon - produced from carbonaceous
materials e.g. wood, pulp-mill char, peat, and lignite. The carbon
is produced by charring the raw material anaerobically below
600 oC followed by an activation step consisting of partial
oxidation.
 Adsorption is a surface process that leads to transfer of atoms,
ions or molecules from a fluid bulk to a solid surface.
 Adsorption on synthetic polymers such as Amberlite (XAD-4),

which have hydrophobic surfaces and strongly attract relatively
240
Removal of Dissolved Inorganics
 Methods for removing dissolved inorganics from water
include:
Distillation: This process relies on evaporation to treat

waste water. The water is heated to form steam. The steam
then cools and condenses to form purified water. However,
distillation is not generally economically feasible.
Reverse osmosis consists of forcing pure water through a

semipermeable membrane (porous cellulose acetate or
polyamide) that allows the passage of water but not of other
materials. Reverse osmosis can effectively remove nearly all
inorganic contaminants from water. It can also effectively
remove radium, natural organic substances, pesticides,
241
bacteria and viruses.
Removal of Dissolved Inorganics…
• Microfiltration is a membrane separation process that involves using
membranes with a pore size of approximately 0.03 to 10 microns (1 micron =
0.0001 mm) and a relatively low feed water operating pressure of
approximately 100 to 400 kPa. Materials removed by MF include sand, silt,
clays, algae, and some bacterial species. MF is not an absolute barrier to
viruses.
• Ultrafiltration has a pore size of approximately 0.002 to 0.1 microns and an

operating pressure of approximately 200 to 700 kPa. UF will remove all
microbiological species removed by MF, as well as some viruses and humic
materials.
• Nanofiltration membranes have a nominal pore size of approximately 0.001

microns, 1 nm. Pushing water through these smaller membrane pores
requires a higher operation pressure than either MF or UF. Operating
pressures are usually near 600 kPa and can be as high as 1,000 kPa. These
242
systems can remove virtually all cysts, bacteria, viruses, and humic materials.
Phosphorus Removal
 Removal of phosphorus to reduce algal growth.
1. Precipitation using Ca(OH)2, Al2(SO4)3, FeCl3 or MgSO4

e.g.
5Ca(OH)2 + 3HPO42-  Ca5OH(PO4)3(s) + 3H2O + 6OH-
Hydroxylapatite
2. Adsorption on activated alumina, Al2O3. Removes up to

99.9% of orthophosphate.
3. Activated sludge process removes some percent of the

phosphorus from sewage (in the aeration chamber of the
activated sludge unit).
243
Nitrogen Removal
 Removal of N to reduce algal growth
1. Air stripping ammonia: The aqueous form (NH4+) and gaseous
form (NH3) as the ammonium ion in aqueous exist together in
equilibrium as: NH4+ + OH air NH3 + H2O
 Ammonium can be removed by raising the pH to approximately
11 with lime, and converting ammonium to ammonia.
Air stripping is the transfer of volatile components of a liquid into an air stream.
2. Nitrification-denitrification This approach involves the conversion of

ammoniacal nitrogen to nitrate by bacteria under aerobic conditions,
2NH4+ + 3O2 + Nitrosomonas  4H+ + 2NO2- + 2H2O
2NO2- + O2 + Nitrobacter  2NO3-
followed by production of elemental nitrogen (denitrification):

4NO3- + 5{CH2O} + 4H+ + denitrifying bacteria  2N2(g) + 5CO2(g) + 7H2O
244
Nitrogen Removal…
3. Chlorination: Reaction of ammonium ion and hypochlorite (from

chlorine) results in denitrification by chemical reactions:
NH4+ + HOCI  NH2Cl + H2O + H+

Hypochlorous chloramine
acid
2NH2CI + HOCI  N2(g) + 3H+ + 3Cl- + H2O

4. Ammonium ion exchange: Clinoptilolite, a natural zeolite,
selectively removes ammonium ion by ion exchange:
Na+{-clinoptilolite} + NH4+  NH4+{-clinoptilolite} + Na+.
The ion exchanger is regenerated with sodium or calcium salts.

Water Disinfection
• Disinfection is the process of destroying pathogenic
organisms or rendering them inert.
• The spread of pathogenic microorganisms through water

supply is the most serious pollution hazard to human health.
The most serious problems are created by the contamination
of drinking water by human wastes.
• The way to prevent microbial contamination is to keep the

water supply as free from wastewater discharges as possible
and to treat it with disinfectants.
• A disinfectant is an agent, such as heat, radiation, or a

chemical, that destroys, neutralizes, or inhibits the growth of
disease-carrying microorganisms. 246
Water Disinfection
• The disinfectants currently in use are:

ozone,
chlorine dioxide, and
chlorine.
• Of these the most common is chlorine.
• Iron(VI), in the form of ferrate ion, FeO 42-, is also a
strong oxidizing agent with excellent disinfectant
properties.
247
Water Disinfection
When chlorine is added to water it disproportionates:
Cl2 + H2O → HOCl + H+ + Cl-
The HOCl (hypochlorous acid) is an oxidant, the Cl is in the
+1 oxidation state and is readily reduced to Cl-
HOCl passes through the cell walls of microorganisms and
kills them by oxidizing vital molecules.
Ozone and chlorine dioxide are powerful and diffusible
oxidants, and kill microbes in the same way.
Ozone is a better disinfectant than Cl2, because of fast
decomposition: 2O3  3O2(g)
Chlorine is an effective and relatively inexpensive
disinfectant.
248
Wastewater Reclamation
 Wastewater reclamation involves the treatment of wastewater
to a quality level acceptable for reuse.
 Reclaimed water, sometimes called recycled water, is former

wastewater (sewage) that has been treated to remove solids
and certain impurities, and then used in sustainable
landscaping irrigation or to recharge groundwater aquifers.
This is done for sustainability and water conservation, rather
than discharging the treated wastewater to surface waters
such as rivers and oceans.
 In most locations, it is intended to be only used for nonpotable

uses, such as irrigation, dust control, and fire suppression.
There is a debate about possible health and environmental
effects with its uses.
249
Benefits of Wastewater Reclamation
 Using reclaimed water for non-potable uses saves

potable water for drinking, since less potable water
will be used for non-potable uses.
 It sometimes contains high levels of nutrients such as
nitrogen, phosphorus and oxygen which may
somewhat help fertilize gardens and agricultural
plants when used for irrigation.
 The usage of water reclamation decreases the
pollution sent to sensitive environments.
 It can also enhance wetlands, which benefits the
wildlife depending on that ecosystem.
250
Concerns About Wastewater Reclamation
 Treated wastewater effluent, or reclaimed water,
contains pathogens that could be transferred to people
through contact.
 Since the number and types of bacteria in a treatment
plant are large, and are exposed to antibiotic
pharmaceuticals in wastewater, a positive environment
exists for transfer of drug resistance.
 There is also concern in the industry about organic
chemicals, including endocrine disruptors in
wastewater.
251

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CH 262

Environmental chemistry is the study of the

 Environmental chemistry is about

 It aims to apply knowledge of chemistry to

 Examples of pollutants: Nitrogen oxides, sulfur

 In the process of environmental pollution, pollutants

 The atmosphere is a thin layer of gases that

 Atmospheric chemists are interested in

 These trace components are where the interesting

The atmosphere: reservoir of gases, moderates

The concentration of a gas in the environment is

 The “parts per …..” units express the number of

 The atmosphere extends from the earth’s

 Functions of the atmosphere include:

 The troposphere contains air and clouds. Nearly

 We live our entire lives within the troposphere.

 The troposphere is denser than the other layers

 It is the layer above the troposphere, separated

 The stratosphere contains the ozone layer; It is the

 The presence of ozone in the stratosphere helps

 The troposphere and the stratosphere

 The lower atmosphere is the domain of

Ozone depletion (stratosphere)

Air pollution (troposphere)

 In the mesosphere, temperature decreases with

 It extends from the mesopause to the

 In the thermosphere, temperature rises with

 High-energy radiations from the sun are absorbed in

 The temperature of the thermosphere gradually increases

 The ionosphere is a region of the atmosphere that is

 Since most of this harmful radiation is absorbed during

he outermost layer of the atmosphere is the exosph

 Extending from the top of the thermosphere

There are simply fewer and fewer molecules

 Air pollution can be

 Secondary pollutants: Formed through

 Those added in high amount are:

 NOx (NO, and NO2)

Others are: NH3, N2O, H2S, Cl2, HCl, and HF.

 Carbon monoxide (CO) is a colorless, odorless,

 Industries using various carbon-based fuels

 Residential sources: E.g. firewood, charcoal,

 Incineration of solid wastes

 Biomass burning: Agricultural clearing

Incomplete burning of biomass:

 The reaction produces hydroperoxy radical

where M is a third body, such as a molecule

HOO• + NO → HO• + NO2

HOO• + HOO• → H2O2 + O2

 Adjustment of air-fuel ratio: The air-fuel ratio acts as a significant role

 Application of catalytic converter: A catalytic converter is an

 Non-anthropogenic sulphur enters the atmosphere

 Decay of organic matter.

SO2 by the following process;

• H2S reacts with hydroxyl radical:

H2S + HO• → SH• + H2O

• Followed by the following two reactions to give SO2

• Much of the SO2 in the atmosphere ultimately is

 Many processes have been proposed for the removal of

1. Lime slurry scrubbing