Air Pollution Chemistry

Air pollution is the toxification of the atmosphere through the

addition of harmful substances in the air. It is an indication of
disturbances to the composition of compounds in the
atmosphere.
Pollutants are substances that have harmful effects on the
health, survival, or activities of humans or other living organisms.
Common Air Pollutants:
•What are these gases?
– NO, NO2, SO2, CO, particulates, lead, ozone, and VOC
•What are their effects on life?
– Health effects, welfare effects
•Where do these gases end up in the environment?
– Acid rain, global warming, etc.
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 Common Air Pollutants
• Particulate matter:
– total suspended particulate (TSP) (typical size <
100 mm)
– respirable suspended particulate (RSP) (typical
size < 10 mm) (PM10, particulate matter of size <
10 mm)

– Sources of PM:
• Natural: wind, sandstorm, forest fires, volcano
eruption
• Anthropogenic: industry, automobiles
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 Particulates
Particulates include aerosol, fog, haze, mists and smoke. The
characteristics of the particulates are described below:
Aerosol = Colloidal-sized atmospheric particle. Formed by
condensation of vapors or reactions of gases or by grinding of
solids, atomization of liquids, or dispersion of dusts.
 Fog = high level of water droplets
Haze = Denotes decreased visibility due to the presence of
particles
 Mists = Liquid particles
Smoke = Particles formed by incomplete combustion of fuel
Combustion processes, including fossil-fuel-fired power plant,
incinerators, stoves and vehicles engines, etc, are the major
chemical processes that produce particles.
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 Air Pollutants Sources
• Photochemical pollutants:
– VOC, O3, CFC, greenhouse gases (CO2, CH4, H2O)
• Natural pollutant sources
Volcano eruption: emitting smoke, particulate
matter, SO2, H2S, CH4…
Fires: emitting smoke, unburnt hydrocarbons,
CO, CO2, NOx...
Dust or sand storms dispersing dust
Oceans are emitting corrosive salt aerosols
Normal human respiration produces CO2
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 Air Pollutants Sources
• Artificial or anthropogenic sources
Stationary sources: combustion, fuel usage, waste
incineration, industrial processes.
Mobile sources: all emissions and exhausts from
transportation.

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 Primary and Secondary Air
Pollutants
• Two types of air pollutants: primary and secondary.
• Primary pollutants: Released directly from sources
– Examples: particulate matter (smokes and dust), methane,
sulfur dioxide, nitrogen oxides (NO, NO 2), carbon oxides
(CO, CO2).
• Secondary pollutants: Formed through chemical
reactions of the primary pollutants and the constituents of
the unpolluted atmosphere in the air.
– Examples: ozone, nitrates, sulfur trioxide, nitric acid,
sulphuric acid, sulphates, peroxides, peroxyacetyl nitrate
(PAN).

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 Types and Sources of Air Pollutants

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 Effects of Particulate Matter Pollution
 Visibility: Particles are able to scatter lights with
wavelengths close to the particle size.
 Because of this particulate matter pollutions
usually yield hazy days and visible smog.

 Health: Asthma, respiratory syndromes,

bronchitis, decreased lung functions.

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 Effects of Particulate Matter Pollution

– Climate: Fine particles can be called condensation

nuclei in meteorology.
• When wet air reaches saturation condition, the
existence of fine particles makes it easier for water
vapour to condense and form tiny droplets, forming
fog and mist.
• It also leads to formation of clouds

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 Air Pollution Control
• Use of filters to stop particles.
• Catalytic converters in cars used to reduce emissions of
NOx, hydrocarbons, and CO.
• Development of hydrogen powered or electric vehicles
to reduce emissions of pollutants.
• Cars must be inspected frequently.
• Reduce indoor pollution e.g. by proper ventilation.
• Avoid the creation of the pollutants.
• Develop nonpolluting energy sources like solar energy,
wind power, and hydropower.
• Encourage mass transit.

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 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 (NO3- etc), 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 wastes.
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 Sources of Water Pollution
• One of the noted cases of surface water pollution is the
excess input of phosphate ion, PO43-.
• Phosphates sources are: the polyphosphates in
detergents, raw sewage and runoff from farms that used
phosphates fertilizers.
• Phosphate ions usually function as the limiting (or
controlling) nutrients for algal growth. The larger the supply
of the ion, the more abundant the growth of algae.
• The sources of water pollution can be considered as point
sources of pollution, and non-point sources of pollution.
• Point sources are factories and other industrial and
commercial installations that release toxic substances into
the water. These toxic chemicals include Cd, Cr, Hg and
Pb, cyanide, and several chlorinated and nonchlorinated
organic compounds.
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 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. They
include:
– Emissions from transport vehicles,
– Agricultural runoff, which carry excess nutrients,
pesticides, silts etc into streams and groundwater
and
– Urban runoff, which can carry toxic metals and
organics through storm drains into sewage treatment
plants or directly into rivers and lakes.

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 Water Pollution
Ground water
– contaminated by chemicals for decades.
Ground water contaminants are:
– Inorganics; NO3- from farms (Fertilizers), Heavy metals
•Organics;
– Chlorinated solvents compounds/solvents
– Hydrocarbons such as benzene, C6H6, and its methylated
derivatives, e.g., toluene, C6H5CH3, and isomers of xylene,
C6H4(CH3)2.
– Organic pesticide
– Drug residues and
– Currently, microplastics
 Emerging Contaminants in Water
• ECs are chemicals occurring in water resources and
identified as being a potential environmental or
public health risk but adequate data do not exist to
determine their risks
• ECs include:
– pharmaceuticals,
– endocrine disrupting compounds
– disinfectant byproducts,
– algal toxins (Blue green algae),
– microplastics

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 SOIL POLLUTION
• Soil pollution 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, percolation of contaminated surface water to
subsurface strata, leaching of wastes from landfills or sewage
sludge and direct discharge of industrial wastes to the soil.
• Soil receives enormous quantities of pollutants.
• 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
of water supplies.

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 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.
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 Classification of pesticides
1. Pesticides can be classified according to targeted pests; i.e.
insecticides (for insects), herbicides (for weeds), fungicides (for
fungi), bactericides (for bacteria), rodenticides (for rodents) etc.
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.
Broad spectrum pesticides-chemicals that kill a wide range of
pests.
Selective pesticides-chemicals that kill only a specific pest or
group of pests.
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Classification and chemistry of pesticides
3.Chemical Classification depending on active
ingredient:
• Pesticides can be grouped according to chemical
structure. Most 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.

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 Classification and chemistry of pesticides
(a) Organochlorine pesticides
• Organochlorine pesticides contain C, H and Cl atoms. They are
insecticides, which readily penetrate the waxy coating of insects.
• 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.
• Have low toxicity to animals, including human beings.
• They undergo bioaccumulation in food chains and cause chronic
health effects .
• Example of the organochlorine insecticides include DDT
(dichlorodiphenyltrichloroethane), endosulfan, aldrin, dieldrin
etc. Commercially available DDT (technical grade) contains two
isomers of DDT: p,p’-DDT and o,p’-DDT. Hexachlorocyclohexane
(HCH) is a name used collectively for eight isomers including α, β,
γ, δ, and ε-HCH. The γ-HCH has the highest pesticidal activity;
however, technical mixtures of all isomers have been widely used.
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Classification and chemistry of pesticides
Examples of organochlorines
Cl Cl Cl
Cl Cl
Cl
Cl
Cl Cl O
Cl S O
Cl O
Cl
DDT γ-Hexachlorocyclohexane
(Lindane = >99% γ-HCH) Endosulfan

Cl Cl

Cl
Cl
O

Cl Cl

Chlordane Aldrin Dieldrin

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Classification and chemistry of pesticides
Examples of organochlorines

Cl Cl

Cl
Cl

Cl
Cl

Heptachlor Cl Dicofol

Cl Cl
Cl
Cl
Cl
Cl Cl

Cl
Cl Cl Cl
Cl

Mirex

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Classification and chemistry of pesticides

(b) Organophosphorus pesticides

• Commonly called organophosphates. They are insecticidal
organic compounds containing phosphorus, e.g.:

Parathion
Malathion

Dichlorvos
Chlorpyrifos
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 Classification and chemistry of pesticides
Organophosphates are extremely toxic; they act by inhibiting
acetylcholinesterase (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.
They are non-persistent; they break down rapidly into harmless
and water soluble products, once released into the environment.
They are reactive and generally susceptible to hydrolysis in the
environment.
Organophosphates do not bioaccumulate.
The organophosphorus pesticides affect and damage the
nervous system and can cause cancer. They cause reproductive
and endocrinal damage also.
Because of their high biodegradability and restricted use,
organophosphates are of comparatively little significance as
water pollutants.

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Classification and chemistry of pesticides
(c) Carbamates e.g. carbaryl and aldicarb are pesticidal organic
derivatives of carbamic acid (CH3NHCOOH). They are non-
persistent insecticides.
• Carbamates are more biodegradable than organochlorine
insecticides and have lower dermal toxicities than most
organophosphate pesticides.
• Carbamates are anticholinesterase compounds that inhibit the
removal or breakdown of acetylcholine.

O NH
CH3

Carbaryl aldicarb

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 Classification and chemistry of pesticides
(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
Deltamethrin

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 Classification and chemistry of pesticides
 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 by mimicking the
female hormone, estrogen, thus causing excessive estrogen
levels in females and lowered sperm counts in human males.
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 Classification and chemistry of pesticides
(e) Phenoxy Acid Herbicides
 The phenoxy acid 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).
 These substances are polar and exhibit relatively high
solubility in water.
 They have comparatively low toxicity to animals.
 Persistence in the environment is also comparatively low.
Cl

Cl OCH2COOH
Cl OCH2COOH

Cl 2,4,5-T
Cl
2,4-D
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 Classification and chemistry of pesticides
(f) Triazines
 Triazine herbicides e.g., atrazine, are cyclic compounds,
containing a ring system composed of three carbon and
three nitrogen atoms.
 They are applied to the soil primarily for their
postemergence activity.
 They are strong inhibitors of photosynthetic electron
transport.

(CH3)2CHNH N Cl

N N

NHCH2CH3

Atrazine

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 Classification and chemistry of pesticides
(g) Urea Herbicides e.g., linuron and isoproturon, are
substituted ureas (H2NCONH2), having their hydrogen
atoms replaced by various carbon chains and rings.
• They are usually applied to the soil as preemergence or
postemergence materials.
• They are strongly absorbed by the soil, then absorbed by
roots.
• Their mechanism of action is inhibition of photosynthesis.
CH3 H3C
Cl NH C N CH3
CH NH C N
OCH3
O H3C CH3
Cl O
linuron Isoproturon

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 Classification and chemistry of pesticides
4. Classification depending on formulation
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, stickers, wetting agents, spreaders, or other
adjuvants (materials added to increase the effectiveness
or change the properties of the pesticide in the spray mix).
This mixture of a.i. and inert (inactive) ingredients is called
a pesticide formulation. Examples of pesticide
formulations are liquids, powders, granules,
baits/attractants, dusts, smoke generators.
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.
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 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.

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 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
Cl Cl
Cl Cl
Cl Cl Cl
Cl Cl
Oxygenation 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

Cl Cl Cl
Cl Cl Cl Cl Cl

Cl Cl Cl Cl Cl
Cl HCH Cl Cl

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 Degradation/Transformation of Pesticides: Examples
•
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
H2O + 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

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 HEAVY METALS

• Heavy metals are metals with a specific gravity greater

than about 5, especially ones that are poisonous, such as
Pb or Hg.
• 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.

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 Trace Inorganic Contaminants
• Important trace elements encountered in
natural waters include;
– Iron,
– Manganese,
– arsenic,
– chromium,
– cadmium,
– copper,
– lead,
– mercury, etc.
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 Iron and Manganese
• Both iron and manganese create serious
problem in public water supplies.
• Iron exists in soils and minerals mainly as
insoluble ferric oxides and iron sulfide
(pyrite).
– It occurs in some areas as ferrous carbonate
which is very slightly soluble.
• Since groundwater contain CO2, appreciable
amount of ferrous carbonate may be
dissolved by the reaction below;
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 Iron and Manganese
– Sources of Iron; Industrial wastes, corrosion, acid
mine water, microbial action.
• Manganese exists in the soil as manganese
dioxide, which is very insoluble in water
containing CO2.
– Under reducing (anaerobic) conditions, the
manganese in the dioxide form is reduced from
Mn(IV) to Mn(II) as that of ferric oxides.
– Sources; Industrial wastes, acid mine water,
microbial action.
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 Other Trace Elements
• Lead; This is toxic element.
• Sources;
– lead arising from a number of industrial and
mining source;
– Fuels; leaded gasoline used to be a major source
of atmospheric and terrestrial lead.
– lead-bearing limestone and galena (PbS)
contribute lead to natural waters in some
locations.
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 Other Trace Elements
• Health effect of lead
• Acute lead poisoning in humans causes severe
dysfunction in the kidneys, reproductive system,
liver, brain and central nervous system.

• Lead poisoning from environmental exposure

cause mental retardation in children.

• Mild lead poisoning cause anemia

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 Other Trace Elements
Cadmium;
•cadmium in water may arise from industrial
discharges and mining wastes.
•It is widely used in metal plating.
– The effects of acute cadmium poisoning in
humans include;
• high blood pressure,
• kidney damage, and
• destruction of red blood cells.

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 Other Trace Elements
• Mercury; Toxic element, mobilized as methyl
mercury compounds by anaerobic bacteria.
• Mercury enters the environment from
Industrial waste, mining, coal, discarded
laboratory chemicals, batteries, broken
thermometers, amalgam tooth fillings
• Among the toxicological effects of mercury
are neurological damage, including paralysis,
blindness, or insanity; chromosome breakage,
and birth defects.
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 Other Trace Elements
• Arsenic, very toxic and suspected to be
carcinogenic. Its sources are mining
byproduct and chemical waste.
• Chromium, Essential as Cr(III), toxic as
Cr(VI). Source; Metal plating.
• Beryllium; Toxic element, source; Coal,
industrial wastes.
• Copper; Essential trace element, toxic to
plants and algae at higher levels. Sources;
Metal plating, mining, Industrial waste.
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 PERSISTENT ORGANIC POLLUTANTS (POPS)
• POPs are chemical substances that persist in the
environment, bioaccumulate through the 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).
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 PERSISTENT ORGANIC POLLUTANTS (POPS)
(b) Industrial chemicals
(i) PCBs (Polychlorinated biphenyls) used in transformers, large
capacitors, as heat exchange, as paint additives, in carbonless copy
paper and in plastics.
(ii) Perfluorooctane Sulphonic Acid (PFOS) and Its Salts used in fire
fighting foams, carpets, insecticides such as sulfluramid etc.
• (iii) Polybrominated diphenyl ethers( PBDE) e.g. Tetrabromodiphenyl
ether, pentabromodiphenyl ether, hexabromodiphenyl ether and
heptabromodiphenyl ether used in cars trains, planes, and ships.
(c) Unintentionally produced combustion substances e.g
Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD and PCDF
or Dioxins and Furans), Polycyclic Aromatic Hydrocarbons (PAHs),
Hexachlorobenzene, Pentachlorobenzene and PCBs. Dioxins are
released into the environment through production of pesticides and
chlorinated substances. Dioxins and furans are emitted from the
incineration of hospital, municipal and hazardous waste, car emissions,
and the incineration of coal, peat and wood. PAHs are products of
combustion from automobiles, airplanes etc.
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 Examples of POPs
• Organochlorines (Pesticides and PCBs)

DDT

PCBs (R = Cl and H)
There are 209 possible PCBs
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 Examples of POPs (Ctd)
• Dioxins and Furans
O

O O Clx
Cly Clx Cly
Chlorinated Dioxins Chlorinated Furans
Cl O Cl Cl Cl

E.g.
Cl O Cl Cl O Cl
2,3,7,8-Tetrachlorodibenzo-p-dioxin 2,3,7,8-Tetrachlorodibenzo-p-furan

 Polycyclic Aromatic Hydrocarbons

(PAHs) e.g.
 PBDEs Benzo(a)pyrene
Phenanthrene

PFOS
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 Why are POPs a problem?
They cause significant adverse effects to human health
and wildlife.
They move through the food chain to humans.
They are passed on from mother to child across the
placenta, and through breast milk.
They clearly pose a hazard on wildlife populations, e.g.
DDT causes the eggshells of birds to become so thin they
break during incubation.
POPs have toxic effects on the nervous, endocrine and
immune systems; some are carcinogenic, teratogenic or
mutagenic
 POPs are persistent in the environment and migrate over
long distances from their source.

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 The Science of POPs
POPs possess the following properties:
1. Toxicity: The lipophilicity of these compounds means that they
bioconcentrate, accumulate and persist and thus, achieve
toxicologically relevant concentrations.
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.

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 The Science of POPs
2. 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.
3. 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.
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
Earth’s surface.
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52
 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
that can also be converted to aldrin-diol.
 Refer Transformation of Pesticides.

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 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 know as the ‘dirty dozen’
i.e.
9 Organochlorine pesticides (DDT, aldrin, dieldrin, endrin, chlordane,
heptachlor, hexachlorobenzene, mirex, and toxaphene,
PCBs, Dioxins and Furans.
• The convention has been 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.
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 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, plastic cans, newspaper,
glass bottles, cardboard boxes, aluminium foil, metal items,
wood pieces, etc, which is classified as dry garbage.

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 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.
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 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.

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 Management of Municipal Solid Wastes
• Management and disposal of municipal solid wastes involve
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 refuse.
• 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.
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 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 - immobilization in glass; imbedding wastes in
a glass material.
• 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
permitted landfill, and (vi) Discarded into the environment.

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 Effects of Water and Soil Pollution
The effects of water and soil pollution are myriad. Example 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.
• Water pollution causes human deaths worldwide. Almost every type
of contamination found in water has a detrimental effect on humans.
• Diseases e.g. blood diseases, heart disease and nervous system
disorders are commonly linked to the effects of water/ soil pollution.
• 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.
• Less severe effects of water pollution can include diarrhoea, skin
lesions, and vomiting.
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 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 composing the city wastes.
• Water treatment of drinking water, industrial water/ effluents,
sewage or wastewater.
• Wastewater reclamation-Reuse of treated water.
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 WATER TREATMENT
 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.

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 Water Treatment

• Municipalities treat their sewage to reduce

water pollution and eutrophication
• Water treatment involves aeration to remove
odours by purging dissolved gases and volatile
organic compounds.

• Aeration also oxidises any Fe2+ to Fe3+, which

forms Fe(OH)3 and precipitates out.
01/23/25 Environmental Chemistry 63
 Water Treatment
• Additional Fe3+ or Al3+ ions are then added
deliberately, usually as the sulphate salt, along
with lime to adjust pH.
– A voluminous Fe(OH)3 or Al(OH)3 precipitate is
produced, which traps solid particles that may be
suspended in the water supply.
• Most municipalities water treatment processes
harness bacteria to metabolise organic
compounds (Biomass), converting them to CO2.
• Thus, Biochemical Oxygen Demand (BOD) is substantially decreased
 Water Treatment Processes
Step 1: Raw water intake and screen:
– Water is delivered from the source (lake, Stream,
river or groundwater) to the water treatment
facility
– Screen - Prevent trash, logs or fish from entering
the treatment facility.
Step 2: Coagulation and Flocculation;
– In coagulation, coagulants like lime and alum are
added to the water, which causes particulates to
clump together.
– Then water is shaken into larger clumps called
flocs.
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 Water Treatment Processes
Step 3: Sedimentation;
•Water is allowed to stand for 24 h, for the
clumps to settle to the bottom in the settling
basin.

Step 4: Filtration;
•Water is then filtered and disinfected (usually
with chlorine or chlorine dioxide)

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Environmental Chemistry 66
 Water Treatment Processes
Step 5: Disinfection;
•Disinfection process is designed to kill or
deactivate most microorganisms in water.
Types of Disinfections
• Physical
– Ultraviolet (UV) rays
– Heat
• Chemical
– Chlorine
– Chlorine dioxide
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 Water Chlorination Chemistry
(chlorine and chlorine-dioxide)
• Chlorine is the most commonly used
disinfectant employed for killing bacteria in
water.
• When chlorine is added to water, it rapidly
hydrolyzes according to the reaction;
– Cl2 + H2O ↔ H+ + Cl- + HOCl
• Hypochlorous acid, HOCl, is a weak acid that
dissociates according to the reaction
– HOCl ↔ H+ + OCl-
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 Water Chlorination Chemistry
(chlorine and chlorine-dioxide)
• The two chemical species formed by chlorine in
water, HOCl and OCl- , are known as free
available chlorine.
• Free available chlorine is very effective in killing
bacteria.
• In the presence of ammonia; monochloramine,
dichloramine, and trichloramine are formed:
• NH3 + HOCl → NH2Cl (monochloramine) + H2O
• NH2Cl + HOCl → NHCl2 (dichloramine) + H2O
NHCl + HOCl →NCl (trichloramine) + H O
01/23/25 Environmental Chemistry 69
 Water Chlorination Chemistry
(chlorine and chlorine-dioxide)
• The chloramines are called combined available
chlorine.
• Chlorination practice frequently provides for
formation of combined available chlorine which,
although a weaker disinfectant than free available
chlorine, is more readily retained as a disinfectant
throughout the water distribution system.
• At sufficiently high Cl:N molar ratios in water
containing ammonia, some HOCl and OCl- remain
unreacted in solution, and a small quantity of NCl3
is formed.
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 Water Chlorination Chemistry
(chlorine and chlorine-dioxide)
• The ratio at which NCl3 occurs is called the breakpoint.
• Chlorination beyond the breakpoint ensures
disinfection.
• Problems can arise from chlorination of organic wastes
as they introduce by-products.
– Typical of such by-products is chloroform and other
trihalomethanes (recognized as potent carcinogens
at low levels of concentrations) produced by the
chlorination of humic substances in water.

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71
Environmental Chemistry
 Water Chlorination Chemistry
(chlorine and chlorine-dioxide)
• Chlorine dioxide, ClO2, is an effective water
disinfectant that does not produce impurity
trihalomethanes in water treatment.
• In acidic and neutral water, respectively, the
two half reactions for ClO2 acting as an
oxidant are;
– ClO2 + 4H+ + 5e- ↔Cl- + 2H2O
– ClO2 + e- ↔ ClO2 -

01/23/25 Environmental Chemistry 72

 Water Chlorination Chemistry
(chlorine and chlorine-dioxide)
• In the neutral pH range, chlorine dioxide in
water remains largely as molecular ClO2
until it contacts a reducing agent.

• As a water disinfectant, chlorine dioxide

does not chlorinate or oxidize ammonia or
other nitrogen-containing compounds.

01/23/25 Environmental Chemistry 73

 Treatment of Water for Industrial Use
 Important Factors: water requirement, quantity and
quality of sources, sequential use of water, water recycle
and discharge standard
 External treatment: aeration, filtration and clarification
 Internal treatment: to modify the properties of water
• reaction of dissolved O2 with hydrazine or sulphite,
• addition of chelating agents,
• addition of precipitants,
• treatment with dispersants to inhibit scale,
• addition of inhibitors to prevent corrosion,
• adjustment of pH,
• disinfection for food processing uses.

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 Sewage Treatment
 Sewage contains oxygen-demanding materials,
sediments, grease, oil, scum, pathogenic bacteria, viruses,
salts, algal nutrients, pesticides, refractory organics, heavy
metals etc.
 Characteristics used to describe sewage include: turbidity,
suspended solids (ppm), total dissolved solids (ppm),
acidity (H+ ion concentration or pH), dissolved oxygen (in
ppm O2).
 BOD is used as a measure of oxygen-demanding
substances. High concentrations of nutrients in water
bodies can potentially cause eutrophication and hypoxia.
Eutrophication is a process whereby water bodies receive
excess nutrients that stimulate excessive algae and plant
growth (nuisance weeds). Hypoxia means "low oxygen."
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 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.
Often the water is treated to remove excess salts that
would make the water unsuitable for many industrial or
agricultural uses.

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