CH 2-EnvChemistry

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ENVIRONMENTAL CHEMISTRY
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ENVIRONMENTAL
CHEMISTRY
2
Navindu Gupta, R.S. Khoiyangbam, and Niveta Jain
2.1 Introduction
Environmental chemistry is the study of the chemical and biochemical
phenomena that occur in nature. It involves the understanding of how
the uncontaminated environment works, and which naturally occurring
chemicals are present, in what concentrations and with what effects.
Without this it would be impossible to study accurately the effects
that humans exert on the environment through the release of chemical
species. It is a multi-disciplinary science that, in addition to chemistry,
involves physics, life science, agriculture, material science, public health,
sanitary engineering, and so on. More or less, it is the study of the
sources, reactions, transport, effects, and fate of chemical species in the
air, water, and land, and the effect of human activities upon the various
environmental segments, such as atmosphere, hydrosphere, lithosphere,
and biosphere.
Importance of the environment across the developed countries
was realized in the 1960s and reached its climax in 1970, with the
celebration of “Earth Day” under the auspices of the United Nation.
From 1972 onwards, with the conclusion of the UN Conference on
Human Environment at Stockholm, the important environmental issues
were percolated across India and other developing nations. The need
for environmental education, both formal and non-formal, was keenly
felt at the national level. The objective of environmental education is to
enlighten the public about the importance of protection and conservation
of our environment and about the needs to restrain human activities that
lead to indiscriminate release of pollutants into the environment.
At present, many environmental issues exist that have grown in size
and complexity day by day, threatening the survival of mankind on earth.
The various incidences of such environmental issues include London smog
of 1952—killing about 4000 people, the Mediterranean sea turning into
Dead Sea in the 1950s—unable to support aquatic life, death of a number
of Japanese people because of eating fish from the Minamata Bay in the
1960s, historical monuments and statues in Greece and Italy getting
damaged by the effect of rainwater, white marble of Taj Mahal in India
16 Introduction to Environmental Sciences
becoming yellow by the action of sulphur dioxide fumes, leakage of methyl

isocyanate (MIC) vapours at Bhopal in India in 1984, and the hazardous
effects of nuclear weapons and radiations on the people of Hiroshima and
Nagasaki. Pollution of river water in India, use of plutonium or other
isotopic fuel-based breeder/nuclear reactors for energy production, use of
dangerous artificial food additives, and ozone hole in the Antarctic and
Arctic regions are some typical chemical issues that need to be resolved
critically.
2.2 ENVIRONMENTAL SEGMENT

There are four environmental segments: atmosphere, hydrosphere,
lithosphere consisting of abiotic or physical environment, and biosphere—
the fourth segment of environment that consists of flora and fauna. Abiotic
and biotic components together constitute the biome environment.
Atmosphere
Atmosphere is a protective blanket of gases surrounding the earth, which
supports life and protects it from the hostile environment of outer space.
Atmosphere absorbs most of the cosmic rays from outer space and a major
portion of the electromagnetic radiation from the sun, and also maintains
the heat balance of the earth. It transmits only near-ultraviolet, visible,
near-infrared (IR) (300–2500 nm), and radio waves (0.14–40 m), and
absorbs energy re-emitted from the earth in the form of IR radiation. It
serves as an insulator against heat loss from the surface of the earth, and
stabilizes weather and climate owing to the heat capacity of the air.
The major gases of the atmosphere are nitrogen and oxygen, while the
minor gases are argon, carbon dioxide, and some trace gases. Atmosphere
is the source of oxygen and carbon dioxide. Several cycles that relate to
the movement of matter between an organism and its environment are
also present in the atmosphere—hydrological cycle, carbon cycle, nitrogen
cycle, phosphorus cycle, and many others. It also supplies nitrogen, which
is used by nitrogen-fixing bacteria and ammonia manufacturing plants
to yield chemically bound nitrogen that is essential for life. The details
of these cycles are discussed in the later part of the chapter.
The atmosphere can be divided into the following five concentric layers,
depending on the temperature variations:
(i) Troposphere: In this layer, humans and other organisms live.
(ii) Stratosphere: In this layer, the the temperature is very low,
because of which there are no clouds, dust, or water vapours.
(iii) Mesosphere: In this layer, the temperature drops to about −95°C.
The principal chemical species in the mesosphere are N2, O2, O2+,
and NO+.
Environmental Chemistry 17
(iv) Thermosphere or ionosphere: In this layer, most of the gaseous

components are ionized under the influence of radiant energy and
so ionosphere contains electrically charged particles such as O+, O2+,
and NO+. Radio messages can be transmitted through this layer
round the curve of the earth.
(v) Exosphere: In this layer, the temperature is very high due to solar
radiation. This region lacks atoms except hydrogen and helium.
Human beings, on the one hand, are enjoying all the advantages of
the development in science and technology and, on the other hand, have
been dumping waste materials into the atmosphere and producing a large
number of pollutants, which are threatening the survival of mankind
itself on earth.
Hydrosphere
Hydrosphere, which covers more than 75% of the earth’s surface, includes
all types of water resources—oceans, sea, rivers, lakes, streams, reservoir,
glaciers, polar ice caps, and groundwater (that is, water below the earth’s
surface). About 97% of the total water available on earth is in the form of
oceans, which cannot be used for human consumption owing to its high
salt content. About 2% of the water resources are locked in the polar
ice caps and glaciers, while only 1% is available as freshwater (surface
water—river, lakes, streams, and groundwater) for human consumption
and other uses. Freshwater is also available in the form of rains, snow,
dew, and so on.
Among all liquid substances, water possesses the highest heat of
fusion and evaporation at ordinary temperature. These properties of
water moderate the temperature of the biosphere. The history of ancient
civilization—growth and decline—is intimately linked with the quantum
of the water supply. The major uses of water are for irrigation (30%) and
thermal power plants (50%), while other uses include domestic (7%) and
industrial consumption (about 12%). Water is also a buoyant medium.
Organisms can survive in it without specialized supportive structures.
Surface water gets contaminated by pesticides and fertilizers from
agricultural run-off water, human and animal wastes in sewage, and
industrial wastes. Salinity in water is one such example. Salinity of
marine water is about 3–3.5%.
Lithosphere
This is the outer mantle of the solid earth, consisting of minerals
occurring in the earth crust and the soil. The earth is a cold, spherical
solid planet of the solar system, which spins on its axis and revolves
around the sun, maintaining a certain constant distance. It comprises
a complex mixture of minerals, organic matter, air, and water.
Lithosphere mainly consists of three layers: crust, mantle, and outer

and inner core. The surface of the crust is covered with soil, which is the
most important part of lithosphere. Soil is a mixture of organic as well
as weathered rock and materials necessary for the growth of plants. It is
a storehouse of minerals, a reservoir of water, a conserver of soil fertility,
a producer of vegetative crops, and a home of wildlife and livestock.
Biosphere
Biosphere denotes the realm of living organisms and their interaction
with the environment, that is, atmosphere, hydrosphere, and lithosphere.
Both the biosphere and the environment are influenced by each other
considerably. Thus, the levels of oxygen and carbon dioxide in the
atmosphere depend entirely on the plant kingdom. As a matter of fact,
green plants alone are responsible for the accumulation of oxygen in the
atmosphere, through photosynthesis and decay; the original atmosphere
was devoid of oxygen. The biological world, in general, is intimately
related to the energy flow in the environment and water chemistry. The
interactions among organisms are symbiotic (living together for mutual
benefits) and antagonistic (living together, but at least one is harmed).
Biosphere as a whole supplies us with food, and there exists a cycling
of materials through expiration, excretion, and extinction of the form.
2.3 TOXIC CHEMICALS IN THE ENVIRONMENT

The chemicals present in the environment are toxic as well as non-toxic
in nature. The toxic chemicals that are discharged by industries into air,
water, and soil get into the human food chain from the environment. Once
these chemicals enter the biological system, they perturb the natural
biochemical processes, causing adverse effects.
Toxic chemicals are huge in number; however, toxicity levels of many
compounds are still unknown. Some useful chemicals are being controlled
rigorously as their non-toxicity has not yet been proved. Many metals
that are known to cause environmental hazards are essential dietary
trace metals required for normal growth and development of animals and
human beings. These elements are Al, Sb, As, Ba, Be, Cd, Co, Cu, Ce,
In, Pb, Hg, Mo, Ag, Te, Tl, Sn, Ti, W, U, and Zn (Table 1). For instance,
As, Pb, and Cd—which are well-known toxic metals—are required in
trace quantities for the growth of animals.
Schwartz used the term “concentration window” to draw the arbitrary
lines of demarcation:
(i) “Essential” at the trace level for sustenance of life processes
(ii) “Deficient” at lower level than (a), causing metabolic disorder

(iii) “Toxic” at higher level than (a), causing adverse effects
According to the “International Register of Potentially Toxic Chemicals”
of the United Nations Environment Programme, 4 million known
chemicals exist in the world today and another 30,000 new compounds
are added to the list every year. Among these, 60,000–70,000 chemicals
are commonly used. Apart from their benefits to increasing production,
living standards, and health, many of them are potentially toxic.
Classification of Toxic Matters

Toxic matters may be classified according to their function and effects, such
as mutagens, carcinogens, and pesticides; food additives, preservatives,
and so on; or heavy metals, metal carbonyls, organochlorine compounds,
radioactive chemicals, and so on.
Mutagens
In reference to the field of genetics, a mutagen is a physical or chemical
agent that changes the genetic material, usually DNA. A large number
of chemicals may interact directly with DNA. However, many chemicals
such as PAHs (polycyclic aromatic hydrocarbons), aromatic amines, and
benzenes are not necessarily mutagenic by themselves, but produce
mutagenic compounds through metabolic processes in cells.
Other chemical species are reactive oxygen species, which include
superoxide, hydroxyl radicals, and hydrogen peroxide. A large number of
these highly reactive species are generated by normal cellular processes,
for example, as by-products of mitochondrial electron transport or
lipid peroxidation. Deaminating agents such as nitrous acid, aromatic
amines (2-acetylaminofluorene), alkaloids, sodium azide, bromine and
its compounds, and alkylating agents such as ethyl nitrosourea, which
transfer methyl or ethyl group to bases or the backbone phosphate
groups, also react with DNA. Guanine when alkylated may be mispaired
with thiamine. Some may cause DNA crosslinking and breakages.
Nitrosoamines are an important group of mutagens found in tobacco;
other alkylating agents include mustard gas and vinyl chloride.
Carcinogens
A carcinogen is a substance that is capable of causing cancer in humans
and animals. If a substance is known to promote or aggravate cancer,
but not necessarily cause cancer, it may also be called a carcinogen.
A number of substances have been identified as being carcinogenic.
Some commonly known carcinogens include asbestos, radon and other
radioactive isotopes, certain pesticides, arsenic and other heavy metals,
and tobacco smoke. In addition to chemical substances, ultraviolet ray is

also known to cause a variety of cancers that affect the skin.
Pesticides
Pesticides are the chemicals used to protect the crops and fodders from
insects and pests, including rodents and weeds. Biochemical processes
constitute the major mechanism by which pesticides in the environment
are degraded and detoxified. One good example of such pesticides is
DDT, whose biological action on the environment has been studied
most extensively. Like many other insecticides, DDT targets the central
nervous system. DDT dissolves in lipid (fat) tissue and accumulates in the
fatty membrane surrounding nerve cells. This is likely to interfere with
the transmission of nerve cells. The net result is disruption of the central
nervous system, killing the target insect. While DDT is fairly stable and
persists in the environment, the other groups—organophosphates and
carbamates—degrade quite rapidly. The latter react with O2 and H2O,
undergoing decomposition within a few days in the environment.
Food additives
Food additives are chemical substances that are added voluntarily to
food to preserve its flavour or enhance its taste and appearance. Some
additives have been used for centuries, for example, for preserving food by
pickling with vinegar, salting, preserving sweets, or using SO2 gas as in
some wines. Food additives are of both natural and artificial origins.
Types of food additives

The different types of food additives, their uses, and examples include
the following:
• Anti-caking agents—prevent ingredients from becoming lumpy, for
example, calcium polyphosphate and potassium aluminium silicate
• Antioxidants—prevent foods from being oxidized or going rancid, for
example, disodium EDTA, oxystearin, and vitamin C
• Artificial sweeteners—increase the sweetness, for example,
saccharin, aspartame, and cyclamates
• Emulsifiers—prevent fats from clotting together, for example,
dimethyl polysiloxane
• Food acids—maintain the right acid level in the food, for example,
sodium or potassium fumarate and 1,4-heptonolactone
• Colours—enhance or add colour to food, for example, niacin,
nicotinamide, tartrazine, riboflavin, and turmeric
• Humectants—keep foods moist, for example, maltitol, lactitol, xylitol,
and triacetin
• Flavours—add flavour to food

• Flavour enhancers—increase the power of a flavour added to food,
for example, monopotassium glutamate, MSG, and zinc acetate
• Foaming agents—maintain uniform aeration of gases in foods
• Mineral salts—enhance texture and flavour of food, for example,
aluminium sodium sulphate, calcium hydroxide, and magnesium
hydroxide
• Preservatives—prevent microbes from multiplying and spoiling the
food, for example, lysozyme, isopropyl citrate, and sodium benzoate
• Thickeners and vegetable gums—enhance texture and consistency
of food
• Stabilizers and firming agents—maintain even food dispersion,
for example, sodium or potassium gluconate
• Flour treatment—improves baking quality
• Glazing agents—improve appearance of food and can protect it
• Gelling agents—alter the texture of foods through gel formation, for
example, agar, alginic acid, and carrageenan
• Propellants—help propel food from a container
• Raising agents—increase the volume of food through the use of
gases
• Bulking agents—increase the volume of food without major changes
to its available energy, for example, starch, mannitol, pectin, and
polydextrose
Reactions due to food additives

A number of food additives are more likely than others to cause various
hypersensitive reactions in people, which include:
• Digestive disorders—diarrhoea and colicky pains
• Nervous disorders—hyperactivity, insomnia, and irritability
• Respiratory problems—asthma, rhinitis, and sinusitis
• Skin problems—hives, itching, rashes, and swelling
2.4 Water pollution

Out of all natural resources, water is the most essential for the existence
of living beings. Water sustains life on the earth. Unfortunately,
civilization has perished it and is responsible for its pollution.
Water pollution may be defined as the deterioration in the physical,
chemical, and biological properties of water, brought about mainly by
anthropogenic activities. It can also be caused by natural weathering
of the product of rocks, minerals, soil sediments, nutrients, as well
as organic matters of soil (decomposed animals, microorganisms, and

vegetable materials) that are transported by erosion. This deterioration
in quality of water body (both surface and ground) has increased during
the past few decades mainly by enhanced human activities in industrial
and agricultural sectors.
In recent years, there has been an increasing concern around the world
regarding the widespread distribution of the pollutants stemming from
human activities and the potential harmful effects of these pollutants
on human or the ecological systems. Some environmental problems such
as contaminated water have arisen from poorly controlled discharges
of industrial effluents into the water bodies, while others such as air
pollution have arisen from poor emission control on the energy generation
industry and motor vehicles.
Parameters of Pollution
The following parameters determine the nature and extent of pollution
in water:
(i) Physical parameters—colour, odour, turbidity, density,
temperature, and so on
(ii) Chemical parameters—pH, total dissolved solids (TDS) and their
ionic composition, suspended solids, dissolved oxygen (DO), residual
chorine, COD, biochemical oxygen demand (BOD), redox potential,
radioactive substances, organic materials, metallic ions (including
heavy metals), oxides, by-products of industries, and so on
(iii) Biological parameters—different types of microorganisms,
bacteria, algae, small animals such as protozoa and crustaceans,
and so on
Water Pollutants
Nature and concentration of the pollutants depend upon their sources,
physical and chemical conditions, and reactivity with the surrounding
environment. The large number of water pollutants may broadly be
classified under the following categories:
(i) Organic pollutants—These include degradable and non-degradable
products, as well as disease-causing agents, plant nutrients, sewage,
synthetic organic compounds, and oil. DO is an essential requirement
for aquatic life. Its level in the water body should be 4–6 ppm.
Decrease in this value is an indication of pollution mainly caused by
organic matter, for example, sewage, industrial wastes, and run-off
from agricultural lands
(ii) Inorganic pollutants—These pollutants consist of inorganic salts,
finely divided metal or metal compounds, trace elements, complexes
of metal with organic moiety mineral acid, and so on
(iii) Sediments—Sediments are insoluble soil particles of unknown

composition that enter water bodies by soil erosion. In fact, sediments
are the most extensive pollutants of surface water. It has roughly
been estimated that suspended solids loading reaching natural
waters are about 700 times as large as the solids loading from
sewage discharge. Several factors such as agricultural practices,
construction activities, and strip mining activities have great
influences on solid erosion rates in the given area.
(iv) Radioactive substances—Radioactive pollution is the worst
pollution among all and it is detrimental to health. Sources of
environmental radioisotopes may broadly be grouped as natural
and artificial. Natural radioisotopes produced by cosmic rays find
their way into soil and water courses through precipitation (rainfall
and snow) and run-off, whereas those occurring on the surface of
the earth and below enter the water-bearing formulations through
weathering. On the other hand, man-made radioisotopes enter the
environment mainly through nuclear installations and research
organizations. Some of the radioisotopes such as K-40; Ra-222,
Ra-226, and Ra-228; Pb-210; and C-14 are incorporated into the
human body through different pathways.
(v) Thermal pollutants—Coal-fired or nuclear fuels used by steam
power plants are among the most important sources of thermal
pollutants, as only a fraction of the heat generated using these fuels
is successfully converted to work and the remaining is wasted. Even
in the modern coal-fired plants, the efficiency does not exceed 40%.
The condensers used in these plants utilize water from nearby river
or lake or municipal sources and discharge the wastewater back to
the water body, with its temperature being raised by about 10°C
in the process. This decreases the DO level of water and adversely
affects the aquatic life.
Main Sources of Pollutants

Water pollution is caused by one or more of the following sources:
1. Point sources: Sources that are readily identifiable at a single
location, such as the following:
(a) Industrial waste disposal
(b) Water treatment plant
(c) Municipal sewage leakage
(d) Combined sewer overflows
(e) Raw sewage disposal
(f) Leaching residue tips
(g) Sanitary landfills
(h) Aerial fallout

(i) Industrial effluent seepage
2. Non-point sources: Sources whose location cannot be identified,
such as the following:
(a) Pollution due to industrial chemicals: With the increase in
global population, industrial activities have also increased. The
effects of population growth have been recorded not only on industrial
areas, but also on global commons such as Antarctic, the Arctic, and
remote natural reserves. In addition, increasing concentrations of
chemical substances originating from industrial sources and other
human activities have been detected in water, air, and soil. Such
elevated concentrations and consequent bioaccumulation of some
substances have given rise to environmental and ecotoxicological
effects. Over 11 million chemical substances are known, of which
60,000–70,000 are in regular use. Data on environmental and
ecotoxicological effects of these chemicals are sparse; however, many
cases have been reported about the heavy metals and metalloids,
pesticides, fertilizer, aromatic polychlorinated compounds, flame-
retardant chemicals, wood preservatives, washing powders and
detergents, polymeric resins, and so on poisoning the water
bodies.
(b) Pollution due to agricultural activities: The key role of
fertilizers in increasing the crop production is now well established.
Fertilizer consumption in India has registered a spectacular growth
during the last four decades. In addition to chemical fertilizers,
large quantities of organic manures and pesticides are also being
used for increasing crop production. Unfortunately, increasing use of
the above-mentioned inputs for achieving the planned agricultural
growth is creating environmental problems. Reports say that, in
India, the efficiency of nitrogen fertilizers is about 30–40% for
paddy and about 50–60% for wheat. For potassium and phosphate
fertilizers, the efficiency values are around 50% and 15–20%,
respectively. This shows that a huge amount of applied fertilizers
not used by plants is available for leaching into groundwater, which
can cause water pollution. Micronutrients added as fertilizers may
be toxic if they get into groundwater. Nutrients can flow into
groundwater at many points. It should be recognized that only
a small portion of the nitrogen load comes from the agricultural
land surface, while the major portion comes from the air and the
domestic and industrial wastes of the cities.
(c) Oil pollution: Besides the problems of dwindling petroleum
reserves and global oil pollution, the use of fossil fuels contributes
to the increase in greenhouse gas (GHG) and change in global
climate. Petroleum hydrocarbons enter freshwater environment in

a variety of ways, including land run-off, airborne contaminants,
shoreline facilities, and leaks and spills from vessels, pipelines and
underground storage tanks.
(d) Eutrophication: The word eutrophication literally means “the
process of becoming well fed”; it can also be referred to as excessive
fertilization of lakes, reservoirs, slow-flowing rivers, and certain
marine coastal waters by nutrients, which result in the nuisance
growth of aquatic plant materials such as algae and macrophytes.
This in turn leads to deterioration of water quality and taste,
odour problems, oxygen depletion, reduced transparency, declines of
fisheries, possible fish kill, and toxic effects on animals and human
beings.
(e) Consequences of eutrophication: Eutrophication of lakes,
reservoirs, impoundments, rivers, and coastal waters is related
to the impairment of recreation for bathers, health concern from
contact dermatitis, and ingestion of toxin-producing algae. In
addition to these factors, eutrophication also causes impairment
of fisheries and consumption of contaminated shell fish, adverse
effects on livestock, drinking of toxicologically contaminated water,
macrophyte-impaired navigation, and increased habitat for some
disease vectors such as schistosomiasis or bilharzias.
(f) Control of eutrophication: Eutrophication can be controlled
effectively by drastic reduction in the total nutrient load in an
overloaded water system. An integrated approach based on water
body nutrient mass balance, taking into consideration specific
geographical, climatological, and ecological conditions, can be
effective.
(g) Heavy metals: When heavy metals on a site, which either may
have been produced by mining operation or occur naturally, are
mobilized, these cause potential health and environmental problems
in the overburden in soil and water. When acid mine drainage
is detected, there is a high probability that heavy metals are
present in abundance. Sulphuric acid derived from the oxidation
of sulphides normally carries many heavy metals usually in fairly
high quantities. The management of acid mine drainage, which
contains these metals, includes neutralization and pH increase of
the solution to precipitate most of these metals, most commonly as
metallic salts. These salts would then become soluble and may enter
the local water regime.
It is, therefore, necessary to review the heavy metals that are
detrimental to humans, animals, plants, and fish life.
• Arsenic, cadmium, lead, nickel, manganese, and molybdenum:

These metals are potentially harmful to human life as they are
bioaccumulative and can seriously affect health even in relatively
small dosages. Also, with the addition of copper and chromium, all
these metals become very detrimental to aquatic life.
• Zinc, lead, aluminium, boron, and iron: These metals may
rapidly become available either in acid soils or as salts precipitated
by neutralizing acid solutions. They are all, to a greater or lesser
extent, toxic to plant growth.
• Mercury: Mercury is highly toxic as a liquid, a vapour, and organic
complexes. It is bioaccumulative and is, therefore, a major health
risk to workers who are handling it. Its detrimental effects on
animals and humans are irreversible. Mercury can be absorbed
through the skin, inhaled as a vapour, or taken in by eating
contaminated fish and drinking contaminated water. Mercury is
used extensively by small mines in some developing countries;
these mine workers should be educated about the health hazards
associated with mercury and how to handle it safely.
Mercury can also cause major environmental damage to all
types of animals and plants. Residual mercury should be carefully
collected and returned to the supplier. In addition, all purchases
and uses of the mercury should be recorded.
• Copper: Copper is commonly toxic to most aquatic vegetation.
Therefore, care must always be taken not to allow copper to enter
drainage systems where there may be aquatic life.
(h) Pesticides: Pesticides are the chemicals used to protect the
crops and fodders from insects and pest including rodents and
weeds. Biochemical processes constitute the major mechanism by
which pesticides in the environment are degraded and detoxified.
One good example of such a pesticide is DDT, whose biological
action on the environment has been studied most extensively. Like
many other insecticides, DDT targets the central nervous system.
DDT dissolves in lipid (fat) tissue and accumulates in the fatty
membrane surrounding nerve cells. This is likely to interfere with
the transmission of nerve cells. The net result is disruption of the
central nervous system, killing the target insect. While DDT is
fairly stable and persists in the environment, the other groups—
organophosphates and carbamates—degrade quite rapidly. The latter
react with O2 and H2O, undergoing decomposition within a few days
in the environment.
(i) Radioactive waste: Radioactive wastes are derived from the mining
and processing of uranium ores. Other sources of radioactive waste
Table 1 Toxic trace elements in natural water and wastewater
Metal Source Effects

Arsenic Mining by-products, pesticides, Toxic, possibly carcinogenic
chemical waste
Cadmium Industrial discharge, mining Replaces zinc biochemically;
waste, metal plating, water causes high blood pressure,
pipes kidney damage, destruction of
testicular tissue and red blood
cells, toxicity to aquatic biota
Beryllium Coal, nuclear power, space Acute and chronic toxicity,
industries possibly carcinogenic
Boron Coal, detergent formulations, Toxic to some plants
industrial waste
Chromium Metal plating, cooling tower Essential trace elements; possibly
water additive; normally found carcinogenic as Cr(VI)
as Cr(VI) in polluted water
Copper Metal plating, industrial and Essential trace elements, not
domestic waste, mining and very toxic to animals, toxic to
mineral leaching plants and algae at moderate
levels
Fluorine (fluoride ions) Natural geological sources, Prevents tooth decay at about
industrial waste, water 1 mg/L, causes mottled teeth
additive and bone damage at about
5 mg/L
Lead Industry, mining, plumbing, Toxic (anaemia, kidney diseases,
coal, gasoline nervous disorder), destroys wild
life
Manganese Mining industrial waste, Relatively non-toxic to animals,
acid mine damage, microbial toxic to plants at a higher level
action on manganese minerals
at low pE
Mercury Mining, industrial waste, Highly toxic
pesticides, coal
Molybdenum Industrial waste, natural Possibly toxic to animals, essential
sources for plants
Selenium Natural geological sources, Essential at low levels but toxic
sulphur, coal at higher levels
Zinc Industrial waste, metal Essential in many metalloenzymes,
plating, plumbing toxic to plants at higher levels
include contamination from radioactive sources used for monitoring

purposes and where radionuclides occur naturally with the ore being
mined, such as some gold and mineral sand deposits. Radioactive
wastes occur as gases, liquids, and solids. Certain characteristics,
such as toxicity, mobility, radioactive half-life, and type of radioactive

emission, govern the choice of management procedures.
The following three basic principles are employed in the disposal of
radioactive waste:
(a) Dilution and dispersion of short-lived or very diluted radioactive
wastes
(b) Delay to allow decay of very short-lived radioactive wastes into non-
radioactive species
(c) Containment of long-lived radioactive wastes by methods such as
water submersion and impervious covers
Biological Effects of Radiation from Radioactive Waste
The biological effects of radiation are thought of in terms of their impacts
on living cells. For low levels of radiation, biological effects are so small
that they may not be detected in epidemiological studies. Body itself
repairs many types of radiation and chemical damages. Biological effects
of radiation on living cells may result in a variety of outcomes, including
the following:
(i) Cells experience DNA damage and are able to detect and repair the
damage.
(ii) Cells experience DNA damage but are unable to repair the damage.
These cells may go through the process of programmed cell death,
or apoptosis, thus eliminating the potential genetic damage from
the larger tissue.
(iii) Cells experience a non-lethal DNA mutation that is passed on to
subsequent cell divisions. This mutation may contribute to the
formation of a cancer.
(iv) Cells experience “irreparable DNA damage”. Low-level ionizing
radiation may induce irreparable DNA damage, leading to
replicational and transcriptional errors needed for neoplasia, or
may trigger viral interactions, leading to premature ageing and
cancer.
Other observations at the tissue level are more complicated, which are
discussed next.
In some cases, a small radiation dose reduces the impact of a
subsequent larger radiation dose. This has been termed as an “adaptive
response” and is related to hypothetical mechanisms of hormesis.
Acute
Acute radiation exposure is an exposure to ionizing radiation that occurs
during a short period of time. There are routine brief exposures, and the
boundary at which it becomes significant is difficult to identify. Extreme
examples include the following:
• Instantaneous flashes from nuclear explosions

• Exposure durations ranging from minutes to hours during handling
of highly radioactive sources
• Laboratory and manufacturing accidents
• Intentional and accidental high medical doses
The effects of acute events are more easily studied than those of
chronic exposure.
Chronic
Exposure to ionizing radiation over an extended period of time is called
chronic exposure. The term chronic (Greek “khronos” means time)
refers to the duration, not the magnitude or seriousness. The natural
background radiation is chronic exposure, but a normal level is difficult
to determine due to variations. Geographic location and occupation often
affect chronic exposure.
Methods of Analysis of Parameters of Wastewater

Several chemical and instrumental analytical methods have been
developed for determining the concentrations of various ions or matters
present in wastewater, since the quantity of these matters can determine
its quality for use as irrigation water (Table 2). The principal factors taken
into consideration when determining water quality are the following
(Table 3):
• DO content
• Turbidity
• Acidity and alkalinity
• Trace elements and nutrients such as nitrogen, phosphorus, halogens
(chloride and fluoride ions), alkali metals (sodium and potassium ions),
calcium and magnesium ions
• Microorganisms status
Table 2 Methods of analysis
Parameter Method Reason for testing

Temperature Use an alcohol thermometer in Temperature influences the amount
a hard plastic cover or digital of DO in water, which in turn infl-
temperature probe uences the survival of aquatic
organisms (raising the temperature
of a freshwater stream from 20°C to
30°C will decrease the DO
saturation level from about 9.2 to
7.6 ppm), which again influences
Table 2 Contd...
the biological status of the water
bodies. Increasing temperature also
increases the rates of chemical reac-
tions taking place in the water.
Increase in temperature is often
associated with hot water discharge
from power stations and industries
pH A pH meter with sensitive The value of pH determines its suit-
electrodes, pH paper, or ability for irrigation, as it measures
Universal Indicator solution the acidity or alkalinity of water.
pH of rainwater is about 5.5–6.6.
Typically, natural water has a pH of
6.5–8.5. A pH <5 (acidic water) is
most damaging to eggs and larvae
of aquatic organisms. Natural alkali-
nity is due to CO2 (g), HCO3−, CO2− 3 ,
and OH−; carbonate rocks such as
limestone and dolomite increase
alkalinity.
Turbidity Use a Secchi disc or 500 mL of Turbidity is a measure of water clarity.
water in a measuring cylinder Suspended solids in water can stop light
made to stand on a paper reaching submerged plants and can raise
marked with a black cross water temperature. Suspended solids
that are often present in water include
mud, clay, algae, bacteria, and minerals
such as silica, calcium carbonate, and
ochre (iron oxide). The amount of these
solids can be increased by the discharge
of wastes (domestic sewage, industrial
and agricultural effluents), leaching of
wastes (from mines), and agitation
(dredging or shipping)
TDS Use an appropriate TDS meter. This is a conductivity test of available
Freshwater meters: 0–1990 ppm. ions in the water, including Ca2+, Na+,
Dual-range brackish water meters: K+, Fe2+, Fe3+, HCO3−, and ions cont-
0–19,900 ppm. Salt-water meters: aining P, S, and N. High levels of
to above 35,000 ppm Na+ is associated with excessive
salinity and is found in many
minerals. Potassium is incorporated
into plant materials and is released
into water systems when plant matter
is decayed or burnt
DO Winkler titration method: Divide The DO test measures the current oxy-
the water sample into two parts. gen levels in the water. The DO level
Table 2 Contd...
Place one part in the dark (for varies with temperature; it is highest in
BOD). To the other part of the the afternoon due to photosynthesis and
sample, add 2 mL MnCl2 (aq.) lowest just before dawn. DO is lowered
+ 2 mL alkaline iodide solution by an increase in temperature (such as
(3.3 g NaOH + 2.0 g KI dissolved by a discharge of hot water from a
in 10 mL distilled water). Shake power station) and increased in aerobic
the sample. Add 2 mL concentr- oxidation (due to increases in organic
ated HCl and shake again. The matter from sewage or due to inorganic
iodine formed is directly fertilizers such as phosphates and nitrate
proportional to the DO. Titrate with over-stimulated algal growth)
50.0 mL of this solution with
0.0125 M sodium thiosulphate
solution using starch as an
indicator. The endpoint is the
disappearance of blue-black
colour. Colorimetric method can
also be used
BOD The first water sample as above BOD measures the rate of consumption
is kept in the dark for 5 days at of oxygen by organisms in the water
the temperature at which the over a period of 5 days. Increases in
sample was collected. Then the BOD can be due to animal and crop
DO is determined using the wastes and domestic sewage
Winkler titration method as
above. Subtract the mass of
oxygen obtained on Day 5 from
the mass of oxygen obtained
on Day 1 to determine the BOD
(mg/L). Unpolluted natural waters
have BOD <5 mg/L.
Treated sewage can have BOD
20–30 mg/L
Salinity Titrate a known volume of the Many aquatic organisms can survive only
water sample with silver nitrate in a narrow range of salt concentrations,
solution (2.73 g AgNO3 per 100 since salt controls their osmotic pressure
mL distilled water), using K2CrO4
as indicator. The endpoint of the
titration is given by the reddening
of the silver chloride precipitate
(AgCl(s)). Volume of AgNO3 used
= chloride content in g/L
Total Perform acid digestion using Total phosphate is used as an indicator
phosphate concentrated H2SO4 and of pollution from run-off in agricultural
test ammonium persulphate. Titrate areas or domestic sewage. Concentra-
with NaOH, using phenolphthalein tions of 0.2 mg/L are common. Concen-
as an indicator. Use few drops trations of 0.05 eutrophication (increas-
Table 2 Contd...
of H2SO4 to turn the solution ed nutrient mg/L indicate the possibility
clear again. Add ammonium possibility of concentrations) and algal
molybdate solution and then solid blooms are likely. Natural phosphate
ascorbic acid. An intense blue occurs due to decayed organic matter
complex (molybdenum blue) is and phosphate minerals.
formed, which can be measured
colorimetrically at 882 nm
Total Kjeldahl digestion: Digestion with Total nitrogen is an important indicator
nitrogen concentrated sulphuric acid conv- of eutrophic waters, especially for those
test erts the nitrogen into ammonium contaminated by animal wastes, ferti-
sulphate. The solution is then lizer run-off, and domestic sewage.
made alkaline. Liberated ammo- Aquatic nitrogen is essential for the
nia is distilled and determined by growth of organisms and is produced
titration with standard acid by natural processes, decay of prot-
Or eins, action of lightning, and action of
Add Nessler’s reagent (100 g nitrogen-fixing bacteria on ammonia
mercuric iodide + 70 g KI in
100 mL distilled water, and then
add 160 g NaOH in 700 mL
distilled water; dilute the solution
to 1 L) to samples containing
<1 mg/L and measure absorbance
colorimetrically at 425 nm
Hardness Calcium ions, Ca2+—complexo Calcium ions are a major contribu-
-metric titration using EDTA at tor to water hardness and enter
a pH of 12–13 (at this pH, Mg2+ water bodies when water is running
is precipitated and not complexed through rocks containing minerals
with EDTA) such as gypsum (CaSO4.2H2O), calcite
Or (CaCO3), and dolomite [CaMg(CO3)2].
Potentiometric techniques using Hard water has a noticeable taste
selective electrodes and produces precipitates with soaps
or that inhibit lathering and form
Atomic absorption spectroscopy precipitates (scale) in boilers, hot
(AAS) water systems, and kettles. Tempo-
Or rary hardness (or bicarbonate
Gravimetric method—measure hardness) is due to Ca(HCO3)2,
the amount of CaCO3 (s) which deposits CaCO3 (s) as a scale on
precipitated by a known volume boiling the water. Magnesium ion
of 0.02 M Na2CO3 levels are often high in irrigation
Or water and can cause scouring in stock.
Flame test—Ca2+ flame test, a Ca2+ and Mg2+ can combine with Cl–
brick-red colour in a non-luminous and SO42−, causing permanent
Bunsen flame hardness, which cannot be removed
Table 2 Contd...
2+
Mg —complexometric titration by boiling. Water can be softened by
using EDTA at pH = 10 (both Ca2+ an ion exchange process using a
and Mg2+ will complex with EDTA solid material such as a resin or clay
at this pH. [Mg2+] can be found by that is capable of exchanging Na+ or
subtracting the results of this H+ for Ca2+ and Mg2+
titration from the results of the
first titration)
Or
Potentiometric techniques using
selective electrodes
Or
AAS
Microor- Microorganisms in a water sample Many protozoa, bacteria, viruses, algae,
ganisms are counted under a microscope. and fungi are found in natural water
Method for finding the number of systems. Some are pathogenic (typhoid,
coliform organisms in a water cholera and amoebic dysentery can
sample: Pass a known volume result from waterborne pathogens). The
of water sample through a filter excessive growth of algae (called algal
that retains microorganisms. bloom) can degrade water quality
Transfer the filter to a sterile because it lowers DO levels, thereby
petri dish containing appropr- killing other living things. The level of
iate agar and incubate at 35°C bacterial contamination of water due to
for 20–40 h. Also, incubate animal waste is measured by determin-
a control plate with agar only. ing the number of coliform organisms
Colonies will develop on the such as E. coli
filter wherever bacteria are
retained. Count the number of
of coliform colonies either
visually or by using a microscope.
Express these values as
CFU/100 mL
Heavy The precipitation methods of Heavy metals in concentrations above
metals various ions are as follows: trace amounts are generally toxic to
Ni2++ dimethylglyoxime in ethanol living things. Trace amounts (<0.05 mg/L)
turns pink-red of Zn, Cu, and Mn are present in most
Fe3+ + ammonium thiocyanate natural waters. Zn and Cu may be pre-
turns blood-red sent in higher levels in irrigation areas
Cu2+ + dithizone due to the use of galvanized iron,
in 1,1,1-trichloroethane turns copper, and brass in plumbing fixtures
yellow-brown and for water storage. In irrigation
Cd2+ + dithizone in 1,1,1- areas, acceptable levels are 0.2 mg/L
trichloroethane turns blue-violet for Cu2+ and 2.0 mg/L for Zn2+ and Mn2+.
Pb2+ + dithizone in 1,1,1-trichloro- Atomic ethane turns brick-red
Pb2+ + 2KI (aq.) Æ yellow absorption spectrophotometer can
precipitate of PbI2 (s) analyse lower levels more accurately
Table 2 Contd...
2+
Zn + dithizone in 1,1,
1-trichloroethane turns pink
The popular methods of
acid digestion or DTPA extraction,
followed by AAS, can be employed
Other ions Al3+ + aluminon Æ pink-red A flame photometer can analyse lower
2+
Mg + magneson I Æ light blue levels more accurately
Na+ flame test Æ yellow flame
K+ flame test Æ lilac flame
NH4+ and NH3 + Nessler’s reagent
(100 g mercuric iodide + 70 g KI
in 100 mL distilled water, then
add 160 g NaOH in 700 mL
distilled water, and finally dilute
to 1 L) Æ yellow-brown
NO – + conc. H SO + FeSO Æ
3 2 4 4
brown ring forms at junction
S2– + lead acetate solution Æ
black deposit of PbS SO42– +
BaCl2 (aq.) Æ white precipitate
of BaSO4 (s)
Source Page A L , R H Miller, and D R Keeney. 1982. Methods of Soil Analysis. Part 2. Chemical and
Microbiological Properties, 2nd ed., Agronomy No. 9. Madison, WI: ASA-SSSA.
5/3 Day BOD test for the examination of water and wastewater
The BOD test is a laboratory procedure used to determine the relative
oxygen requirements of clean waters, wastewaters, effluent, and polluted
waters. It measures the oxygen used in the breakdown of organic matter
and in the oxidation of inorganic substances. In other words, this test
measures the potency of a particular pollutant in that it shows the
amount of oxygen which will be removed from water to dissipate each
litre of the pollutant.
Principle: In this method, a bottle is filled with sample and incubated
for 5 days at 20°C or for 3 days at 27°C. DO is measured before and after
incubation. BOD is calculated from the difference between initial and
final DO. Because the initial DO is determined immediately after the
dilution is made, all oxygen uptake is included in the BOD measurement
(Table 4).
Sampling and storage: Samples for BOD analysis may degrade

significantly during storage, resulting in low BOD values. Minimize
reduction of BOD by analysing sample promptly and keep holding time
to a minimum.
Samples should be kept cool/cold until analysed. Ideally, analysis should
be initiated within 24 h and in no case should it be delayed longer than
48 h.
2.5 Air Pollutants

Air is composed of around 78% nitrogen, 21% oxygen, 1% argon, and
0.03% CO2. Air pollution refers to the presence of any substance in
air at a concentration that is enough to produce an undesirable effect
on humans, animals, vegetation, or materials, or to alter the natural
balance of any ecosystem significantly. Air pollutants can be solids,
liquids, or gases, and can have local, regional, and global impacts.
The main air pollutants are carbon monoxide, particulates, sulphur
oxides (SOx), nitrogen oxides (NOx), volatile organic compounds (VOCs),
and so on.
Table 3 Water quality of a typical natural aquatic system—an example
Substance or quality Yamuna River water Sea water
pH 6.8 8.0
DO (ppm) 6–8 6–8
Na+ (ppm) 6.7 1.1 × 104
K+ (ppm) 1.5 380
Ca2+ (ppm) 17.5 400
Mg2+ (ppm) 4.8 1.3 × 103
Cl– (ppm) 4.2 1.9 × 104
SO42−/HSO4− (ppm) 17.5 2.6 × 103
CO2− −
3 /HC3 (ppm) 33.0 142
2+
Hg (ppb) <1 0.03
Cd2+ (ppb) <1 0.1
Pb2+ (ppb) <1 4–5
Table 4 Saturated DO levels

Temperature (°C) Saturated level of DO (ppm)
Freshwater Sea water
10 10.9 9.0
20 8.8 7.4
30 7.5 6.1
40 6.6 5.0
Source Kemker, Christine. 2013. Dissolved oxygen. Fundamentals of Environmental

Measurements. Fondriest Environmental, Inc.
Carbon Monoxide
It is one of the most serious air pollutants, poisonous in nature, and
96.5% as heavy as air. Since CO is an odourless gas, its presence in
the air is not detectable during breathing. The main source of carbon
monoxide in the air is automobile exhaust. CO constitutes 80% of all
automobile exhausts. Other sources of CO include combustion processes,
such as stove, open fire, furnace, power plants, factories, coal mines,
and smoke. Its natural sources are various plants and animals. Plants
produce about 15–20 tonnes of CO per year. Breakdown of photosynthetic
pigment in algae also releases some C into the atmosphere. Higher
animals produce some CO during breakdown of haemoglobin and also
from bile juice.
Chemical reactions that release CO in the atmosphere are the
following:
(i) Incomplete combustion of fuel or carbon-containing compounds
2C + O2 Æ 2CO
(ii) A high-temperature reaction between CO2 and carbon-containing
material resulting in the formation of CO (for example, blast
furnace)
CO2 + C Æ 2CO
(iii) Dissociation of CO2 at high temperature
CO2 Æ 2CO + O
1% dissociation of CO2 occurs at 1745°C.
(iv) Methane produced by the decomposition of organic matter reacting
with hydroxyl radicals (OH*) to yield CO
CH4 + OH* Æ *CH3 + H2O
*CH3 + OH* Æ CH2 + H2O
CH2 + OH* Æ *CH + H2O
*CH + OH* Æ CO + H2
Decomposition of chlorophyll also gives CO:
C35H70MgN4O6 Æ CO + Other products
(v) Production of CO from haemoglobin breakdown in some animals:
CO is the most widespread human poison on record, which can
cause asphyxiation, resulting in instantaneous death. It has 200–
300 times as great affinity for the haemoglobin of the blood as
oxygen. In case of inhalation of CO, carry the patient to fresh air
immediately and do not allow him to walk. Loosen all tight clothing.
Apply artificial respiration if breathing has stopped or is irregular.
Wrap the patient in a blanket to prevent chilling. If the patient is
convulsing, keep him/her in the bed in a semi-dark room; avoid
jarring or noise. Life can also be saved by blood transfusion, by

injecting methylene blue, or by making the person inhale carbogen
(a mixture of 95% O2 and 5% CO2).
Particulates
Particulates are naturally found in the atmosphere in the form of dust,
soot, sand, smoke, pollen, and ash. Combustion of fossil fuel also emits
particulates. Solid- and liquid-phase materials in the atmosphere are
variously referred to as particulate matter, particulates, particles, and
aerosols. Although these terms are often used interchangeably, all refer
to particles with diameters between approximately 1 nm and 10 µm
that remain suspended in the atmosphere for long periods. The greatest
threats to health are associated with the smallest particles because
they have the greatest possibility of getting deposited deep within the
respiratory system. Somewhat counter-intuitively, particles about 1 µm
in size can remain suspended in the atmosphere much longer than
gases, although those much larger than 1 µm in size will quickly settle
out of the atmosphere because of gravity. The smallest particles will
coagulate and coalesce quickly, forming larger particles. But particles of
approximately 1 µm diameter do not grow as quickly as smaller particles
and can remain suspended in the atmosphere for a week or more. It is
not unusual, for example, for Saharan dust or particle plumes from Asia
to be detected in the United States. Consequently, particulate matter
is a continental- to global-scale air pollution problem. Unlike ozone and
other gas-phase pollutants that are specific chemical species, particulate
matter is a collection of chemical species defined mainly on the basis
of particle size. The chemical constituents that make up particulate
matter vary with particle size. Windblown dust is a main contributor
to particles larger than 10 µm in diameter, whereas sulphates, nitrates,
and organic compounds are the main constituents of smaller particles
that can penetrate deep into the respiratory system and engender health
effects. Organic particles can be emitted directly as soot from combustion
processes or can be formed when large hydrocarbon molecules react
with oxidants in the atmosphere and form chemicals that condense onto
particles. Sulphate particles are formed via a series of reactions that
convert sulphur dioxide (SO2), which is released into the atmosphere by
the combustion of sulphur-containing fuels, into sulphuric acid. Nitrate
particles are formed via reactions that convert oxides of nitrogen, which
are released into the atmosphere by combustion processes, into nitric
acid. If particles containing sulphuric acid, nitric acid, and organic
compounds retain their acidity and are washed out of the atmosphere
by rainfall, the rainfall becomes acid rain. The continental and global
scale of air pollution problems is not limited to particulate matter.
Emission of GHGs causes global climate change. The presence of ozone-

depleting compounds in the stratosphere has created polar ozone holes.
Atmospheric releases caused by volcanic eruptions and fires have global
effects. Atmospheric particles also influence climate and rainfall. The
challenges of reducing air pollution call for a sophisticated understanding
of atmospheric chemistry, applied at local, regional, continental, and
global scales.
Composition of particulates
Particulates include organic and inorganic matters, nitrogen compounds,
sulphur compounds, PAH, several metals, and radionuclides. An estimate
indicates that particulate contaminants contain nearly 22 metallic
elements. The most abundant elements are Ca, Na, Si, Al, and Fe.
Considerable quantities of Zn, Pb, Cu, Mg, and Mn are also present in air.
The concentration of these particulate matters depends upon the nature
of industrial emission. For instance, the level of Pb increases with the
traffic density because lead tetraethyl is added as an antiknock to the
petroleum fuel. Spectrographic studies on the organic fraction conclude
that a variety of aliphatic and aromatic hydrocarbons, organic bases,
phenols, cresols, organic acids, carcinogenic compounds, and various
types of complex compounds occur in the atmosphere as particulate
matters.
Physical methods involved in particulate formation include the
following:
(i) Dispersion process mainly yields dispersion aerosol, for example,
dusts that are solid dispersion aerosols. Particulates nearly 1 µm
in size are formed by disintegration of larger particles.
(ii) Adhesion of smaller particles by chemical process yields particulates
of size ranging from 10 to 20 µm.
(iii) Natural sources also produce dispersed aerosols from sea spray,
windblown dust, dust during cultivation, volcanic dust, and so on.
(iv) By coagulation, extremely small particles from larger aggregates,
sorption, absorption, adsorption, and chemisorptions also result in
the formation of particulate matter.
Formation of inorganic particulate matter: Inorganic particulates
generally originate from metallic oxides, sulphides, carbonates, and so
on when fuel-containing metals are burned. For instance,
(i) The particulate Fe3O4 is formed during the combustion of pyrites
containing coal.
3FeS2 + 8O2 Æ Fe3O4 + 6SO2
(ii) A part of calcium carbonate in the ash fraction of coal gets converted
to calcium oxide, which is released into the atmosphere through
stack.
CaCO3 Æ CaO + CO2
(iii) Organic vanadium in residual fuel oil is converted to particulate
vanadium oxide.
(iv) Lead halides are generated by the combustion of leaded gasoline.
Tetraethyl lead, Pb(C2H5)4, in leaded gasoline combines with oxygen
and halogenated scavengers, dibromoethane, and dichloroethane.
These lead halides emerge through the exhaust system and condense
to form particulates after entering the atmosphere.
(v) Aerosol mists are formed by the oxidation of atmospheric sulphur
dioxide to sulphuric acid, that is, 2SO2 + O2 + 2H2O Æ 2H2SO4.
It forms salts with basic air pollutants such as ammonia or calcium
oxide:
H2SO4 + 2NH3 Æ (NH4)2SO4
H2SO4 + CaO Æ CaSO4 + H2O
Formation of organic particulate matter: Organic particulate matter
originates mainly from combustion of fuels, automobiles, and vegetation.
Chrysene, benzofluoroethane, benzo-alpha-pyrene, and so on are some
organic particulate matter of carcinogenic nature. PAH compounds
generally occur in urban atmosphere at the level of 20 µg/m3. Such
particulates pose a serious health hazards and lie in the range of 1 µm
size. Aldehyde, ketone, peroxide, epoxide, ester, quinine, and lactones
are found among the oxygenated neutral organic compounds. Organic
acids present in OPM include lauric, palmitic, stearic, myristic, oleic,
linoleic, and behenic. Particulate paraffin is pyrolysed to yield C10H22,
which again disintegrates into fine particles. Oxidized, polymerized
hydrocarbons and nitrogenous azo heterocyclic compounds are released
into the atmosphere from automobile exhaust. PAH compounds remain
absorbed in soot particles. Soot itself is a highly condensed product
of these compounds. A soot particle is composed of several thousands
of interconnected crystallites, that is, graphitic platelets, each having
100 condensed aromatic rings. It consists of 1–3% hydrogen and 5–10%
oxygen due to partial oxidation. Soot particles contain toxic trace metals
such as Be, Cr, Mn, Ni, V, Cd, and Fe and poisonous organic compounds
such as benzo-alpha-pyrene.
At urban scales, air pollution is frequently referred to as photochemical
smog. “Smog” is a contraction of the words “smoke” and “fog” and was
originally used to describe air pollution caused by coal burning in London.
Urban smog is photochemical in nature because many of the chemicals
found in urban air are formed by chemical reactions driven by sunlight.

Ozone (O3) is one of the most abundant air pollutants in urban smog
that are produced by photochemical reactions. In contrast to the ozone
found in the upper atmosphere (stratospheric ozone), which protects the
planet from ultraviolet radiation, ground-level or tropospheric ozone
is a lung irritant and a danger to human health. It is also responsible
for crop damage and is suspected to contribute to forest decline in
Europe and in parts of the United States. Ground-level ozone and
other photochemical pollutants are formed in urban atmospheres by
the reactions of oxides of nitrogen (mainly NO and NO2, which are
by-products of combustion processes) in the presence of hydrocarbons.
At the high temperatures generated during combustion, some of the
N2 and O2 in air are converted to oxides of nitrogen and, in general,
the higher the combustion temperature, the greater the amounts of
oxides of nitrogen produced. Hydrocarbons are emitted from natural
sources and as a result of activities that involve using organic solvents,
coatings, or fuel. These hydrocarbons and oxides of nitrogen participate
in reactions that yield not only ozone, but also aldehydes, hydrogen
peroxide, peroxyacetyl nitrate (C2H3NO5), nitric acid, and molecular
species of low volatility that accumulate in fine particles suspended in
the atmosphere. Although many of these constituents of photochemical
smog have environmental impacts, fine particulate matter presents the
greatest health endangerment in most urban areas.
Sulphur Oxides
The combustion of coal is a man-made source of SO2 and SO3. Volcanoes
also emit SO2.
Reaction of SO2 in the atmosphere
In the atmosphere, SO2 does not remain in gaseous state for a long time.
It reacts with the atmospheric moisture in the presence of sunlight to
from sulphuric acid and comes down on land along with rainwater (acid
rain).
SO2 + OH* Æ HSO3
HSO3 + O2 Æ HSO5
HSO5 + NO Æ HSO4 + NO2
In the presence of sunlight, the photochemically generated free radicals
react as a catalyst in these reactions. Thus, sunny weather enhances the
rate of conversion to acid, which decreases rapidly after sunset. HSO4 as
well as NO2 undergoes hydrolysis to form their respective acids H2SO4
and HNO3. Although the actual mechanism of these reactions is not
clear, these seem to occur in the presence of trace metal catalysts or
oxidizing agents such as ozone or hydrogen peroxide. Recent studies have
shown that manganese, and not iron, is the only metal that can act as
a catalyst in cloud droplets.
Sulphur dioxide undergoes several chemical reactions in air, forming
particulate matter and aerosols, which are scavenged from the atmosphere.
The SO2 and SO3 gases are washed down from the atmosphere in the
form of sulphuric acid. The presence of H2SO4 in increasing concentration
in the troposphere is indicated by the increasing and more widespread
occurrence of acid rain. A number of factors such as temperature,
light, intensity, humidity, air traffic, and SPM may influence these
reactions.
Sulphur dioxide reacts through several ways in the atmosphere, which
are as follows:
(i) Photochemical reactions
(ii) Chemical reactions in presence of NOx and hydrocarbons
(iii) Chemical reactions in water droplets and solid particles
In the photolysis of air containing SO2, olefin hydrocarbons, and NOx,
the rate of oxidation of SO2 has been found to increase, which results in
the formation of aerosols.
Control of SOx pollution
SOx can be reduced and controlled by the following important methods:
(i) Removal of the sulphur from fuel before burning
(ii) Use of low-sulphur content fuel
(iii) Using other energy sources for fuel combustion
(iv) Removal of SOx from fuel gases
(v) Use of natural gases
(vi) Use of nuclear power to generate electricity from power plants
About 15% of SO2 emission is caused by oil combustion. General
fuel oil is distilled over or left as residue in boiler during vaporization.
While refining, the distillate gets separated from the residual mixture,
leaving behind low content of S, which merely accounts for 0.05–0.035%
by weight. Substitution of energy sources is a better technique to solve
SOx pollution problem.
For example, hydroelectric plants do not need any fuel, and so they are
free from SOx pollution. Removal of three forms of S (pyrites, sulphates,
and organic sulphides) from fuel before burning can be achieved by
adopting the physical technique. However, coal can be converted to gases
by gasification process, in which powered coal reacts with stream and
oxygen in a fluidized bed at a high pressure ranging from 600 to 1000
psi. The product formed constitutes H2, CO, CO2, CH4, and H2S. CO and
H2 react to form CH4, thereby reducing the S content. Some refining
processes are also operated in petroleum industry, which lowers the
S content by 2.5–3%. Huge investment and heavy recurring costs are

involved in the current technology for removal of SOx from flue gases.
However, double alkali process has been used commercially to some
extent. SO2 is scrubbed off by two alkalis, that is, Ca(OH)2 and NaOH,
in two steps.
Nitrogen Oxides (NOx)
Nitrogen naturally comes from thunderstorms and biological processes.
Combustion engines in jets or cars also produce NO. In the atmosphere,
the average residence life of NO is 4 days and that of NO2 is 3 days.
The residence life of NOx may decrease in a highly polluted atmosphere
because of formation of nitric acid, which is predicated as nitric salts
with ammonia. HNO3 reacts rapidly to form a particulate substance
in the atmosphere and causes air pollution. Nitric acid as such is not
considered to be a health hazard at the level it is found in the urban air;
however, when it comes in contact with the atmospheric air, it undergoes
a series of chemical reactions to form various secondary pollutants such
as PAN, O3, and carbonyl compounds. On coming in contact with air, it
readily forms NO2, which is the chief constituent of photochemical smog
in metropolitan cities.
Reactions of NOx in the atmosphere are given below:
NO is formed by the reaction of O2 with atomic nitrogen:
N2 Æ N + N N + O2 Æ NO + O
High temperature favours the formation of NO; hence, automobiles such
as motor and heavy engine vehicles that operate at higher temperatures
are major sources for the production of NO. Oxidation of atmospheric NO
is a very slow process, which may generally take place over a period of
6 days.
2NO + O2 Æ 2NO2 NO + O + M Æ NO2 + M
When NO and O3 are formed in equal amounts, they combine together
to produce NO2 and O2.
O2 + O + M Æ O3 + M NO +O3 Æ O2 + NO2
NO2 is a highly reactive species occurring in atmosphere. It penetrates
into the troposphere and absorbs UV light as well as visible light. NO2
undergoes photodissociation using photo energy below 380 nm and is
reduced to NO and atomic oxygen by UV light. The atomic oxygen reacts
with oxygen to form ozone.
NO2 Æ NO + O
O + O2 Æ O3
Ozone reacts with NO to form NO2 and O2.
NO + O3 Æ NO2 + O2
Microorganism reduces N2O under anaerobic condition, producing the

pollutant NO. NO2 mainly exists as N2O4 (10%) in solid state. In gaseous
state, there is 90% NO2 and 10% N2O4.
2NO + O2 Æ 2NO2 + N2O4
NO2 reacts with water to form nitric acid and photochemical smog.
2NO2 + H2O Æ HNO2 + HNO3
N2O5 + H2O Æ 2HNO3
NO2 also reacts with hydroxyl ions in the stratosphere.
HO* + NO2 Æ HNO3
Nitric acid thus formed is reduced to NO2 by the attack of hydroxyl
radicals.
HO* + HNO3 Æ H2O + NO3
HNO3 Æ HO* + NO2
Sometimes atomic oxygen formed as a result of photochemical reduction
of NO2 also reacts with reactive hydrocarbons such as CH4, C2H6, and
C6H5CH3, which are generated by the burning of fossil fuels to from
radicals in the presence of UV light and oxygen.
O + Hydrocarbon Æ Radicals
These photochemically generated radicals are extremely reactive and
undergo a series of reactions in the presence of UV light to form more
reactive radicals, which combine with a number of pollutants in the
air to form NO2, O3, H2O2, and a number of other toxic substances
such as aldehydes, formaldehydes, and PAN. All these collectively form
photochemical smog.
Oxides of nitrogen produce toxic and corrosive gases through the
photochemical chain reaction. These gases produce nitric acid, which is
washed down and contributes to acid rain. Acidity of rainwater increases
when the amount of oxides of nitrogen and sulphur increases in the
atmosphere to produce more nitric and sulphuric acids. Acid rain reduces
fertility of the soil.
Photochemical Smog
NOx, in combination with unsaturated hydrocarbons, CO, O3, hydrogen
peroxide, and organic peroxide, forms photochemical smog in the presence
of sunlight. Photochemical reactions are initiated by UV light in the air.
Peroxybenzoyl nitrate is also produced in photochemical smog in the
presence of NO2 and olefins. The smog may have a 50 ppb of PAN also.
Peroxybenzoyl nitrate is 100 times more toxic than PAN and 200 times
as powerful as formaldehyde.
Effects of photochemical smog on human

(i) Photochemical smog is characterized by a yellowish grey haze in the
atmosphere. This smog along with ozone may irritate the eyes and
nose, affect lung function, degrade physical performance of humans,
and exacerbate asthma.
(ii) Symptoms such as nasal block and discharge, sneezing, hacking
cough, and airway obstruction may persist in highly vehicular
areas.
(iii) Studies have also revealed prevalence of chest problem and upper
airway morbidity in the area with higher levels of oxidants, such
as Mumbai and Delhi.
(iv) Occurrence of cold, cough, and sputum and breathlessness are closely
related to peaking of vehicular pollution.
(v) Photochemical smog leads to respiratory problem, reduces visibility,
alters various blood parameters, and aggravates diseases such as
headache and bronchitis.
Effect of photochemical smog on plants
(i) Photochemical smog is reported to cause injuries to petunia, lettuce,
pinto bean, citrus, salad crops, and coniferous trees even at a very
low concentration of 0.001 ppm.
(ii) PAN causes injury in beets, celery, pepper, and aster. It causes
silvering of leaves and death of forest tree.
(iii) PAN inhibits important Hill reactions of photosynthesis.
(iv) Photochemical smog is believed to cause early maturity in plants.
(v) Exposure of 4 ppb of PAN for 4 h is known to create visible damage in
plants. Vegetation damage may take several forms, such as chlorosis,
leaf abscission, and curling.
(vi) Photochemical smog alone or in conjunction with O3, PAN, and NOx
causes damage to forest, agriculture, and other materials such as
rubber, paints, fibres, and polymers.
2.6 Control Techniques for air pollutants

Some controls techniques can be used to remove gaseous contaminants from
industrial gas streams. The appropriateness of these techniques depends
on the chemical and physical characteristics of the specific gas- and
vapour-phase compounds present in the gas stream. Commercially, four
major techniques are used for the control of gaseous contaminants.
(i) Adsorption onto solid surfaces: Adsorption involves the
interaction between gaseous contaminants and the surface of a
solid adsorbent. The adsorbent can be available in a wide variety

of physical forms, such as pellets in a thick bed, small beads in a
fluidized bed, or fibres pressed onto a flat surface. There are two
types of adsorption mechanisms: (1) physical and (2) chemical. The
basic difference between physical and chemical adsorptions is the
manner in which the gas or vapour molecule is held to the adsorbent
surface.
(ii) Absorption into liquids: Gaseous contaminants that are soluble
in aqueous liquids can be removed by the absorbers. This is one of
the main mechanisms used for the removal of acid gas compounds
(for example, sulphur dioxide, hydrogen chloride, and hydrogen
fluoride) and water-soluble organic compounds (for example, alcohols,
aldehydes, and organic acids). The contaminant gas or vapour is
absorbed from the gas stream as it comes into contact with the
liquid.
• Oxidation to form non-toxic compounds: Oxidizers can be
used for the destruction of a wide variety of organic compounds.
There are three main categories—thermal oxidizers, catalytic
oxidizers, and flares. Thermal oxidizers and catalytic oxidizers
are used for sources such as surface coaters, gasoline storage and
distribution terminals, and synthetic organic chemical plants.
Flares are used primarily to treat emergency vent gases in
synthetic organic chemical plants and petroleum refiners.
(iii) Chemical reduction to form non-toxic compounds: Reduction
systems are used primarily for the destruction of NOx compounds
emitted from combustion processes. These systems include selective
non-catalytic reduction systems (SNCRs) and selective catalytic
reduction (SCR) systems. In both types of systems, a chemically
reduced form of nitrogen is injected into the gas stream to react
with the oxidized nitrogen compounds, such as NO and NO2. The
reactions between the reduced and oxidized forms of nitrogen result
in molecular N2, the major constituent of clean air.
(iv) Condensations of vapours to form liquids: Condensation
systems are used exclusively for the recovery of organic compounds
present at moderate-to-high concentrations in industrial process for
effluent gas steams. Based on the general operating temperature
range, condensation systems may be grouped into three main
categories:
• Water-based direct and indirect condensers (40°F to 80°F)
• Refrigeration condensers (–50°F to –150°F)
• Cryogenic condensers (–100°F to –320°F)
The most common types of condensers are those using cooling water
in direct contact or indirect contact vessels. Refrigeration and cryogenic
systems are used primarily for the high-efficiency recovery of high-value
contaminants. Condensation systems are used primarily for the control
of high concentrations of organic contaminants.
NOx Control Technique

Flue gas treatment
Selective non-catalytic reduction—These systems are used to control
NOx emissions from boilers and waste incinerators. An SNCR system uses
ammonia or urea to react with NOx in a complex set of high-temperature,
homogeneous gas-phase reactions. Ammonia can be used in an anhydrous
or an aqueous form. The aqueous ammonia storage and feeding systems
are similar to those used for urea. Ammonia is diluted prior to use,
and the flow rate to each set of nozzles is controlled individually. In
anhydrous ammonia injection systems, ammonia is stored in pressurized
storage tanks and fed as a gas. The products of the reactions between
ammonia and urea with NOx are molecular nitrogen and water. In both
ammonia and urea systems, small quantities of ammonia can remain
in the gas stream after the reactions are completed. These emissions
are termed as “ammonia slip”. The ammonia or urea should be injected
into a portion of the boiler when the combustion gas temperature is in
the range of 870–1100°C. Effectiveness of NOx reduction depends on the
adequacy of the gas temperature range at the area of injection. If the
gas stream is in the 1600–2000°F temperature range, NOx reductions
of up to 60% are possible. If some of the ammonia or urea reagent is
injected in portions of the combustion gas stream that are too cold, high
ammonia slip emissions can occur. Injection of reagents in portions of
the gas stream that are above 2000°F can result in the oxidation of the
nitrogen in the reagents to form additional NOx.
SCR systems—The SCR system uses a catalyst-impregnated bed to
reduce NOx emissions. Because of the effect of the catalyst, the chemical
reduction reaction between ammonia and NOx occurs at temperatures
much lower than those required for SNCR systems. Most SCR systems
operate in the range of 550–750˚F (290–400˚C), which is a very convenient
temperature range that exists at the exit of the feedwater economizers
in the boiler. The gas stream can be withdrawn from the boiler at this
point, passed through a series of catalyst beds, and returned to the boiler
upstream of the air preheater. When properly designed and operated,
SCR systems are capable of sustained NOx reductions in the range of
60–90%. However, to minimize reagent costs, SCR systems are applied
after all reasonable combustion modifications required to minimize the

NOx formation rates have been installed in the boiler.
Control Methodologies for Sulphur Oxides

Sulphur dioxide emissions from fossil fuel-fired combustion sources
can be reduced by five techniques. Fuel treatment and FGD are the
most common techniques being used to comply with the Clean Air Act
requirements.
(i) Low sulphur fuel firing: One of the most straightforward ways
to reduce SO2 emissions from combustion sources is by burning a
low-sulphur-containing fuel. The coal-fired boilers use low-sulphur
coal, low-sulphur fuel oil, or natural gas, instead of a high-sulphur
coal. The use of low-sulphur coal can reduce SO2 by more than
80%. Low-sulphur coal usually contains between 0.4% and 1% of
sulphur, whereas high-sulphur coal contains sulphur between 1%
and 5%.
(ii) Flue gas desulphurization (FGD): FGD is the most common
technology used for controlling emissions of sulphur oxides from
combustion sources. FGD technology is also used to reduce SO2
emissions from copper smelters. In this method, SO2 gaseous
emissions are usually removed by a post-combustion absorption
process. FGD scrubbing processes can be “wet” or “dry”. Wet
scrubbing processes use a liquid absorbent to absorb the SO2
gases.
(iii) Dry scrubbing: Dry scrubbing is basically a two-step chemical
process. In the first step, the flue gas leaving the boiler or
incinerator is scrubbed with a stream of alkali, usually calcium
hydroxide. In the second step, the reaction products are collected
in a high-efficiency particulate matter control device, such as a
pulse jet bag house, a reverse air bag house, or an electrostatic
precipitator. There are two types of dry scrubbers: spray dryer
absorption and dry injection absorption.
(iv) Fluidized-bed combustion: A fluidized-bed boiler using an
alkali such as limestone can reduce emissions of sulphur oxides.
In this type of boiler, a grid supports the bed of coal and limestone
(or dolomite) in the firebox of the boiler. Combustion air is forced
upwards through the grid, suspending the coal and limestone bed
in a fluid-like motion. Natural gas is used to ignite the pulverized
coal. Once the coal is ignited, the gas is turned off. The sulphur
in the coal is oxidized to SO2 and consequently combined with
limestone to form calcium sulphate (CaSO4). The CaSO4 and fly
ash particulate matter are usually collected in a bag house or in
an electrostatic precipitator. Fluidized-bed boilers usually require a

calcium-to-sulphur stoichiometric ratio of 2.0:1.0 to 4.0:1.0 because
of the limited amount of calcium oxide surface area available.
(v) Fuel treatment
• Coal gasification: Over 70 different processes have been
developed for producing a combustible gas from coal. Three basic
steps are common to all coal gasification processes: pretreatment,
gasification, and gas cleaning. Coal pretreatment involves coal
pulverizing and washing. The pulverized coal is gasified in
a reactor with limited oxygen, producing a gas with a low,
medium, or high heating value by applying heat and pressure
or by using a catalyst to break down the components of the coal.
The gas produced contains carbon monoxide, hydrogen, carbon
dioxide, water, methane, and contaminants, such as hydrogen
sulphide and char. During gasification, the sulphur content
in the coal is converted to H2S, which is then converted to
elemental sulphur by partial oxidation and catalytic conversion.
The synthetic gas produced is free of sulphur and can be burnt
without releasing harmful pollutants.
• Coal liquefaction: A process for changing coal into synthetic
oil is called coal liquefaction. It is similar to coal gasification.
Two basic approaches are used for liquefaction. One approach
uses gasifiers to convert coal to carbon monoxide, hydrogen,
and methane, followed by condensation to convert the gases to
oils. The other approach uses a solvent or a slurry to liquefy
pulverized coal and then converts this liquid into a heavy fuel
oil. Some processes produce both a synthetic gas and a synthetic
oil. Hydrogen is used to convert sulphur present in the coal
to hydrogen sulphide gas, which is partially oxidized to form
elemental sulphur and water. More than 85% of the sulphur
can be removed from coal by liquefaction.
• Coal cleaning: There are two types of coal cleaning processes:
physical and chemical. Physical coal cleaning is used to remove
the inorganic (mainly pyritic) sulphur compounds present in
the coal, whereas chemical coal cleaning is used to reduce
organic sulphur compounds. Physical coal cleaning is a well-
established technology that has been used for more than 50
years to reduce the sulphur and ash content of high-sulphur
coal supplies. Physical coal cleaning uses the differences in
density of both the coal and the sulphur-bearing impurities in
the coal. The coal is crushed, washed, and then separated by
settling processes, using cyclones, air classifiers, or magnetic
separators. Approximately 40–90% of the pyrite sulphur content
can be removed by physical coal cleaning. Its effectiveness

depends on the size of pyritic sulphur particles and the amount
of pyritic sulphur contained in the coal.
Chemical coal cleaning methods that reduce the organically bound
sulphur are currently under development. In microwave desulphurization,
the coal is crushed and then heated for 30–60 s by exposure to microwaves.
Mineral sulphur selectively absorbs this radiation, forming H 2S gas,
which is reduced to elemental sulphur by the Claus process. In another
microwave process, calcium hydroxide [Ca(OH)2] is added to crushed coal.
The organic sulphur present in coal converts to CaSO3 when exposed to
this radiation. The coal is washed with water to remove the CaSO3 and
other impurities. As much as 70% of the sulphur can be removed by the
microwave process.
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Chapter · January 2015

Navindu Gupta R S Khoiyangbam

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National Innovations in Climatic Resilient Agriculture (NICRA) View project

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becoming yellow by the action of sulphur dioxide fumes, leakage of methyl

2.2 ENVIRONMENTAL SEGMENT

(iv) Thermosphere or ionosphere: In this layer, most of the gaseous

Lithosphere mainly consists of three layers: crust, mantle, and outer

2.3 TOXIC CHEMICALS IN THE ENVIRONMENT

(ii) “Deficient” at lower level than (a), causing metabolic disorder

Classification of Toxic Matters

and tobacco smoke. In addition to chemical substances, ultraviolet ray is

Types of food additives

• Flavours—add flavour to food

Reactions due to food additives

2.4 Water pollution

as organic matters of soil (decomposed animals, microorganisms, and

(iii) Sediments—Sediments are insoluble soil particles of unknown

Main Sources of Pollutants

(h) Aerial fallout

climate. Petroleum hydrocarbons enter freshwater environment in

• Arsenic, cadmium, lead, nickel, manganese, and molybdenum:

Table 1 Toxic trace elements in natural water and wastewater

Metal Source Effects

include contamination from radioactive sources used for monitoring

such as toxicity, mobility, radioactive half-life, and type of radioactive

• Instantaneous flashes from nuclear explosions

Methods of Analysis of Parameters of Wastewater

Table 2 Methods of analysis

Parameter Method Reason for testing

Sampling and storage: Samples for BOD analysis may degrade

2.5 Air Pollutants

Table 4 Saturated DO levels

Source Kemker, Christine. 2013. Dissolved oxygen. Fundamentals of Environmental

jarring or noise. Life can also be saved by blood transfusion, by

Emission of GHGs causes global climate change. The presence of ozone-

found in urban air are formed by chemical reactions driven by sunlight.

S content by 2.5–3%. Huge investment and heavy recurring costs are

Microorganism reduces N2O under anaerobic condition, producing the

Effects of photochemical smog on human

2.6 Control Techniques for air pollutants

solid adsorbent. The adsorbent can be available in a wide variety

NOx Control Technique

after all reasonable combustion modifications required to minimize the

Control Methodologies for Sulphur Oxides

an electrostatic precipitator. Fluidized-bed boilers usually require a

can be removed by physical coal cleaning. Its effectiveness

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