6 Environmental Chemistry

Anthrosphere the environment i.e., part of

made or modified by
Anthrosphere may human
be defined as man-made
activities. part of
Prehistoric humans made littleimpact on environment
environment
with industrialization, particularly after Industrial Revolution (1780), this impact became more and
effects on the
environment as a whole.
bu

Like the environmental Segments terms of

described its
above, anthrosphere also consists of several parts
more pronounced as a separate area in

"Structures/houses used for living

manufacturing, education and other activities.
" Infrastructure
Structures usedincluding water, fuel and electricity distribution systems and waste disposal
for commerce,

systems such as sewers

" railways, airports and waterways.
Infrastructure
Natural processes transport - roads,
have led to a finely tuned balance among the systems composing Earth's
natural environment. Life forms on Earth have influenced Earth's climate which determines its
suitability for life. According to Gaia hypothesis, as proposed by James Lovelock, a British Chemist,
atmospheric O,/CO, balance is established and sustained by organisms which determine and maintain
Earth's climate and other environmental conditions. It is essential that the delicate balance
(Man-Environment) is not upset but sustained by Man for his oWn surviVal.

1.4 THE NATURAL CYCLES OF THE ENVIRONMENT

Ihe biosphere in its widest sense consists of the earth's crust, the atmosphere and various
Species of life, which exist in the zone 600 metres above and 10,000 metres below sea level. The
biosphere is very large and complex and hence divided into smaller units called ecosystems. An
ecosystem consists of plants, animals and micro0-organisms, which live in a definite zone along with
the physical factors such as soil, water andair. Within an ecosystem, there are dynamic
between the living forms and their physical environment. These relationships areinterrelationships
manifested as
natural cycles which provide a continuous circulation of the essential constituents
The natural cycles and ecosystems operate in a balanced manner which necessary for life.
and sustains the life processes on earth. stabilises the entire biosphere

1.4.1 Endogenic and Exogenic Cycles

Material/Natural cycles can be broadly divided into endogenic cycles which mainly involve
subsurface rocks and exogenic cycles which occur largely on Earth's surface. These two cycles
have an atmospheric component and are illustrated in Figure 1.5. Sediment and soil can be
considered
as being shared between the two cycles and constitute the predominant interface
Soil can be considered as being shared between the two cycles and between them.
constitute the
interface between them.
Most biogeochemical cycles are described as elemental cycles involving nutrient
predominant
as C, N, 0, P and S. Many are exogenic cycles in which the element concerned spends
Pdo not have a
elements
part of
such
cycle in the atmosphere - O, N, and Cas CO,, Others notably gaseous the
and is in endogenic cycle. All sedimentary
dissolved substances leached from weathered
cycles involve salt
minerals-these
solutions or soil solutions
substances may component
which contaasin
be deposited
nutrients.
mineral formations or taken up by organisms as
 Introduction 7

Exogenic
cycle
Atmosphere

Biosphere

Hydrosphere
Endogenic Soil Sediments
cycle

Sedimentary
rock

Igneous
rock
Metamorphic
rock

Magma

Fig. 1.5 The endogenic and exogenic cycles

1.4.2 The Hydrologicai Cycie

The hydrological cycle is a continuous natural process, which
helps in exchange of water
between the atmnosphere, the land, the sea, living plants and animals. About
flux absorbed by the earth is used to drive the one-third of the solar
from the
hydrological cyclemassive evaporation of water
oceans, cloud formation andprecipitation which provides us with our supply and reserves
of fresh water.
Water as rain, hail or snow is precipitated on all land and water surfaces. Water on land
surfaces seeps into the soil as ground water. Below the ground, there is a natural water level or water
table. The soil below the water table is sustained by the underlying clay and rock strata.
water does not remain stationary but moves in various directions. Water moves up above theGround
water
table by capillary action and thereby maintains a continuous supply of water to the surface layer of
soil, where it is absorbed by plant roots in absence of rain. Another important underground water
 8 Environmental Chemistry

Tesource is the aquifer. The latter exists above impermeable rock strata--
porous rocks and forms underground lakes or reservoirs. From these water
aquifeperrs,colates
the
extracted by sinking wells, tube wells and pumping it to the surface.
In the event of good rainfall, all the rainwater precipitates on land does
SOl. Surface water or nn-off flows into streams, rivers, lakes and catchmentnot
The land surface and all water
surfaces on the earth lose water by evaporation by or areaspercolate
Normal evaporation from the oceans exceeds precipitation by rain into the seas by about
This excess 10 per cent
ultimately moves as water vapour over land surface and 10 solarTeS rvoeitnety
hydrological cycle and thereby per cen
excess water through leaves by the process of transpiration. This is balances
meets our requirements for additional water. Plants absorb th
salts throughout capilanary ground
water but give off
process which ensures conduction water
of and
dissolved
Hence, the hydrological cycle consists ofa balanced continuous process the plantim.portant
mineral

transpiration, precipitation, surface run-off of

quantum of annual rainfall and
cubic metre = 102 ie., one evaporation
and ground water movements. Arough
may be given. Each year approx. 50 Tm (1 e1Tmivdaeaporation
of the,
litres) =1Tena
million cubic 1 cubic metre or Im' = 1000
evaporated and the same quantity of water ismetres;precipitated over the earth's surface. From i water
about 44.5 Tm' water flows to
The
the sea per year and this is available for man's water the land
hydrological cycle
About one third of the solar consists of five parts which supplies.
flux absobed by the earth'sprovide
surface
the global water supply
is used to drive the
(Fig. 15%
cyclemassive
provides us with evaporation
of water from the hydrological
our supply and reserves of freshoceans, cloud formation and precipitation, which
The solar energy-powered water.
hydrological cycle acts as an endless conveyor belt to move
essential for life through ecosystems. materials
1.4.3 The Carbon Cycle
The Cartbon Cycle operates the
through the environment. It shows carbon circulation of Carbon, the backbone of Organic
constituent of the atmosphere. Part of it is present in inthe atmosphere as CO,, aminor but important Chemistry,
major portion is dissolved in sea and dissolved surface water and ground water as
ocean
sealocean bottoms while part of carbon is water where it is finally fixed as carbonate HCO,
fixed by photosynthesis (by green
carbon, CH,0 which is a constituent of all life minerals at the
plants) as
lignite, petroleum and natural gas (Fig. 1.6). molecules. Another fraction of carbon is biological
It should be noted that the fixed as coal,
significance theof
to biological systems and ultimately to geosphere carbon- cycle is based on the transfer of
which they extract their food, minerals and fuels) as(solid earth upon which carbon
fossil carbon humans live and from
Micro-organisms play an important role in the carbon cycle and fossil fuels.
reactions. Photosynthetic algae in water are important
carbonn-fi xin gmediating significant biochemical
up CO, causing precipitation of CaCO, and CaCO, MgCO,. compounds in water; they take
carbon by geochemical processes to fossil petroleum, coal and
carbon into CO, from biomass, fossil fuel and finally return itlignite. Micro-organisms convert organic
to the They also degrade organic
method of removing oil spill on seas and also carbon-containing hazardous
micro-organisms.
atwastes
mospherise.by theAn important
action of
 Introduction 9

Sun
Cloud Cloud

etiitahon Transpiration

Run off Plants

Evaporation Evaporation

Lake Ground water

Fig. 16 The hydrologic eycle (Reprinted by permision of Brooks/Cole Publisting Company, Monterey, Caliífomia
93940, USAfrom Environmental Chemistry, 3rd edn, S.E. Manahan, p. &, 1979, Willard Grant Press, Statler
Office Building, Boston, Massachusetts)

1.4.4 The Oxygen Cycle

Oxygen is the major component of all living organisms. Hence, its adequate supply is vital for
sustenance of life in the biosphere. Oxygen is needed by most of the plants and animals and all human
beings for aerobic respiration or enzymatic oxidation of organic food, which sustains growth and
general metabolism. Thus, it is absorbed from the environment during aerobic respiration but released
by plants during photosynthesis thereby setting up the oxygen cycle. There is also continuous
exchange ef O, between the atmosphere and all water surfaces on the earth. The total amount of O,
in the biosphere is relatively constant so that the oxygen cycle may get stable.
Oxygen contributes largely to the processes on the earth's surface. It participates in combustion
reactions e.g., burning of fossil fuels (C, CH)

Atmosphere
CO2 Uptake by
photosynthesis
CO,
Ocean
|uptake

Plants
Auto
exhaust

Ocean
Factories (Biomass)
Plants
\CO) HCO,
Organic co
carbon
Mineral deposit

Fig. 1.7 The gítbon cycle

 10 Evironmental Chemistry
C+0, - CO,
gas) + 20, ’ CO, + 2H,0
CH,(in natural processes of minerals:
oxidative weathering
Oxygen is consumed by some
4FeO + O, ’ 2Fe,0,
consumed bulk of O,
soluble iron (Fe) (1)
In the primitive stage of the earth,
deposits of Fe,0,:
2Fe,0,+ 8H*
gvIng latp
4Fe +O, + 4H,0
atmosphere through the process of photosynthesig:
Green plants returm O, to the
+ O,
CO, + H,0+ hv ’ (CH,0] (5)
oxygen stock in the
This process was responsible for building the original
continues to maintain the oxygen balance in the atmosphere. It
may be noted that
of fossil fuels and of reducing gases (CO) from volcanoes consume large
quantities of thoughatmoscombus
phere tion
and
fO, it has litle
operation of the
impact on the total OXygen stock in the atmosphere because of the Oxygen cycle.
The oxygen cycle is based on the exchange of oxygen among the environmental
atmosphere, lithosphere, hydrosphere, and biosphere. It has a key role in atmospheric segments: the
geochemical transformation and life processes (Fig. 1.8). chemistry,
hy

O, + hv 0 + O, Ozone shield absorption

0 + O, + M ’ O, + M of ultraviolet radiation
from 220 nm to 330 nm

O, + hv -0 + o

200 + O, = 2C0,
Oxygen consumed by
reducing gases of
volcanic origin
CO, CO,

CH,0) + O, = CO, + H,0 C0,

respiration by animals
C+ O, = CO,
Oxygen consumed by CO, + H,0 + hv = (CH,0) + O,
burning fossil fuels O, + 4FeO = 2Fe,O, (Photosynthesis)
Oxidative weathering of
reduced minerals ECazt + CO = CaCO,
Combined oxygen held
in sediments

Fie. 1.8Oxygen cycle (Reprinted by permission of Brooks/Cole Publishing Company, Monterey,

USA from Environmental Chemistry, 3rd edn., S.E. Manaban, p. 289, 1979, Williard California-93940,
Grant Press, Statier
Ofice Building, Boston, Massachusetts)
 Introduction 11

Oxygen contributes largely to the processes on earth's surface, It participates in combustion

reacttons, degradation of organic materials and some oxidative weathering processes.
C+0, CO,
CH,(in natural gas) + 20, ’ C0, + 2H,0
4FeO + O, ’ 2Fe,0,
1.4.5 The Nitrogen Cycle
"Today, nitrogen atom may be throbbing in the cells of the meadow grass; tomorrow it may be
pulsating through the tissues of aliving animal. The nitrogen atom afterwards may rise from decaying
animal refuse and stream to the upper regions of the atmosphere where it may be yoked with oxygen
n a flash of lightning and retum as plant food to the soil in a torrent of rain or it may be directly
absorbed from the atmosphere by the soil and there rendered available for plant food by the action of
symbiotic bacteria. Thus, each nitrogen atom has doubtless undergone aneverceasing cycle of
changes through countless aeons of time"-Mello.

Atmosphere

Nitrogen
Denitrifying Nitrogen
Lightning
and
rain bacteria

Plants Animals
(proteins) (proteins)

Nitrifying Nitrosifying
bacteria bacteria

Dead organic
Nitrate Nitrite Ammonia residues

Run-off

Rivers Micro-organisms

Fig. 1.9 The antrogen cyle

Nitrogen and its compounds are essential for the maintenance of life processes in the biosphere.
There is continuous exchange of nitrogen within ecosystems, operating the nitrogen cycle (Fig. 19).
Plants and animals continuously produce proteins, which are organic compounds containing nitrogen.
Plants absorb nitrates from the soil to produce proteins,. The death and decay of plants and animals as
well as exCreta of animals comprise the major load of organic residues containing proteins to the soil.
 12 Environmental Chemistry
Various types of micro-organisms in the soil utilize these nitrogenous organic residues for their
chain of intermediate products such as ammonia, nitrites
metabolism. The resulting reactions yield a nitrogen cycle. Some
soil micro-organisms break
and nitrates. Plants absorb nitrates and re-enter the nitrogen into
while others transform soluble
down soil nitrate into N, by denitrification process hectare per year.
nitrogen compounds at a rate of about 0.1 tonne per hectare is added to the soil each year. There
per
In the total cycle, about 4-7 tonnes of nitrogen courses and the
into fresh water
is some loss from the soil through the leaching of nitrates
N, concentration inseas.
balanced and thus the the
However, by all these processes, the nitrogen cycle is this natural cycle is upset by modern
atmosphere relatively constant.
is It should be noted that each
nitrogenous fertilizers year to the
agricultural practices which dump about 40 million tonnes of
world'sFresh
cultivated land.
water resources Viz., streams, rivers and lakes get polluted by agricultural run-off i.e.,

leaching of excessive nitrate from agricultural lands.

1.4.6 The Phosphorus Cycle
of animal bones and teeth while
riospnates are necessary for the growth and maintenance
Organophosphates are essential for cell division involving the production of nuclear DNA and RNA.
Plants and animals derive their nutrition via eneroy metabolicpathways with chemical-utilizing ATP,
adenosine triphosphate.
Phosphate minerals are located in rocks and soil. where phosphates exist in soluble and
insoluble forms. Terrestrial plants absorb inorganic phosphate salts from the soil and convert these
ganephosphate. Animals obtain their phosphate by eating plants. Plants and animals after their
death and decay returm phosphates to the soil, which are finally converted to humus by the action or
soil micro-organisms. Bulk of the phosphate in the soil is fixed or absorbed onto soil particles, but
part of it is lost by leaching out (run-off) into water courses (Fig. 1.10).

Animals Plants

Soil Run-off to
Dead organic residues rivers
phosphates

Micro-organisms Rocks (phosphates)

Fig. Z10The phosphorus cycle on land

In fresh water, phytoplankton (floating algae) quickly absorbs soluble inorganic phosphates and
convert them into organophosphates. Algae are the sources of food for zooplankton, which in turn
are eaten by other aquatic animals. All these forms of life, after their death and decay settle to the
bottom of water. In due course, the organic waste decomposes by the action of micro-organisms,
recycling again (Fig. 1.10).sies o
releasing phosphates intothe water body for
 Introduction 13
River discharges

Soluble
phosphates Phytoplankton Zooplankton

Plants Animals

Dead organid
residues Micro-organisms
Fig. 1.11 The
phosphorus cycle in
The natural phosphate cycle, as discussed above, is badly water by
agricultural run-off containing superphosphate or affected pollution, mainly from
sewage containing
Jakes is the cause ofphosphates
triple-superphosphate
derived from excreta and detergents.
and also from domestic
Phosphate pollution of rivers and
algal bloom
disrupts the natural food chains. (eutrophication), which reduces the dissolved oxygen in water and
1.4.7 The Suiphur Cycle
Plants and animals depend on continuous supply of
some amino acids and proteins. Some sulphur bacteria sulphur and its compounds for synthesis of
serve as the media for exchanges of sulphur
within ecosystems. The sulphur cycle illustrates the circulation of sulphur and
its compounds in the
environment (Fig. 1.12).

Atmosphere SO,

Sulphides Sulphates

Plants and
animals (proteins)
Anaerobic Aerobic

Organic residues
(proteins)

Micro-organisms

Fig. 1.12The sulphur cycle

 14 Environmental Chemistry

The sulphur oxidation process is shown in the upper half of the cycle. The lower section
the conversion of sulphate into plant and animal cellular proteins and the shows
decay of dead
animal material by bacterial action. In nolluted waters under anaerobic conditions, H,S is plant and
produced by
0acteria giving deposits of FeS. In unpolluted waters under aerobic condítions, the sulphur bacteria
transform sulphides into sulphates for further production of proteins.
1.5 NATURAL AND MAN-MADE DISASTERS
Natural Disasters
Sometimes, there are drastic changes in environment due to natural disasters, e.g., cyclone,
typhoon, hurricane, tsunami, tornado, earthquake, volcanic eruption etc. within a very short time.
Cyclone, typhoon and hurricane are synonyms for the same weather phenomenon. Storms that
arise in the Indian Ocean and cause extensive flooding and damage in the Indian
sub-continent
including Sri Lanka and Myanmar are called cyclones. Those in the Pacific Ocean that threaten south
east Asia are typhoons and those in the north Atlantic Ocean that inflict heavy damages in the
Carribbean and south-eastern USA are hurricanes.
Over very warm areas of ocean warm, moist air starts rising so fast that it creates a region of
intense low pressure below it pulling more warm air from the surroundings. This gives rise to a vast
spiralling cyclone. The cyclones drift at a very high speed from 250 km/br to 800 km/hr (supercycl
and the whole weather system may be 800 km across.
Tornadoes are also caused by rising spiral of air but they are on a smaller scale affectin
Smaller area with shorter duration than those of cyclones. But they can be as devastating as cyclones