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UNIT 14 ENVIRONMENTAL CHEMISTRY After studying this unit, you will be able to understand the meaning of environmental chemistry; define atmospheric pollution, list reasons for global warming. green house effect and acid rain; identify causes for ozone layer depletion and its effects; give reasons for water pollution and know about international standards for drinking water; describe causes of soil pollution; suggest and adopt strategies for control of environmental pollution; appreciate the importance of green chemistry in day to day life. You have already studied about environment in your earlier classes. Environmental studies deal with the sum of all social, economical, biological, physical and chemical interrelations with our surroundings. In this unit the focus will be on environmental chemistry. Environmental chemistry deals with the study of the origin, transport, reactions, effects and fates of chemical species in the environment. Let us discuss some important aspects of environmental chemistry. 14.1 ENVIRONMENTAL POLLUTION Environmental pollution is the effect of undesirable changes in our surroundings that have harmful effects on plants, animals and human beings. A substance, which causes pollution, is known as pollutant. Pollutants can be solid, liquid or gaseous substances present in greater concentration than in natural abundance and are produced due to human activities or due to natural happenings. Do you know, an average human being requires nearly 12-15 times more air than the food. So, even small amounts of pollutants in the air become significant compared to similar levels present in the food. Pollutants can be degradable, like discarded vegetables which rapidly break down by natural processes. On the other hand, pollutants which are slowly degradable, remain in the environment in an unchanged form for many decades. For example, substances such as dichlorodi- phenyltrichloroethane (DDT), plastic materials, heavy metals, many chemicals, nuclear wastes etc., once released into the environment are difficult to remove. These The world has achieved brilliance without wisdom, power without conscience. Ours is a world of nuclear giants and ethical infants.

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Page 1: ENVIRONMENTAL CHEMISTRY - Prashanth Ellinancertbooks.prashanthellina.com/.../Unit14(6).pdf · In this unit the focus will be on environmental chemistry. Environmental chemistry deals

CHEMISTRY398

UNIT 14

ENVIRONMENTAL CHEMISTRY

After studying this unit, you will beable to

••••• understand the meaning ofenvironmental chemistry;

••••• define atmospheric pollution, listreasons for global warming. greenhouse effect and acid rain;

••••• identify causes for ozone layerdepletion and its effects;

••••• give reasons for water pollutionand know about internationalstandards for drinking water;

••••• describe causes of soil pollution;

••••• suggest and adopt strategiesfor control of environmentalpollution;

••••• appreciate the importance of greenchemistry in day to day life.

You have already studied about environment in your earlierclasses. Environmental studies deal with the sum of allsocial, economical, biological, physical and chemicalinterrelations with our surroundings. In this unit the focuswill be on environmental chemistry. Environmentalchemistry deals with the study of the origin, transport,reactions, effects and fates of chemical species in theenvironment. Let us discuss some important aspects ofenvironmental chemistry.

14.1 ENVIRONMENTAL POLLUTION

Environmental pollution is the effect of undesirable changesin our surroundings that have harmful effects on plants,animals and human beings. A substance, which causespollution, is known as pollutant. Pollutants can be solid,liquid or gaseous substances present in greaterconcentration than in natural abundance and areproduced due to human activities or due to naturalhappenings. Do you know, an average human beingrequires nearly 12-15 times more air than the food. So,even small amounts of pollutants in the air becomesignificant compared to similar levels present in the food.Pollutants can be degradable, like discarded vegetableswhich rapidly break down by natural processes. On theother hand, pollutants which are slowly degradable, remainin the environment in an unchanged form for manydecades. For example, substances such as dichlorodi-phenyltrichloroethane (DDT), plastic materials, heavymetals, many chemicals, nuclear wastes etc., once releasedinto the environment are difficult to remove. These

The world has achieved brilliance without wisdom, powerwithout conscience. Ours is a world of nuclear giants andethical infants.

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ENVIRONMENTAL CHEMISTRY 399

pollutants cannot be degraded by naturalprocesses and are harmful to living organisms.In the process of environmental pollution,pollutants originate from a source and gettransported by air or water or are dumped intothe soil by human beings.

14.2 ATMOSPHERIC POLLUTION

The atmosphere that surrounds the earth isnot of the same thickness at all heights. Thereare concentric layers of air or regions and eachlayer has different density. The lowest regionof atmosphere in which the human beingsalong with other organisms live is calledtroposphere. It extends up to the height of~ 10 km from sea level. Above the troposphere,between 10 and 50 km above sea level liesstratosphere. Troposphere is a turbulent,dusty zone containing air, much water vapourand clouds. This is the region of strong airmovement and cloud formation. Thestratosphere, on the other hand, containsdinitrogen, dioxygen, ozone and little watervapour.

Atmospheric pollution is generally studiedas tropospheric and stratospheric pollution.The presence of ozone in the stratosphereprevents about 99.5 per cent of the sun’sharmful ultraviolet (UV) radiations fromreaching the earth’s surface and therebyprotecting humans and other animals from itseffect.

14.2.1 Tropospheric Pollution

Tropospheric pollution occurs due to thepresence of undesirable solid or gaseousparticles in the air. The following are the majorgaseous and particulate pollutants present inthe troposphere:

1. Gaseous air pollutants: These are oxidesof sulphur, nitrogen and carbon, hydrogensulphide, hydrocarbons, ozone and otheroxidants.

2. Particulate pollutants: These are dust,mist, fumes, smoke, smog etc.

1. Gaseous air pollutants(a) Oxides of Sulphur: Oxides of sulphurare produced when sulphur containing fossilfuel is burnt. The most common species,

sulphur dioxide, is a gas that is poisonous toboth animals and plants. It has been reportedthat even a low concentration of sulphurdioxide causes respiratory diseases e.g.,asthma, bronchitis, emphysema in humanbeings. Sulphur dioxide causes irritation tothe eyes, resulting in tears and redness. Highconcentration of SO2 leads to stiffness of flowerbuds which eventually fall off from plants.Uncatalysed oxidation of sulphur dioxide isslow. However, the presence of particulatematter in polluted air catalyses the oxidationof sulphur dioxide to sulphur trioxide.

2SO2 (g) +O2 (g) → 2SO3(g)

The reaction can also be promoted byozone and hydrogen peroxide.

SO2 (g) +O3 (g) → SO3(g) + O2 (g)

SO2(g) + H2O2(l) → H2SO4(aq)

(b) Oxides of Nitrogen: Dinitrogen anddioxygen are the main constituents of air.These gases do not react with each other at anormal temperature. At high altitudes whenlightning strikes, they combine to form oxidesof nitrogen. NO2 is oxidised to nitrate ion, 3NO−

which is washed into soil, where it serves as afertilizer. In an automobile engine, (at hightemperature) when fossil fuel is burnt,dinitrogen and dioxygen combine to yieldsignificant quantities of nitric oxide (NO) andnitrogen dioxide ( NO2 ) as given below:

N2 (g) + O2 (g) 1483K→ 2NO(g)

NO reacts instantly with oxygen to give NO2

2NO (g) + O2 (g) → 2NO2 (g)

Rate of production of NO2 is faster whennitric oxide reacts with ozone in thestratosphere.

NO (g) + O3 (g) → NO2 (g) + O2 (g)

The irritant red haze in the traffic andcongested places is due to oxides of nitrogen.Higher concentrations of NO2 damage theleaves of plants and retard the rate ofphotosynthesis. Nitrogen dioxide is a lungirritant that can lead to an acute respiratorydisease in children. It is toxic to living tissuesalso. Nitrogen dioxide is also harmful tovarious textile fibres and metals.

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CHEMISTRY400

(c) Hydrocarbons: Hydrocarbons arecomposed of hydrogen and carbon only andare formed by incomplete combustion of fuelused in automobiles. Hydrocarbons arecarcinogenic, i.e., they cause cancer. Theyharm plants by causing ageing, breakdown oftissues and shedding of leaves, flowers andtwigs.

(d) Oxides of Carbon(i ) Carbon monoxide: Carbon monoxide (CO)is one of the most serious air pollutants. It is acolourless and odourless gas, highlypoisonous to living beings because of its abilityto block the delivery of oxygen to the organsand tissues. It is produced as a result ofincomplete combustion of carbon. Carbonmonoxide is mainly released into the air byautomobile exhaust. Other sources, whichproduce CO, involve incomplete combustionof coal, firewood, petrol, etc. The number ofvehicles has been increasing over the years allover the world. Many vehicles are poorlymaintained and several have inadequatepollution control equipments resulting in therelease of greater amount of carbon monoxideand other polluting gases. Do you know whycarbon monoxide is poisonous? It binds tohaemoglobin to form carboxyhaemoglobin,which is about 300 times more stable than theoxygen-haemoglobin complex. In blood, whenthe concentration of carboxyhaemoglobinreaches about 3–4 per cent, the oxygencarrying capacity of blood is greatlyreduced. This oxygen deficiency, results intoheadache, weak eyesight, nervousness andcardiovascular disorder. This is the reason whypeople are advised not to smoke. In pregnantwomen who have the habit of smoking theincreased CO level in blood may inducepremature birth, spontaneous abortions anddeformed babies.

(ii) Carbon dioxide: Carbon dioxide (CO2) isreleased into the atmosphere by respiration,burning of fossil fuels for energy, and bydecomposition of limestone during themanufacture of cement. It is also emittedduring volcanic eruptions. Carbon dioxide gasis confined to troposphere only. Normally itforms about 0.03 per cent by volume of the

atmosphere. With the increased use of fossilfuels, a large amount of carbon dioxide getsreleased into the atmosphere. Excess of CO2

in the air is removed by green plants and thismaintains an appropriate level of CO2 in theatmosphere. Green plants require CO2 forphotosynthesis and they, in turn, emit oxygen,thus maintaining the delicate balance. As youknow, deforestation and burning of fossil fuelincreases the CO2 level and disturb the balancein the atmosphere. The increased amount ofCO2 in the air is mainly responsible for globalwarming.

Global Warming and Greenhouse Effect

About 75 % of the solar energy reaching theearth is absorbed by the earth’s surface, whichincreases its temperature. The rest of the heatradiates back to the atmosphere. Some of theheat is trapped by gases such as carbondioxide, methane, ozone, chlorofluorocarboncompounds (CFCs) and water vapour in theatmosphere. Thus, they add to the heating ofthe atmosphere. This causes global warming.

We all know that in cold places flowers,vegetables and fruits are grown in glasscovered areas called greenhouse. Do you knowthat we humans also live in a greenhouse? Ofcourse, we are not surrounded by glass but ablanket of air called the atmosphere, which haskept the temperature on earth constant forcenturies. But it is now undergoing change,though slowly. Just as the glass in agreenhouse holds the sun’s warmth inside,atmosphere traps the sun’s heat near theearth’s surface and keeps it warm. This iscalled natural greenhouse effect because itmaintains the temperature and makes theearth perfect for life. In a greenhouse, visiblelight passes through the transparent glass andheats up the soil and the plants. The warmsoil and plants emit infrared radiations. Sinceglass is opaque to infrared (heat) radiations, itpartly reflects and partly absorbs theseradiations. This mechanism keeps the energyof the sun trapped in the greenhouse.Similarly, carbon dioxide molecules also trapheat as they are transparent to sunlight butnot to the heat radiation. If the amount of

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ENVIRONMENTAL CHEMISTRY 401

carbon dioxide crosses the delicate proportionof 0.03 per cent, the natural greenhousebalance may get disturbed. Carbon dioxide isthe major contributor to global warming.

Besides carbon dioxide, other greenhousegases are methane, water vapour, nitrousoxide, CFCs and ozone. Methane is producednaturally when vegetation is burnt, digestedor rotted in the absence of oxygen. Largeamounts of methane are released in paddyfields, coal mines, from rotting garbage dumpsand by fossil fuels. Chlorofluorocarbons (CFCs)are man-made industrial chemicals used inair conditioning etc. CFCs are also damagingthe ozone layer (Section 14.2.2). Nitrous oxideoccurs naturally in the environment. In recentyears, their quantities have increasedsignificantly due to the use of chemicalfertilizers and the burning of fossil fuels. Ifthese trends continue, the average globaltemperature will increase to a level which maylead to melting of polar ice caps and floodingof low lying areas all over the earth. Increasein the global temperature increases theincidence of infectious diseases like dengue,malaria, yellow fever, sleeping sickness etc.

Acid rainWe are aware that normally rain water has apH of 5.6 due to the presence of H+ ions formedby the reaction of rain water with carbon

Fig. 14.1 Acid deposition

Think it Over

What can we do to reduce the rate of globalwarming?

If burning of fossil fuels, cutting downforests and trees add to greenhouse gasesin the atmosphere, we must find ways touse these just efficiently and judiciously.One of the simple things which we can doto reduce global warming is to minimise theuse of automobiles. Depending upon thesituation, one can use bicycle, publictransport system, or go for carpool. Weshould plant more trees to increase thegreen cover. Avoid burning of dry leaves,wood etc. It is illegal to smoke in publicplaces and work places, because it isharmful not only for the one who is smokingbut also for others, and therefore, we shouldavoid it. Many people do not understandthe greenhouse effect and the globalwarming. We can help them by sharing theinformation that we have.

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CHEMISTRY402

dioxide present in the atmosphere.

H2O (l) + CO2 (g) H2CO3 (aq)

H2CO3 (aq) H +(aq) + HCO3

–(aq)

When the pH of the rain water drops below5.6, it is called acid rain.

Acid rain refers to the ways in which acidfrom the atmosphere is deposited on theearth’s surface. Oxides of nitrogen andsulphur which are acidic in nature can beblown by wind along with solid particles in theatmosphere and finally settle down either onthe ground as dry deposition or in water, fogand snow as wet deposition. (Fig. 14.1)

Acid rain is a byproduct of a variety ofhuman activities that emit the oxides ofsulphur and nitrogen in the atmosphere. Asmentioned earlier, burning of fossil fuels (whichcontain sulphur and nitrogenous matter) suchas coal and oil in power stations and furnacesor petrol and diesel in motor engines producesulphur dioxide and nitrogen oxides. SO2 andNO2 after oxidation and reaction with waterare major contributors to acid rain, becausepolluted air usually contains particulatematter that catalyse the oxidation.

2SO2 (g) + O2 (g) + 2H2O (l) → 2H2SO4 (aq)

4NO2 (g) + O2 (g)+ 2H2O (l) → 4HNO3 (aq)

Ammonium salts are also formed and canbe seen as an atmospheric haze (aerosol of fineparticles). Aerosol particles of oxides orammonium salts in rain drops result in wet-deposition. SO2 is also absorbed directly onboth solid and liquid ground surfaces and isthus deposited as dry-deposition.

Acid rain is harmful for agriculture, treesand plants as it dissolves and washes awaynutrients needed for their growth. It causesrespiratory ailments in human beings andanimals. When acid rain falls and flows asground water to reach rivers, lakes etc. it affectsplants and animal life in aquatic ecosystem. Itcorrodes water pipes resulting in the leachingof heavy metals such as iron, lead and copperinto the drinking water. Acid rain damagesbuildings and other structures made of stoneor metal. The Taj Mahal in India has beenaffected by acid rain.

Activity 1You can collect samples of water fromnearby places and record their pH values.Discuss your results in the class. Let usdiscuss how we can help to reduce theformation of acid rain.

This can be done by reducing theemission of sulphur dioxide and nitrogendioxide in the atmosphere. We should useless vehicles driven by fossil fuels; use lesssulphur content fossil fuels for powerplants and industries. We should usenatural gas which is a better fuel than coalor use coal with less sulphur content.Catalytic converters must be used in carsto reduce the effect of exhaust fumes onthe atmosphere. The main component ofthe converter is a ceramic honeycombcoated with precious metals — Pd, Pt andRh. The exhaust gases containing unburntfuel, CO and NOx, when pass through theconverter at 573 K, are converted into CO2and N2. We can also reduce the acidity ofthe soil by adding powdered limestone toneutralise the acidity of the soil. Manypeople do not know of acid rain and itsharmful effects. We can make them awareby passing on this information and savethe Nature.

Taj Mahal and Acid RainThe air around the city of Agra, where theTaj Mahal is located, contains fairly highlevels of sulphur and nitrogen oxides. It ismainly due to a large number of industriesand power plants around the area. Use ofpoor quality of coal, kerosene and firewoodas fuel for domestic purposes add up tothis problem. The resulting acid rainreacts with marble, CaCO3 of Taj Mahal(CaCO3 +H2SO4 → CaSO4 + H2O+ CO2)causing damage to this wonderfulmonument that has attracted people fromaround the world. As a result, themonument is being slowly disfigured andthe marble is getting discoloured andlustreless. The Government of Indiaannounced an action plan in early 1995to prevent the disfiguring of this historicalmonument. Mathura refinery has alreadytaken suitable measures to check theemission of toxic gases.

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ENVIRONMENTAL CHEMISTRY 403

2. Particulate Pollutants

Particulates pollutants are the minute solidparticles or liquid droplets in air. These arepresent in vehicle emissions, smoke particlesfrom fires, dust particles and ash fromindustries. Particulates in the atmospheremay be viable or non-viable. The viableparticulates e.g., bacteria, fungi, moulds,algae etc., are minute living organisms that aredispersed in the atmosphere. Human beingsare allergic to some of the fungi found in air.They can also cause plant diseases.

Non-viable particulates may be classifiedaccording to their nature and size as follows:

(a) Smoke particulates consist of solid ormixture of solid and liquid particles formedduring combustion of organic matter.Examples are cigarette smoke, smoke fromburning of fossil fuel, garbage and dryleaves, oil smoke etc.

(b) Dust is composed of fine solid particles(over 1µm in diameter), produced duringcrushing, grinding and attribution of solidmaterials. Sand from sand blasting, sawdust from wood works, pulverized coal,cement and fly ash from factories, duststorms etc., are some typical examples ofthis type of particulate emission.

(c) Mists are produced by particles of sprayliquids and by condensation of vapours inair. Examples are sulphuric acid mist and

herbicides and insecticides that miss theirtargets and travel through air and formmists.

(d) Fumes are generally obtained by thecondensation of vapours duringsublimation, distillation, boiling andseveral other chemical reactions. Generally,organic solvents, metals and metallicoxides form fume particles.

The effect of particulate pollutants arelargely dependent on the particle size. Air-borne particles such as dust, fumes, mist etc.,are dangerous for human health. Particulatepollutants bigger than 5 microns are likely tolodge in the nasal passage, whereas particlesof about 1.0 micron enter into lungs easily.

Lead used to be a major air pollutantemitted by vehicles. Leaded petrol used to bethe primary source of air-borne lead emissionin Indian cities. This problem has now beenovercome by using unleaded petrol in most ofthe cities in India. Lead interferes with thedevelopment and maturation of red blood cells.

Smog

The word smog is derived from smoke and fog.This is the most common example of airpollution that occurs in many citiesthroughout the world. There are two types ofsmog:

(a) Classical smog occurs in cool humidclimate. It is a mixture of smoke, fog andsulphur dioxide. Chemically it is areducing mixture and so it is also calledas reducing smog.

(b) Photochemical smog occurs in warm, dryand sunny climate. The main componentsof the photochemical smog result from theaction of sunlight on unsaturatedhydrocarbons and nitrogen oxidesproduced by automobiles and factories.Photochemical smog has highconcentration of oxidising agents and is,therefore, called as oxidising smog.

Formation of photochemical smogWhen fossil fuels are burnt, a variety ofpollutants are emitted into the earth’s

This plan aims at clearing the air inthe ‘Taj Trapezium’– an area that includesthe towns of Agra, Firozabad, Mathura andBharatpur. Under this plan more than2000 polluting industries lying inside thetrapezium would switch over to the use ofnatural gas or liquefied petroleum gasinstead of coal or oil. A new natural gaspipeline would bring more than half amillion cubic metres of natural gas a dayto this area. People living in the city willalso be encouraged to use liquefiedpetroleum gas in place of coal, kerosene orfirewood. Vehicles plying on highways inthe vicinity of Taj would be encouraged touse low sulphur content diesel.

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CHEMISTRY404

troposphere. Two of the pollutants that areemitted are hydrocarbons (unburnt fuels) andnitric oxide (NO). When these pollutants buildup to sufficiently high levels, a chain reactionoccurs from their interaction with sunlight inwhich NO is converted into nitrogen dioxide(NO2). This NO2 in turn absorbs energy fromsunlight and breaks up into nitric oxide andfree oxygen atom (Fig. 14.2).

NO2(g) NO(g) + O(g) (i)

Oxygen atoms are very reactive andcombine with the O2 in air to produce ozone.

O(g) + O2 (g) O3 (g) (ii)

The ozone formed in the above reaction (ii)reacts rapidly with the NO(g) formed in thereaction (i) to regenerate NO2. NO2 is a browngas and at sufficiently high levels cancontribute to haze.

NO (g) + O3 (g) → NO2 (g) + O2 (g) (iii)

Ozone is a toxic gas and both NO2 and O3

are strong oxidising agents and can react withthe unburnt hydrocarbons in the polluted air

to produce chemicals such as formaldehyde,acrolein and peroxyacetyl nitrate (PAN).

3CH4 + 2O3 → 3CH2 = O + 3H2O

Formaldehyde

CH2=CHCH=O CH3COONO2

OAcrolein Peroxyacetyl nitrate (PAN)

Effects of photochemical smogThe common components of photochemicalsmog are ozone, nitric oxide, acrolein,formaldehyde and peroxyacetyl nitrate (PAN).Photochemical smog causes serious healthproblems. Both ozone and PAN act as powerfuleye irritants. Ozone and nitric oxide irritate thenose and throat and their high concentrationcauses headache, chest pain, dryness of thethroat, cough and difficulty in breathing.Photochemical smog leads to cracking ofrubber and extensive damage to plant life. Italso causes corrosion of metals, stones,building materials, rubber and paintedsurfaces.

Fig. 14.2 Photochemical smog occurs where sunlight acts on vehicle pollutants.

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How can photochemical smog becontrolled ?Many techniques are used to control or reducethe formation of photochemical smog. If wecontrol the primary precursors ofphotochemical smog, such as NO2 andhydrocarbons, the secondary precursors suchas ozone and PAN, the photochemical smogwill automatically be reduced. Usually catalyticconverters are used in the automobiles, whichprevent the release of nitrogen oxide andhydrocarbons to the atmosphere. Certainplants e.g., Pinus, Juniparus, Quercus, Pyrusand Vitis can metabolise nitrogen oxide andtherefore, their plantation could help in thismatter.

14.2.2 Stratospheric Pollution

Formation and Breakdown of OzoneThe upper stratosphere consists ofconsiderable amount of ozone (O3), whichprotects us from the harmful ultraviolet (UV)radiations (λ 255 nm) coming from the sun.These radiations cause skin cancer(melanoma) in humans. Therefore, it isimportant to maintain the ozone shield.

Ozone in the stratosphere is a product ofUV radiations acting on dioxygen (O2)molecules. The UV radiations split apartmolecular oxygen into free oxygen (O) atoms.These oxygen atoms combine with themolecular oxygen to form ozone.

O2 (g) O(g) + O(g)

O(g) + O2 (g) O3 (g)

Ozone is thermodynamically unstable anddecomposes to molecular oxygen. Thus, adynamic equilibrium exists between theproduction and decomposition of ozonemolecules. In recent years, there have beenreports of the depletion of this protective ozonelayer because of the presence of certainchemicals in the stratosphere. The mainreason of ozone layer depletion is believed tobe the release of chlorofluorocarboncompounds (CFCs), also known as freons.These compounds are nonreactive, nonflammable, non toxic organic molecules andtherefore used in refrigerators, air conditioners,

in the production of plastic foam and by theelectronic industry for cleaning computerparts etc. Once CFCs are released in theatmosphere, they mix with the normalatmospheric gases and eventually reach thestratosphere. In stratosphere, they get brokendown by powerful UV radiations, releasingchlorine free radical.

CF2Cl2 (g) (g) + F2Cl (g) (i)

The chlorine radical then react withstratospheric ozone to form chlorine monoxideradicals and molecular oxygen.

C•l (g) + O3 (g) → ClO

• (g) + O2 (g) (ii)

Reaction of chlorine monoxide radical withatomic oxygen produces more chlorineradicals.

ClO•

(g) + O (g) → C•l (g) + O2 (g) (iii)

The chlorine radicals are continuouslyregenerated and cause the breakdown ofozone. Thus, CFCs are transporting agents forcontinuously generating chlorine radicals intothe stratosphere and damaging the ozone layer.

The Ozone HoleIn 1980s atmospheric scientists working inAntarctica reported about depletion of ozonelayer commonly known as ozone hole over theSouth Pole. It was found that a unique set ofconditions was responsible for the ozone hole.In summer season, nitrogen dioxide andmethane react with chlorine monoxide(reaction iv) and chlorine atoms (reaction v)forming chlorine sinks, preventing much ozonedepletion, whereas in winter, special type ofclouds called polar stratospheric clouds areformed over Antarctica. These polarstratospheric clouds provide surface on whichchlorine nitrate formed (reaction iv) getshydrolysed to form hypochlorous acid(reaction (vi)). It also reacts with hydrogenchloride produced as per reaction (v) to givemolecular chlorine.

ClO•

(g) + NO2 (g) → ClONO2(g) (iv)

C•l (g) + CH4 (g) → C

•H3(g) + HCl(g) (v)

ClONO2(g) + H2O (g) → HOCl (g) + HNO3 (g) (vi)

ClONO2(g) + HCl (g) → Cl2 (g) + HNO3 (g) (vii)

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When sunlight returns to the Antarctica inthe spring, the sun’s warmth breaks up theclouds and HOCl and Cl2 are photolysed bysunlight, as given in reactions (viii) and (ix).

HOCl (g) hν→ O•

H (g) + C•l(g) (viii)

Cl2 (g) hν→ 2C•l (g) (ix)

The chlorine radicals thus formed, initiatethe chain reaction for ozone depletion asdescribed earlier.

Effects of Depletion of the Ozone LayerWith the depletion of ozone layer, more UVradiation filters into troposphere. UVradiations lead to ageing of skin, cataract,sunburn, skin cancer, killing of manyphytoplanktons, damage to fish productivityetc. It has also been reported that plantproteins get easily affected by UV radiationswhich leads to the harmful mutation of cells.It also increases evaporation of surface waterthrough the stomata of the leaves anddecreases the moisture content of the soil.Increase in UV radiations damage paints andfibres, causing them to fade faster.

14.3 WATER POLLUTION

Water is essential for life. Without water therewould be no life. We usually take water asgranted for its purity, but we must ensure thequality of water. Pollution of water originatesfrom human activities. Through differentpaths, pollution reaches surface or groundwater. Easily identified source or place ofpollution is called as point source. e.g.,municipal and industrial discharge pipes

where pollutants enter the water-source. Nonpoint sources of pollution are those where asource of pollution cannot be easily identified,e.g., agricultural run off (from farm, animalsand crop-lands), acid rain, storm-waterdrainage (from streets, parking lots and lawns),etc. Table 14.1 lists the major water pollutantsand their sources.

14.3.1 Causes of Water Pollution

(i) Pathogens: The most serious waterpollutants are the disease causing agentscalled pathogens. Pathogens include bacteriaand other organisms that enter water fromdomestic sewage and animal excreta. Humanexcreta contain bacteria such as Escherichiacoli and Streptococcus faecalis which causegastrointestinal diseases.

(ii) Organic wastes: The other major waterpollutant is organic matter such asleaves, grass, trash etc. They pollute water asa consequence of run off. Excessivephytoplankton growth within water is also acause of water pollution. These wastes arebiodegradable.

The large population of bacteriadecomposes organic matter present in water.They consume oxygen dissolved in water. Theamount of oxygen that water can hold in thesolution is limited. In cold water, dissolvedoxygen (DO) can reach a concentration up to10 ppm (parts per million), whereas oxygen inair is about 200,000 ppm. That is why even amoderate amount of organic matter whendecomposes in water can deplete the water ofits dissolved oxygen. The concentration of

Table 14.1 Major Water Pollutants

Pollutant Source

Micro-organisms Domestic sewage

Organic wastes Domestic sewage, animal excreta and waste, decaying animalsand plants, discharge from food processing factories.

Plant nutrients Chemcial fertilizers

Toxic heavy metals Industries and chemical factories

Sediments Erosion of soil by agriculture and strip mining

Pesticides Chemicals used for killing insects, fungi and weeds

Radioactive substances Mining of uranium containing minerals

Heat Water used for cooling in industries

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dissolved oxygen in water is very importantfor aquatic life . If the concentration of dissolvedoxygen of water is below 6 ppm, the growth offish gets inhibited. Oxygen reaches watereither through atmosphere or from the processof photosynthesis carried out by manyaquatic green plants during day light.However, during night, photosynthesis stopsbut the plants continue to respire, resultingin reduction of dissolved oxygen. Thedissolved oxygen is also used bymicroorganisms to oxidise organic matter.

If too much of organic matter is added towater, all the available oxygen is used up. Thiscauses oxygen dependent aquatic life to die.Thus, anaerobic bacteria (which do not requireoxygen) begin to break down the organic wasteand produce chemicals that have a foul smelland are harmful to human health. Aerobic(oxygen requiring) bacteria degrade theseorganic wastes and keep the water depletedin dissolved oxygen.

Thus, the amount of oxygen required bybacteria to break down the organic matterpresent in a certain volume of a sample ofwater, is called Biochemical Oxygen Demand(BOD). The amount of BOD in the water is ameasure of the amount of organic material inthe water, in terms of how much oxygen willbe required to break it down biologically. Cleanwater would have BOD value of less than5 ppm whereas highly polluted water couldhave a BOD value of 17 ppm or more.

(iii) Chemical Pollutants: As we know thatwater is an excellent solvent, water solubleinorganic chemicals that include heavy metalssuch as cadmium, mercury, nickel etcconstitute an important class of pollutants. Allthese metals are dangerous to humansbecause our body cannot excrete them. Overthe time, it crosses the tolerance limit. Thesemetals then can damage kidneys, centralnervous system, liver etc. Acids (like sulphuricacid) from mine drainage and salts from manydifferent sources including raw salt used tomelt snow and ice in the colder climates(sodium and calcium chloride) are watersoluble chemical pollutants.

The organic chemicals are another groupof substances that are found in polluted water.Petroleum products pollute many sources ofwater e.g., major oil spills in oceans. Otherorganic substances with serious impacts arethe pesticides that drift down from sprays orrunoff from lands. Various industrialchemicals like polychlorinated biphenyls,(PCBs) which are used as cleansing solvent,detergents and fertilizers add to the list ofwater pollutants. PCBs are suspected to becarcinogenic. Nowadays most of the detergentsavailable are biodegradable. However, their usecan create other problems. The bacteriaresponsible for degrading biodegradabledetergent feed on it and grow rapidly. Whilegrowing, they may use up all the oxygendissolved in water. The lack of oxygen kills allother forms of aquatic life such as fish andplants. Fertilizers contain phosphates asadditives. The addition of phosphates in waterenhances algae growth. Such profuse growthof algae, covers the water surface and reducesthe oxygen concentration in water. This leadsto anaerobic conditions, commonly withaccumulation of abnoxious decay and animaldeath. Thus, bloom-infested water inhibits thegrowth of other living organisms in thewater body. This process in which nutrientenriched water bodies support a dense plantpopulation, which kills animal life by deprivingit of oxygen and results in subsequent loss ofbiodiversity is known as Eutrophication.

14.3.2 International Standards forDrinking Water

The International Standards for drinking waterare given below and they must be followed.

Fluoride: For drinking purposes, watershould be tested for fluoride ion concentration.Its deficiency in drinking water is harmful toman and causes diseases such as tooth decayetc. Soluble fluoride is often added to drinkingwater to bring its concentration upto 1 ppmor 1 mg dm–3. The F– ions make the enamel onteeth much harder by convertinghydroxyapatite, [3(Ca3(PO4)2.Ca(OH)2], theenamel on the surface of the teeth, into muchharder fluorapatite, [3(Ca3(PO4)2.CaF2].

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However, F– ion concentration above 2 ppmcauses brown mottling of teeth. At the sametime, excess fluoride (over 10 ppm) causesharmful effect to bones and teeth, as reportedfrom some parts of Rajasthan.

Lead: Drinking water gets contaminated withlead when lead pipes are used fortransportation of water. The prescribed upperlimit concentration of lead in drinking wateris about 50 ppb. Lead can damage kidney,liver, reproductive system etc.

Sulphate: Excessive sulphate (>500 ppm) indrinking water causes laxative effect, otherwiseat moderate levels it is harmless.

Nitrate: The maximum limit of nitrate indrinking water is 50 ppm. Excess nitrate indrinking water can cause disease such asmethemoglobinemia (‘blue baby’ syndrome).

Other metals: The maximum concentrationof some common metals recommended indrinking water are given in Table 14.2.

pollution levels. Ensure that appropriateaction is taken. You can write to the pressalso. Do not dump waste into ahousehold or industrial drain which canenter directly to any water body, such as,river, pond, stream or lake. Use compostinstead of chemical fertilizers in gardens.Avoid the use of pesticides like DDT,malathion etc., at home and try to usedried neem leaves to help keep insectsaway. Add a few crystals of potassiumpermanganate (KMnO4) or bleachingpowder to the water tank of your house.

14.4 SOIL POLLUTION

India being an agriculture based economygives high priority to agriculture, fisheries andlivestock development. The surplusproduction is stored by governmental andnon-governmental organisations for the leanseason. The food loss during the storage alsoneeds special attention. Have you ever seen thedamages caused to the crops, food items byinsects, rodents, weeds and crop diseases etc?How can we protect them? You are acquaintedwith some insecticides and pesticides forprotection of our crops. However, theseinsecticides, pesticides and herbicides causesoil pollution. Hence, there is a need for theirjudicious use.

14.4.1 Pesticides

Prior to World War II, many naturallyoccurring chemicals such as nicotine (byplanting tobacco plants in the crop field), wereused as pest controlling substance for majorcrops in agricultural practices.

During World War II, DDT was found to beof great use in the control of malaria and otherinsect-borne diseases. Therefore, after the war,DDT was put to use in agriculture to controlthe damages caused by insects, rodents, weedsand various crop diseases. However, due toadverse effects, its use has been banned inIndia.

Pesticides are basically synthetic toxicchemicals with ecological repercussions. Therepeated use of the same or similar pesticidesgive rise to pests that are resistant to that

Metal Maximum concentration(ppm or mg dm–3 )

Fe 0.2

Mn 0.05

Al 0.2

Cu 3.0

Zn 5.0

Cd 0.005

Table 14.2 Maximum Prescribed Concen-tration of Some Metals inDrinking Water.

Activity 2

You can visit local water sources andobserve if the river/lake/tank/pond areunpolluted/slightly polluted/ moderatelypolluted or severely polluted by lookingat water or by checking pH of water.Document the name of the river and thenearby urban or industrial site fromwhere the pollution is generated. Informabout this to Pollution Control Board’soffice set up by Government to measure

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group of pesticides thus making the pesticidesineffective. Therefore, as insect resistance ofDDT increased, other organic toxins such asAldrin and Dieldrin were introduced in themarket by pesticide industry. Most of theorganic toxins are water insoluble and non-biodegradable. These high persistent toxinsare, therefore, transferred from lower trophiclevel to higher trophic level through food chain(Fig.14.3). Over the time, the concentration oftoxins in higher animals reach a level whichcauses serious metabolic and physiologicaldisorders.

Fig. 14.3 At each trophic level, the pollutantgets 10 times concentrated.

sodium chlorate (NaClO3), sodium arsinite(Na3AsO3) and many others. During the firsthalf of the last century, the shift frommechanical to chemical weed control hadprovided the industry with flourishingeconomic market. But one must remember thatthese are also not environment friendly.

Most herbicides are toxic to mammals butare not as persistent as organo-chlorides.These chemicals decompose in a few months.Like organo-chlorides, these too becomeconcentrated in the food web. Some herbicidescause birth defects. Studies show that corn-fields sprayed with herbicides are more proneto insect attack and plant disease than fieldsthat are weeded manually.

Pesticides and herbicides represent only avery small portion of widespread chemicalpollution. A large number of other compoundsthat are used regularly in chemical andindustrial processes for manufacturingactivities are finally released in the atmospherein one or other form.

14.5 INDUSTRIAL WASTE

Industrial solid wastes are also sorted out asbiodegradable and non-degradable wastes.Biodegradable wastes are generated by cottonmills, food processing units, paper mills, andtextile factories.

Non-biodegradable wastes are generatedby thermal power plants which produce flyash; integrated iron and steel plants whichproduce blast furnace slag and steel meltingslag. Industries manufacturing aluminium,zinc and copper produce mud and tailings.Fertilizer industries produce gypsum.Hazardous wastes such as inflammables,composite explosives or highly reactivesubstances are produced by industriesdealing in metals, chemicals, drugs, pharma-ceuticals, dyes, pesticides, rubber goods etc.

The disposal of non-degradable industrialsolid wastes, if not done by a proper andsuitable method, may cause serious threat tothe environment. New innovations have led todifferent uses of waste material. Nowadays,fly ash and slag from the steel industry areutilised by the cement industry. Large

In response to high persistence ofchlorinated organic toxins, a new series of lesspersistent or more bio-degradable productscalled organo-phosphates and carbamateshave been introduced in the market. But thesechemicals are severe nerve toxins and hencemore harmful to humans. As a result, thereare reports of some pesticides related deathsof agricultural field workers. Insects havebecome resistant to these insecticides also. Theinsecticide industry is engaged in developingnew groups of insecticides. But one has tothink, is this the only solution to pest menace?

These days, the pesticide industry hasshifted its attention to herbicides such as

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quantities of toxic wastes are usually destroyedby controlled incineration, whereas smallquantities are burnt along with factorygarbage in open bins. Moreover, solid wastesif not managed effectively, affect thecomponents of the environment.

household discards, there are medical,agricultural, industrial and mining wastes. Theimproper disposal of wastes is one of the majorcauses of environmental degradation.Therefore, the management of wastes is ofutmost importance.

Collection and DisposalDomestic wastes are collected in small bins,which are then transferred to community binsby private or municipal workers. From thesecommunity bins, these are collected andcarried to the disposable site. At the site,garbage is sorted out and separated intobiodegradable and non-biodegradablematerials. Non-biodegradable materials suchas plastic, glass, metal scraps etc. are sent forrecycling. Biodegradable wastes are depositedin land fills and are converted into compost.

The waste if not collected in garbage bins,finds its way into the sewers. Some of it is eatenby cattle. Non-biodegradable wastes likepolythene bag, metal scraps, etc. choke thesewers and cause inconvenience. Polythenebags, if swallowed by cattle can cost their livesalso.

As a normal practice, therefore, alldomestic wastes should be properly collectedand disposed. The poor management causeshealth problems leading to epidemics due tocontamination of ground water. It is speciallyhazardous for those who are in direct contactwith the waste such as rag pickers and workersinvolved in waste disposal, as they are the oneswho handle waste materials mostly withoutprotective device such as gloves or water proofboots and gas masks. What can you do forthem?

14.7 GREEN CHEMISTRY

14.7.1 Introduction

It is well known fact that self-sufficiency in foodhas been achieved in India since late 20th

century by using fertilizers and pesticides andexploring improved methods of farming, goodquality seeds, irrigation etc. But over-exploitation of soil and excessive use offertilizers and pesticides have resulted in thedeterioration of soil, water and air.

Do you know about waste recycling?

••••• Fuel obtained from plastic waste hashigh octane rating. It contains no leadand is known as “green fuel”.

••••• Due to recent developments made inchemical and textile industries, clotheswill be made from recycled plasticwaste. These will be available soon inthe global textile market.

••••• In India, our cities and towns faceendless hours of power cut. We can alsosee piles of rotting garbage here andthere. There is a good news that we canget rid from both these problemssimultaneously. Technology has nowbeen developed to produce electricityfrom the garbage. A pilot plant has beenset up, where after removing ferrousmetals, plastic, glass, paper etc. fromgarbage, it is mixed with water. It is thencultured with bacterial species forproducing methane, commonly knownas biogas. The remaining product isused as manure and biogas is used toproduce electricity.

14.6 STRATEGIES TO CONTROLENVIRONMENTAL POLLUTION

After studying air, water, soil and industrialwaste pollution in this unit, by now you musthave started feeling the need of controllingenvironmental pollution: How can you saveyour immediate environment? Think of thesteps/activities, which you would like toundertake for controlling air, water, soil andindustrial waste pollution in yourneighbourhood. Here, an idea about thestrategies for the management of waste is given.

14.6.1 Waste Management

Solid waste is not the only waste, which yousee in your household garbage box. Besides

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The solution of this problem does not lie instopping the process of development that hasbeen set in; but to discover methods, whichwould help in the reduction of deterioration ofthe environment. Green chemistry is a way ofthinking and is about utilising the existingknowledge and principles of chemistry andother sciences to reduce the adverse impacton environment. Green chemistry is aproduction process that would bring aboutminimum pollution or deterioration to theenvironment. The byproducts generatedduring a process, if not used gainfully, addto the environmental pollution. Suchprocesses are not only environmentalunfriendly but also cost-ineffective. Thewaste generation and its disposal both areeconomically unsound. Utilisation of existingknowledge base for reducing the chemicalhazards along with the developmentalactivities is the foundation of greenchemistry. Have you perceived the idea of greenchemistry ? It is well known that organicsolvents such as benzene, toluene, carbon

tetrachloride etc., are highly toxic. One shouldbe careful while using them.

As you know, a chemical reaction involvesreactants, attacking reagents and the mediumin which the reaction takes place. Extent of anyreaction depends upon physical parameterslike temperature, pressure and use of catalyst.In a chemical reaction, if reactants are fullyconverted into useful environmental friendlyproducts by using an environment friendlymedium then there would be no chemicalpollutants introduced in the environment.

During a synthesis, care must be taken tochoose starting materials that can be convertedinto end products with yield approximatelyupto 100 per cent. This can be achieved byarriving at optimum conditions of synthesis.It may be worthwhile to carry out syntheticreactions in aqueous medium since water hashigh specific heat and low volatility. Water iscost effective, noninflammable and devoid ofany carcinogenic effects.

Nobel goes to Green Chemists

Yves Chauvin, Institut Français du Pétrole, Rueil-Malmaison France, Robert H. GrubbsCalifornia Institute of Technology (Caltech), Pasadena, CA, USA and Richard R. SchrockMassachusetts Institute of Technology (MIT), Cambridge, MA, USA won the 2005 Nobel Prizein chemistry for work that reduces hazardous waste in creating new chemicals. The trio wonthe award for their development of the metathesis method in organic synthesis –a way torearrange groups of atoms within molecules that the Royal Swedish Academy of Scienceslikened to a dance in which couples change partners. The metathesis has tremendouscommercial potential in the pharmaceuticals, biotechnology and food stuffs productionindustries. It is also used in the development of revolutionary environmentally-friendlierpolymers.

This represents a great step forward for ‘green chemistry’, reducing potentially hazardouswaste through smarter production. Metathesis is an example of how important application ofbasic science is for the benefit of man, society and the environment.

Yves Chauvin Robert H. Grubbs Richard R. Schrock

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14.7.2 Green Chemistry in day-to-day Life

(i) Dry Cleaning of ClothesTetra chlroroethene (Cl2C=CCl2) was earlierused as solvent for dry cleaning. Thecompound contaminates the ground water andis also a suspected carcinogen. The processusing this compound is now being replacedby a process, where liquefied carbondioxide,with a suitable detergent is used. Replacementof halogenated solvent by liquid CO2 will resultin less harm to ground water.

These days hydrogen peroxide (H2O2) isused for the purpose of bleaching clothes inthe process of laundary, which gives betterresults and makes use of lesser amount ofwater.

(ii) Bleaching of Paper Chlorine gas was used earlier for bleachingpaper. These days, hydrogen peroxide (H2O2)with suitable catalyst, which promotes thebleaching action of hydrogen peroxide, is used.

(iii) Synthesis of ChemicalsEthanal (CH3CHO) is now commerciallyprepared by one step oxidation of ethene inthe presence of ionic catalyst in aqueousmedium with an yield of 90%.

( )( )

( )

Catalyst2 2 2 Pd(II)/Cu II in water

3

CH CH O

CH CHO 90%

= + →

Think it Over

What is our responsibility as a humanbeing to protect our environment?

Some concepts, if followed by an individual,contribute towards a better quality of ourenvironment and human life. Always set upa compost tin in your garden or any otherplace in your home and use it to producemanure for your plants to reduce the useof fertilizers. Use a cloth bag and avoidasking for plastic carry bags when you buygroceries, vegetables or any other item. Seethat all newspapers, glass, aluminum andother items in your area are recycled. Wemight have to take little trouble to locatesuch dealers. We must realize that we donot have solutions for every problem butwe can concentrate on issues, which we feelstrongly about and can do some thingabout. We should take care to put intopractice whatever we preach. Alwaysremember environment protection beginswith us.

Green chemistry, in a nutshell, is a costeffective approach which involves reduction inmaterial, energy consumption and wastegeneration.

SUMMARY

Environmental chemistry plays a major role in environment. Chemical species presentin the environment are either naturally occurring or generated by human activities.Environmental pollution is the effect of undesirable changes in the surrounding thathave harmful effects on plants, animals and human beings. Pollutants exist in all thethree states of matter. We have discussed only those pollutants, which are due to humanactivities, and can be controlled. Atmospheric pollution is generally studied astropospheric and stratospheric pollution. Troposphere is the lowest region of theatmosphere (~10 km) in which man along with other organisms including plants exist.Whereas stratosphere extends above troposphere up to 50 km above sea level. Ozonelayer is one of the important constituents of stratosphere. Tropospheric pollution isbasically due to various oxides of sulphur, nitrogen, carbon, halogens and also due toparticulate pollutants. The gaseous pollutants come down to the earth in the form ofacid rain. 75% of the solar energy reaching earth is absorbed by the earth surface andrest is radiated back to the atmosphere. These gases mentioned above trap the heatwhich result into global warming. It is important to realise that these very gases arealso responsible for the life on the earth as they trap the requisite amount of solar

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EXERCISES

14.1 Define environmental chemistry.14.2 Explain tropospheric pollution in 100 words.14.3 Carbon monoxide gas is more dangerous than carbon dioxide gas. Why?14.4 List gases which are responsible for greenhouse effect.14.5 Statues and monuments in India are affected by acid rain. How?14.6 What is smog? How is classical smog different from photochemical smogs?14.7 Write down the reactions involved during the formation of photochemical smog.14.8 What are the harmful effects of photochemical smog and how can they be

controlled?14.9 What are the reactions involved for ozone layer depletion in the stratosphere?14.10 What do you mean by ozone hole? What are its consequences?14.11 What are the major causes of water pollution? Explain.14.12 Have you ever observed any water pollution in your area? What measures would

you suggest to control it?14.13 What do you mean by Biochemical Oxygen Demand (BOD)?14.14 Do you observe any soil pollution in your neighbourhood? What efforts will you

make for controlling the soil pollution?14.15 What are pesticides and herbicides? Explain giving examples.14.16 What do you mean by green chemistry? How will it help decrease environmental

pollution?14.17 What would have happened if the greenhouse gases were totally missing in the

earth’s atmosphere? Discuss.14.18 A large number of fish are suddenly found floating dead on a lake. There is no

evidence of toxic dumping but you find an abundance of phytoplankton. Suggesta reason for the fish kill.

14.19 How can domestic waste be used as manure?14.20 For your agricultural field or garden you have developed a compost producing

pit. Discuss the process in the light of bad odour, flies and recycling of wastesfor a good produce.

energy for the sustainance of life. The increase in the greenhouse gases is raising thetemperature of the earth’s atmosphere which, if not checked, may eventually result inmelting of polar ice caps and consequently may submerge the costal land mass. Manyhuman activities are producing chemicals, which are responsible for the depletion ofozone layer in the stratosphere, leading to the formation of ozone hole. Through theozone hole, ultraviolet radiations can penetrate into the earth’s atmosphere causingmutation of genes. Water is the elixir of life but the same water, if polluted by pathogens,organic wastes, toxic heavy metals, pesticides etc., will turn into poison. Therefore, oneshould take care to follow international standards to maintain purity levels of drinkingwater. Industrial wastes and excessive use of pesticides, result into pollution of landmass and water bodies. Judicious use of chemicals required for agricultural practicescan lead to sustainable development. Strategies for controlling environmentalpollution can be: (i) waste management i.e., reduction of the waste and proper disposal,also recycling of materials and energy, (ii) adopting methods in day-to-day life, whichresults in the reduction of environmental pollution. The second method is a new branchof chemistry, which is in its infancy known as green chemistry. It utilizes the existingknowledge and practices so as to bring about reduction in the production of pollutants.