Atmosphere See The atmosphere has, broadly speaking, three categories of constituents—major, minor trace. For pollution-free dry air at ground level, the components may be expressed as per cent by volume, as follows (within parentheses): Major components: Nitrogen (78.09) Oxygen (20.94) Water vapour (0.1-5) Minor components: Argon (9.34 x 107) Carbon dioxide (3.25 x 10%)" Trace components: Neon (1.82 x 10°) Helium (5.24 x 10-4) Methane (2 x 10-*) Krypton (1.14 x 10-4) Nitrous oxide (2.5 x 10°) Hydrogen (5 x 10°) Xenon (8.7 x 10%) Sulphur dioxide (2 x 10°*) Ozone (trace) Ammonia (1 x 10) Carbon monoxide (1.2 x 10-5) Nitrogen dioxide (1 x 10°5) Todine (trace) ‘The parameters of the atmosphere vary considerably with altitude. The density of the atmospher| shows a sharp decrease with increasing altitude. Pressure drops from 1 atmosphere at sea level 3 x 10°” atmosphere at 100 km above sea level, while temperature varies from -92 to 1200 °C. Ti total mass of the atmosphere is approximately 5 x 10'S tonnes, which is roughly 1 millionth of earth's total mass. ‘The atmosphere may be broadly divided into four regions as shown in Table 2.1. It extends to 500 km with temperatures varying from a minimum of ~92 to a maximum of 1200 °C.om ible Major regions of the atmosphere . ins 70% of the mass of the atm imi ¢ troposphere contains I ‘sphere. The upper limit of the troposph Th by kilometre or more, depending on factors such as temperature, nature of tenretrial ‘tc. Air is far from uniformity with respect to density and temperature, Density decreases tially with increasing altitude. In respect of Composition, the troposphere is more or | eset in the absence of air pollution, mainly due to the constant circulation of aamascsales this epion. The water content, however, varies due to the hydrological cycle. The troposphere is also a turbulent region due to the global energy flow arising from imbalances of heating and cooling rates ‘between the equator and the poles. The temperature in the troposphere falls off uniformly with increasing altitude. The air near ground level is heated by radiation from the earth. The cold layer (-56 °C) at the top of the troposphere is called the tropopause, which marks temperature inversion, ie., transition from negative to positive lapse rates (slopes of temperature-altitude curve: Fig. 2.1). The stratosphere is the quiescent layer having a positive lapse rate. The temperature increases with increase in altitude, with a maximum of -2 °C at the upper limit of the stratosphere. Ozone in this region absorbs ultraviolet radiation and raises the temperature causing a positive lapse rate may Vary 100 90 deo 80 onosphere 70 (©},0* NOt e°) Altitude (km) 3 = i rate Aa (O) = Negative bps Troposphere 200 300 (250 “Temperature (K) il ile Fig. 2.1 Major regions of the atmosphere, with temperature profilIt plays an important role in the stratosphere. It acts as a protective shield for life on earth from the injurious effects of the sun’s ultraviolet rays and at the same time, supplies the heat source for Partitioning the atmosphere into a quiescent stratosphere and turbulent troposphere. O, + Av (220 -330 mm) > 0, +O Because of slow mixing in the stratosphere, the residence times of molecules or particles in this) region are quite long. If the pollutants can somehow reach or are injected into the stratosphere, they pose long-term global hazards compared to their impact in the much-denser troposphere. The mesosphere shows negative lapse rate, i.e., temperature falls with increasing altitude. This is due to low levels of ultraviolet-absorbing species, particularly ozone. In the thermosphere immediately above the mesosphere, the temperature rises once again, giving a positive lapse rate (maximum temperature, 1200°C). Here, the atmosphere gases, particularly oxygen and nitric oxide, split into atoms and also undergo ionization after absorption of solar radiation in the far-ultraviolet region.‘The earth receives a very large input of energy daily from the sun and maintains.a steady state siving off the bulk of this energy at the same rate. The solar spectrum incident of the earth’s face has a peak at 483 nm (visible region), indicating the surface temperature of the sun as ximately 6000 K. The earth’s spectrum shows a peak of about 10,000 nm (infrared region), ith the surface temperature of the earth about 290 K (17 °C). In other words, the earth absorbs jation mainly in the visible region but emits radiation at the same rate in the infrared region (2~40 1 ith maximum at 10 1). ‘The solar flux incident on earth’s upper atmosphere is 1340 watts m min”. If all this energy absorbed by the earth, then it would have evaporated long ago. There are various complex anisms by means of which the earth manages to maintain its heat balance within narrow limits thereby retains optimum climatic conditions for supporting life. The earth absorbs about 66% of the solar flux incident on it, ie., 19.5 k cal m? min", while reflects and scatters back into space about 34% (albedo) of the solar flux. Energy transport plays nical role in the earth’s radiation balance. This proceeds through the mechanisms of (a) radiationof energy in the infrared region from the earth; (b) conduction of energy through the interaction 9 atoms or molecules, and (c) convection of energy through massive air circulation. The latter tw, mechanisms are responsible for loss of heat from the earth’s surface through transport to clouds and consequent radiation from the clouds. ‘The average surface temperature of the most of the outgoing infrared radiation (2-40) by wat carbon dioxide (12-16.3 2). The combined effect of water vapour and carbon dioxide leads to th greenhouse effect* which is of grea significance in governing the climate on earth. This will by discussed in the following section. Increasing agricultural and industrial outputs can also upset the earth’s radiation balance }; changing the albedo (fraction of sunlight reflected and scattered back to the armosphere). Deforestatioy and the consequent soil erosion increase the albedo, Furthermore, both agriculture and industr release large quantities of dust and fum into the atmosphere. The effects of these human practice are small compared to the natural forces (wind, sea, spray, volcanoes, etc.) which contribute to, large extent to the particle loading cof the atmosphere. These atmospheric particles have a coolin effect on the earth's surface through increased scattering of the sun's rays. Dark particles (deposite fon soot) can absorb light whereas light particles reflect light. The former helps in the heating of th earth’s atmosphere, while the latter removes heat. The effect of particles on climate can be understoo by a detailed analysis of the sources of these particles and their overall loading in the atmosphe (Sec. 2.9). earth is maintained around 15 °C due to reabsorption g er vapour (4-8 [1), and to a lesser extent by Particles are the important contents of the troposphere. They may vary in the number fro several hundred per cubic centimetre in very pure ajr to more than 10° per cubic centimetre in high! sehfuted ar. Tei size is inthe range of 01-10 B. The patclate mass level ranges from 19 igh Porstean air to 60-2000 jig/m* in the polluted air in urban areas. Hem an gidal-size particles inthe atmosphere are known as aerosols. AerOsOls Of natural origin wi than 0.2 [1 are called Aitken particles. These particles originate from Weenies with ion, Othe ash diameter less eae f natural origin in the atmosphere are bacteria, fog, pollen grains and volcanj, ic particles © Fi . " TRUSA, about 13.4 MT (metric tonnes) of primary particles are emitted per yea, : smaller than 3 1. The chemical nature and size of the particles arg ,,, Ut Of which ae about 5 MT are Satter load in the atmosphere, Particles in the size range 0, re importa than the particulal Be OL] yy a portant 1 effects. : . — importan ponsile for electrical phenomen in he atmosphere, cloud and fo, oc ‘ant role in determining the heat balance of the earth's a1 08 fo import 8 Atmosphertion, Fight reflection | for the formation of ice erystals and water droplets through (c) They 52m¥e oe ein several chemical reactions in the atmosphere: () Neutralig, (d) They are De ) catalytic cffects of small particles of metal oxides o9 gion ry, Jets; (il Xidatig, “*tions On pe,tO8S inProcesses for Formation of inorganic Particulate Metal oxides form a major group of inorganic particles in the atmos os i combustion of fuels. Thus, the particulate iron oxide originates in isla re fom containing coal: 3FeS, + 80, > Fe,0, + 6SO, re Part of the CaCO; in the ash fraction of coal is converted to CaO and discharged through fa stack: CaCO, + heat -» CaO + CO, (4) ‘Automobiles are sources of lead particles in the atmosphere. Combustion of leaded gasoline discharged lead halides through the exhaust system: Pb (C;Hs); + O, + (halogenated scavengers) > PbCl, + PbBr, + PbBrCl + CO, + H,O (5) (The halogenated scavengers are dichloroethane and dibromoethane). In USA, more than 2x 105 tonnes of lead is dumped into the atmosphere every year. In recent years, however, this quantity is decreasing with the use of unleaded gasoline. Aerosol mists arise from sulphuric acid, obtained by oxidation of sulphur dioxide which collects water vapour to form small liquid droplets: 280, + O; + 2H,O > 2H,S0, © In the presence of basic air pollutants such as ammonia or calcium oxide, salts are formed: H,SO, + 2NH, > (NH,),SO, a (droplet) (gas) (droplet) H,SO, + CaO ->CaSO, + H,0 (8) (droplet) (particle) __ (droplet) Figure 2.2 illustrates the components of inorganic particulate matter and their origins. ‘Atmosphere H,0 HBr p SO, NH, HCI 3 > NH; “Materials formed by Particle Elements present from natural sources, particularly terrestrial dust_and sea salt matter and theit origins (Reprinted by Monterey, California 93940 USA from 369, 1979, Willard Grant Press, Statler Fig. 22 Some of the components of inorganic particulate permission of Brooks/Cole Publishing Company, Environment Chemistry, 3rd edn., SE. Manahan, p Office Building, Boston, MassachusettsE 7 —— in the air in United States urban locations rev " «of particulate matter in the 2 tter (105), NHt Caled A pi ao = em Total suspended parce oon Ca (0.002), 22 NOs a fltowing composition Ore organics (68), Sb CNS Qo) Ti (0.04). V (0.05) and G SO; (10.6, rrr .79), Ma (0.10). Ni (0.034), Sn (0.02), TH OOD. YOO) and 25 (0.09), Fe (1.58) organi arcuate Mater ‘cal Processes for Formation OF . Chemical p ‘culate matter originates from a wide variety of oa ©-B- emissions 5, Organic Partie x combustion of fuel, etc. Typical organic patuichlate matter, as objaingy vegetation ant avon extractable fraction from 200 air samples in USA showed an average form my bd na a Sere hale os alkoxyo 2" - Such particles are in the I- size range and are Poteni Crs ode Benzo-a-pyrene Polycyclic (polynuclear) aromatic hydrocarbons (PAH) in organic particulate matter are know to have carcinogenic effect. Among these, benzo (a-) pyrene is well known. PAH compounds commonly occur in urban atmospheres at about the 20 g/m? level. They originate from the pyrolyss of higher paraffins present in fuels and plant material. High molecular weight paraffins are pyrolyzed to yield Cig, which undergoes further pyrolysis: 0) Ss Cin > ——> polycyclic aromatic hydrocarbons Most of the PAH compounds remain adsorbed on soot particles. Soot is formed as a residue on combustion of fuel in power plants and automobiles. It accouns for 50% of the particulate load in urban areas. Chemically, it is highly condensed product polynuclear aromatic hydrocarbons, consisting of several thousand interconnected crystallites ie., graphic platelets each having about 100 condensed aromatic rings. The hydrogen content of so ne and ae Content about 5-10% due to partial surface oxidation. Because of its lar on. beryl oan as a cartier for toxic organics, e.g., benzo (@) pyrene, and, toxic trace m, cadmium, chromium, manganese, nickel, vanadium, etc. Adsorbed organics (c.g., benzo-c-pyrene) ‘Adsorbed toxic metals Be, Ca, Cr, etc.)atmospheric particles enter human bodies through the respiratory tract. Among In gem cles (0.1-1 pt size) reach the lungs and are retained there, causing health hazards. eral ce, small particles on: removal of particulate matter from gas streams is an important strategy for air pollution control, mp will be discussed in & subsequent section (Ch. 10). whic Ions and Radicals ‘re ions dominate above the stratosphere in the region known as the ionosphere. Both positive qs (0; 0", NO", ete.) and electrons exist at significant levels in the ionosphere. They persist for faa periods without recombining to give neutral species due to rarefied conditions in the upper atmosphere Ultravi night in the al the original neutral the species exist in rel magnetic field, giving ri ionizing particles encircling the earth. Besides ions, free radicals are ge let radiation is primarily responsible for the production of ions in the ionosphere. At sence of ultraviolet light, the positive ions slowly recombine with free electrons to form 1 species. This process occurs rapidly in the lower regions of the ionosphere where Jatively high concentrations. The ions are strongly influenced by the earth's ise to the phenomenon of Van Allen belts. The latter consist of two belts of mnerated by electromagnetic radiation. They consist of atoms or roop of atoms with impaired electron, having half-lives of several minutes or more in the rarefied tpper atmosphere. They are highly reactive. They take part in chain reactions in which one of the products of each reaction isa free radical. Finally, one of the free radicals in a chain is destroyed and the chain is terminated: RH + 0 +0, — ROO’ + HO" (10) where RH = aliphatic hydrocarbon CH, - CHO + Av > CH; + HCO” al (12) CH, +CH, > CH, ‘adicals play an important role in photochemical smog formation. oblems due to the very low The study of chemical reactions in the atmosphere poses serious p mely Gmeeatations involved, which makes the detection and analysis of reaction products extrei cult. High altitude reactions at very low pressure can not be simulated in the laboratory. Chemicals in the atmosphere participate in photochemical reactions by absorption of solar ion. Such reactions occur even in the absence of chemical catalysts at much lower temperaturrs. photochemical reactions play a Key role in governing the ultimate fate of a chemical in the “mosphere that fom typical chemical and photochemical reactions will now be illustrated. It should be noted compet mosphere is tremendously dynamic system with wide “fluctuations of the parameters, viz. abet temperature, humidity and intensity of sunlight. Obviously, different processes will be Whe varying atmospheric conditions. | ©, plays an important role in the troposphere, Oy plays @ key role in the “"Wosphere,cl-0'+0 cl-0+NO, se sourees and sinks for Cl are discussed. sources |, Chlorofluo pert in tHe troposph i ation at ‘about 200 nm generating Cr fi ‘on of upto 100,000 molecules of Oy ‘he use of CPCS was being phased out by Conference 1990: 2. Volcanoes inject Cl, By reaction with CH,, CI' is trapped gn (200 am) ‘Troposphere Fig. 26 Ch > cr+0, > C1-0-NO < Chlorine nitrate (60) (61) oO o rocarbons (CFC) used as refrigerants and aerosol spray can propellants—they are ere but slowly diffuse into the stratosphere where they are subjected to ultraviolet ee radical. The latter immediately reacts with O,. crcl, > CPCI, + cr cr +O, 5 C10" + 0, co’ +0 > Cr +0, ina cyclic reaction, each CIO" can initiate a series of without being destroyed itself in the process. the end of 20th century (Montreal Protocol 1987/ see Sec. 2.8 Ozone Hole). ‘and HC! directly into the stratosphere. Cl, HCI reacts with OH" to give CI’. chemical reactions which lead to on exposure to UV radiation 300-400 nm) forms CI while C1+0, > ClO’ + 0, (62) clo" +0 = CI +0, (63) cr+CH, > CH; + HCI (64) Clo" + NO, > CIONO, Jes ~ (65) as HCI which is rained out in the troposphere. 0; o. cH are cr Oe Fo? Se crcl, + cr oe me HC, r No; 300 - 400 am ‘aoa & H,0 Stratosphere Hel cr Barth Jorine reactions in the stratosphereThe reaction of CIO" with NO, to form a stable product chlorine nitrate is significant sing. reduces the catalytic cycles of Chand NO, for Oy destruction thereby lowering the overaly «| depletion rates. Organic Compounds organic compound chemical and phote nediaten 2 e atmosphere are susceptible 10 oxida al reactions. AS a result, many nox, which belong to the category «| ning the ochemit Hydrocarbons and other re produced, through a series of steps of secondary pollutant products and intern photochemical smog (See, 10.1.3): . 4 HC + HO" % CH, + HOT > HAC + H,0 o, HC + 0, + M (Third body) —> H,COO" +M : aa Organic compounds in the atmosphere readily enter into reactions with Oz, NOs, and fre radicals such as HOO", HO", etc, Hot + CH,CH = CH, — CH, ~ CH’ CH,OH oy ions as well as several chemical reaction (10, CH, + Op (propylene) are generated from photochemical react Free radical CH,CHO + hv > H,C + HCO" C,H,00" —» CH,COCH, + HO" a, ) Metal oxides and charcoal in particulate matter catalyse the oxidation of hydrocarbons. he atmosphere play an important role in photochemical smog Organic compounds in tl formation (Sec. 10.1.3). Carbon dioxide (present level 356 ppm), although a relatively insignificant non-pollutar) species in the atmosphere, is of serious environmental concern. It has the potential to rival nucles ‘wars in terms of massive irreversible damage to the environment, ‘Among the constituents of the atmosphere, only carbon dioxi absorb infrared radiation (14000-25000 nm) and effectively block a | emitted radiation (Fig. 2.7). The radiation thus absorbed by CO, and H,O vapour is part to the earth's surface, The net result is that the earth's surface gets heated up by 4 called the greenhouse effect (Fig. 2.8). with increased combustion of fossil fuels have The current global trend in deforestation along cumulative effect on the net increase in carbon dioxide content. Forests are the areas where ee di i deal of photosynthesis occurs. Moreover, they maintain vast reservoirs of fixed but readily 0» carbon in the form of wood and humus. The overall result is that they serve to maintain 4 the atmospheric CO, level. The combustion of fossil fuel has little effect on the oxygen stock of the atmosphere, which 4 relatively large, but it has considerable impact on the carbon dioxide content which is only 356 me) the rate of increase of carbon dioxide is only about 50% of the © ut present. However, nagnitude. The removal mechanisms, i., sinks of carbon dioxide are shown in Fig. 29. large fraction of r sy re-emitiIR radiation emitted from earth's surface absorption spectrum Intensity CO; absorption spectrum ‘4900300012000 16000 20000 24000 Wavelength (nm) Fig. 2.7 ompion of terrestrial radia by water and carbon donde Unabsorbed radiation in region of atmos: ‘pheric window (8000 to 13000 nm.) Outer space \~ fo b ) no $.c0, i Sa CO, Nae Earths surface (emitter of IR radiation) Fig. 2.8 The greenhouse effect nag mall® sink isthe ocean which contains the bulk of dissolved carbon dioxide as bicarbonate, known ee sink is the biomass, viz. living green plants, in which the photosynthesis rate is accelerate with increase in the carbon dioxide level.Plant's (Biomass) Organic carbon coy Fig. 2.9 Sources and sinks of carbon dioxide The temperature effects of carbon dioxide and water vapour combine together to have a long range impact on the global climate, As the surface temperature increases with increase in level of carbon dioxide, the evaporation of surface water increases, thereby raising the temperature further. I has been estimated that this combined effect will bring about a 3 °C rise in surface temperature for a doubling of the carbon dioxide concentration, which may occur around 2050 A.D. It may be noted that a slight increase in surface temperature, say 1°C, can adversely affect the world food production. Thus, the wheat growing zones in the northern latitude will be shifted from the USSR and Canada to the poles, i.e., from fertile to poor soils (in the north pole). The biological productivity of the ocean would also decrease due to warming of the surface layer, which in tum reduces the transport of nutrients from deeper layers to the surface by vertical circulation. Another effect is the rise in sea levels, Since oceans act as reservoirs of heat, it could result in tise of sea levels by as much as 2 metres due to expansion of sea water at increased temperatures, partial melting of glaciers, icecap of Greenland and also polar icecaps. This rise of sea levels would threaten coastal countries: some 60 odd island nations who face deep inroads by the sea, like the Maldives, Bangladesh may be totally submerged. In India, coastal cities such as Chennai and Got may meet similar fates. As mentioned before, rising temperatures could alter climate radically. Some of the more fertile belts of north America and the mediterranean could tum arid. In India, some climate models predic! a drop in wheat production in the fertile northern belt. More violent cyclones and floods are expected on the eastern coast. Thus carbon dioxide, which constitutes a fraction of the atmospheric gases, 0.03 per cent the total, plays an important role in changing the global climate. Without carbon dioxide the earth would be as cold as the moon. By trapping the heat radiating from the earth's surface, carbon dioxide regulates global temperature to life-sustaining 15°C. But if its quantity increases too much, the eat) may share the fate of its neighbouring planet, Venus with surface temperature of 450°C. Other Greenhouse Gases Carbon dioxide is not the only culprit contributing to greenhouse effect and global warming. ! is the major greenhouse gas but there are other greenhouse gases—methane, chlorofluorocarbon nitrous oxide and water vapour. The relative contribution of the radiatively active gases are shown i" Fig. 2.10.b figure shows that the main influence is by CO; but the contributions of other greenhouse The i ji - «petal CH, cannot be ignored. 360 ion hectares of rice fields and 1.2 billion cattle emit a Hy Fig. 2.10 Relative contributions of radiatively-active gases to temperature rise The following table shows that the concentration of these radiatively active gases is increasing significantly each year. ‘The concentration of CO, has increased from 283 ppm in 1880 (Pre- industrial revolution period) to 356 ppm at present. However, it is difficult to predict the concentration levels of CO, CH,, N;O for the next 50 or 100 years due to uncertainties in calculations based on the models used. Most models describe a decrease of the icecap on Antarctica but in some studies the opposite effect is postulated: the icecap grows as a result of increased rainfall on Antarctica. Table 2.2 Concentration and increase of radiatively-active (greenhouse) gases e to the developed countries in respect of |t is imteresting to find out India’s position relativ ‘A, 1000; CIS (formerly USSR) 690; Brazil ae £as emissions (in million tonnes of carbon): US. ae 380; India 230; Japan 220. inco, fennel ‘flux is an important parameter in balancing CO, in the atmosphere. Increase oa in the atmosphere will induce enhanced growth of vegetation with increased rate of ON, Pang I Part of biospheric fixation may due to global eutrophication. The increased availability Yeetation C compounds, due to pollution, can act as fertilisers and lead to faster growth rates of | Coastal waters have also fertilization effect. Higher concentrations of nitrates, phosphates “4 sulphat "hose mle, can lead to enhanced growth of micro-organisms leading to larger uptake of CO; by 610,of the fluxes per year is given; ? (bi tonnes of CO2 Cillion vos x 10° tonnes of CO, Sources and Sinks of co,—A Summary : iew "There are uncertainties in the fluxes of os An over¥ i i s 0x I (i) Emissions by use of fossil fuel, 2 . Gi) Emissions by deforestation and changes in land use, ii i ‘ans, 5.5 X 10° tonnes CO2 Ee CoE 3x 10° tonnes COz (iv) Uptake by CO, fertilization. ‘This is illustrated in the following figure. ‘Atmosphere 2700 Deforestation Fuel 20 37-74 . 10° tonnes CO,) oad [SS important fluxes of CO, (in billion tonnes i ‘The balance sheet shows a net increase of CO, in the atmosphere of 11 x 10° (billion) tonnes per year. This can be cut down to 50 per cent if we can stop deforestation. Tt may be noted that the CO, concentration in the atmosphere is the resultant of exchang: fluxes between very large reservoirs viz., the atmosphere, biosphere and the oceans. The atmospher vegetation plus soil about 6600 billion tonnes ani contains 2700 billion tonnes of CO,; the biosphere, the oceans including very deep layers about 1,36,000 billion tonnes of CO>. Fig. 2.11 Overview of the most iAlthough scientists agree with the theory of greenhouse warming, debate contisues as to etter the increase in these greenhouse gases have actually begun to warm the global climate. They ope to settle the question with measurements of the speéd of sound by sending pulses of underwater, “und around the world through all five of its ocean basins. ‘The experiment is directed by Walter Munch of the Scripps Institute of Oceanography, La Jolle, slfomia, USA and conducted by an international team of eight nations. It is based on the principle the speed of sound in water (1.609 km sec!) depends on the temperature of water; the warmer water, the faster sound propagates through it. An the experiment, a small ship is anchored near Heard Island, a remote Australian Island in the uthem Indian Ocean, An underwater loudspeaker is lowered to a depth of 250 metres and for nine Lays the speaker broadcasts signals of low notes at high volumes. Heard Island was selected because t pemnits extension of direct paths through each of world’s five oceans: sound conducted along ese paths should be audible to acoustic sensors placed thousands of kilometres away. Underwater ictophones are installed in the Antarctic, near Bermuda and San Francisco and along the coasts of South Africa, India, Australia, New Zealand and Canada. The distances between Heard Island and the “aul microphones are all known precisely, so that careful measurements of the time an acoustic 'ndl takes to reach a sensor will permit calculations of the average speed of sound over the course. spec tistions of global warming are correct and the temperature of the ocean is rising as knw om Will travel significantly faster each year over the 17,920 km distance from Heard lod pout Francisco. According to Munch, travel time for sound covering this route should be Y a much as 0.25 seconds each year.More About Greenhouse Gases as. It is responsible for about half oj Carbon dioxide is commonly known as the greenhouse g¢ (0% of the greenhouse effect. On | the atmospheric heat retained by trace gases and also for 5 molecule for molecule basis, methane, CH, is 20-30 times more effective than CO, in trapping heat The potential of a greenhouse gas to cause greenhouse warming is expressed by “Global Warmin Potential’ (GWP), originally defined by the United Nations Intergovernmental Panel on Climatk Change, which is a function of both the infrared sorption characteristics and the lifetime of the ges ‘The greenhouse gases can be arranged in GWP sequence as follows: 10000x 150x 25x CFC’ > NO > CH > CO, In other words, CFC is 38 million times stronger, than CO, in terms of GWP. Since the Industrial Revolutior environment through agricultural and industrial practices. Before this, few gases into the atmosphere. N,O 3800 times and CH, 25 times stronge' mn more than 200 years ago we started altering our climate ani human activities released ve"Now, whenever We watch TV, use air-conditioner, turn on light, use hair di in a car, a video game, Wash or dry clothes, use a dish-washer or a micro-oven, fly on an aeroplane or Pte, we help t© send greenhouse gases into air. To perform many of these functions we need clectricity which comes from power plants. Most power plants burn coal and oil to generate tleetrcity and in the process produce greenhouse gases. The trash that we send to landfills produces 4 greenhouse gas, methane. Methane is also produced by animals we raise for dairy and meat ‘and when we mine coal from coal-pits. And when the factories make the things we buy and use everyday, they too are sending greenhouse gases into the air. According to the latest Report of the United Nations Inter-governmental Panel of Climate Change (2001), the present levels of carbon dioxide have not been exceeded during the last 4,20,000 years and probably not during the last 20 million years. All records, maintained since the mid 19th century, for average global temperatures, have been broken during the last 20 years. Six of the hottest years occurred in the 1990s and four in the 1980s. The effects are already apparent throughout the world (as narrated above) with reports of disruption of normal weather patterns with hurricane winds, catastrophic flooding, and drought. By 2025, over 5 billion people all over the world will face severe water crisis while northern Europe will suffer increased flooding. Diseases such as malaria and cholera will rise dramatically while urban areas will suffer the most. Warmer temperatures allow mosquitoes (which spread malaria and dengue fever) to extend their range and increase both their biting rate and ability to infect humans. Spring now arrives earlier in many parts of the world. Evidence comes from earlier thaw dates for rivers and lakes, earlier dates for plant blooming and leafing and earlier animal egg laying, ae and migration. An earlier spring may disrupt animal migrations and alter competitive hi her a species. In the event of warmer temperatures, plants and animals tend to move to litudes and elevations. fate playWhen chlorofluorocarbons (CFC) were first introduced ie., some 75 years ago), they were hailed as miracle chemicals because of their non-toxic, non-inflammable and stable nature. ‘They were used as coolants in refrigerators and air-conditioners, in blowing plastic foams and in spray cans and in cleaning computer circuits. But during the last decade, they were found to be responsible for ozone depletion in the stratosphere. ; In September 1980, scientists reported a large hole in the ozone layer over Antarctica where ozone level dropped by 30 per cent. CFC was the prime suspect for causing ozone depletion. It was established that one molecule of CFC is capable of destroying one lakh O; molecules in the stratosphere. Subsequently, a similar hole was discovered over the thickly-populated northern hemisphere. This stirred the citizens of north Europe and USA, the potential victims of skin cancer, into action. A study by NASA scientists (National Aeronautics and Space Administration, USA) revealed that the amount of ozone over the northern hemisphere decreased by 3 per cent between 1969 and 1986. Each 1 per cent reduction in O; may cause as much as 6 per cent increase in skin cancer cases annually from exposure to UV radiation. The overall reduction in the O3 layer is now estimated to be about 8 per cent.i treal and sign, nce in Montr gned py 1987 at @ ones and a reduction of upto 50, me 4 ay agreement mae IO Ds se of “s century before they finally breakgy® An internation nol) called for @ sist as (OMB as ok, A recent study by the Environme, ‘countries hh ces Because CFCS struction in cape Jd be necessary just 10 preven, by the end of 2 enough t0 hold Os reduction nies producing CFCs e these efforts may not De A pat an 85 riher. The companies P! ate hy s : ; Protection Agency cone CFCs. oe i CEC levels in the atmospl ical substitutes He been found to disappear at a faster raye : ion of chem! p : seeking me Poy protocol, the oon ed that they had found that the ozone hoje Since sts ference the scientist 1990 at London Con! exc. 9 than ha en 198 Tad of 50 per cent a per reseed 10 percent ban of CRCSBY 2D ANY’ ay 1 ondon amendment ty Fee, ha TOyeartmeag for he eveORNE COUTTS 10, 1992. Feel protocol wae ratified in May 1992 and came 7 So aratogere ozone experiment yi oA team of 100 scientists is engaged Daag they used 39 balloons with pay i |. During winter of 7 Saree es a0 cent pes. Their findings revealed that ozone layer was reduced by 1529 pe See eet te in the atmosphere in active form. The volcanic eruptions cet. Further, cine was fund inthe atmosphere in acts emt. The Woh Me. Pinatubo in the Philippines in 1991 are responsible for mu More About Ozone Hole {B. Lacoste—“Our Planet”, UNEP Magazine, Vol. 4, NO. 4, 4-7 (1992).] As mentioned the major culprit in ozone depletion consists of CFC compounds, commonly known as “freons”, extreme chemical stability and non-toxicity of CFCs enable them to persist for years in the r and to enter the stratosphere. In the stratosphere, CFCs are subjected to Photochemical dissociatice| by intense UV radiation, O, % cs: < clo" 2 ocr (regenerated) The net result is regeneration of Cl radi Tadical which . one Cl atomvradical can destroy ch sustains the chaii i i, years, one lakh Os molecules, CRC, ie ies he vee The Antarctic ozone hole ea ele depleted ozone (upto 50%) over te one Antarctic’s late oe i ; normal effect of NO, in limiting Cleatom-qqr eo The reasons eahes early spring of severe C1O0-+ NO, Sgn Sd destruction pty this occurs are related to Hf But these NO, gases in Antarciog oO °F ozone by combining with C10: 0te, chlo ‘ing in polar stratosphe » Chlorine speci iil » reactions in species can be the cloud ice, followed ion t0 yield ozone. Pounds Photodissociati re CIO, NO, + Hg ving: | “HCI byThe destruction of O, by Cl involves an intermediate ClO*, which should be observed if Cl is the cause of Os depletion. Satellite measurements have confirmed the presence of CIO (radical) in both the Arctic and Antarctic atmospheres during periods of severe O, depletion [J.W. Waters, L. Froidevaux, W.G. Read et al.—Nature, 362: 597-602 1993] CFC substitutes—The frequently-used CFCs are CFC-11 (CFCI;) and CFC-12 (CF, Cl,). As a safeguard against ozone depletion, the recommended CFC substitutes are hydrohaloalkanes, compounds containing at least one H-atom—HCFCs (hydrochloroflurocarbons) or HFCs (hydroflurorcarbons). Typical such compounds are HCFC-22 (CHCIF,), HCFC-142 (CH,CCIF,); HFC-134a (CH, FCF) and HFC-152a (CH;CHF,). Each of such molecules has an H—C bond, susceptible to attack by HO" in the troposphere thereby eliminating the compound with its potential to produce O;—depleting Cl atom before it reaches the stratosphere. All these substitutes have low O, depletion potential, short tropospheric lifetime so that the compound is destroyed before migrating to the stratosphere. Current Status Report | The hole in the ozone layer is now three times larger than USA—the largest it has ever been. An ‘ozone hole layer larger than 11 million square miles has been detected. Atmospheric variations from year to year combine with man-made gases to determine the hole’s size. Further circular winds, known as vortices, trap air, giving chemicals the chance to react with ozone. Chlorine compounds, used in refrigerants, aerosol sprays, solvents, foam-blowing agents and bromine compounds used in fire-fighting etc. cause most ozone depletion. The temperature over , Antarctica also contributes significantly to each year’s hole. | For most of year, the stratosphere over Antarctica has fairly high concentration of ozone. The } ozone formed over the tropics level along with CFC to polar regions via atmospheric motion. This ; traps the ozone over the south pole for several months except winter. It is within this vortex the Ozone loss was first detected in 1980 (about 30% loss was reported). The major damage due to ozone hole occurs during winter when tiny ice particles are formed in polar stratosphere. These Particles act as catalyst to enhance, directly or indireetly, the conversion of chlorine into its ozone destroying form, chlorine monoxide, ClO" (radical). The mechanism of ozone depletion is shown in the preceding sub-section. The reactions are particularly intense within stratosphere clouds over Antarctica in the winter { O¥eT southern hemisphere, Reactions which occur on the surfaces of ice particles within the clouds / Telease chlorine and bromine from CFC and halogens in active form that accumulate through winter (May-August). When the sun rises in the spring, the clouds break up to release active chlorine and j mine which rapidly destroy ozone. Thus ozone hole appears during Antarctica spring. | (ia -‘The Asian Brown Cloud was first identified in 1980 by US pilots working at the Diego Gareig Air Force base in the Indian Ocean and subsequently confirmed by satellites and research ships, h 1995, the United Nations commissioned “Indian Ocean Experiment” ($40 million research Proje, Scripps Institution of Oceanography, San Diego, USA—Project Co-ordinator) networking research Tesources over several countries, Paul Crutzen (1995 Nobel Laureate/work on Ozone Hol that 2 million people in India were dying each year from tespiratory diseases caused by According to the UN Report, the brown haze hovered over south Asia spreading from Sri Lanka and was 3 km thick. It was a cocktail of fly ash, sulphates, nitrates, black carbon, acids, aerosols, soot and other pollutants spread over an area of 10 million square kilometers or about the size of USA. This “dynamic soup of pollutants’? is the Product of forest fires, burning of agricultural ‘wastes and fossil fuels, vehicular emissions and even from chullahs using wood, coal or cow dung le) reported air pollution Afghanistan 0 Brown Cloud in Malayasia —o Le ee ee and surrounding towns, a noxious haze-brown cloud thickened '0 Was around $00 mene Lol, 2005. The Government declared a State of emergency as visibilit) ‘ancelled and people urged to stay indoors “Scripps Institution of Oceanography San Piezo. USA-Project Co-ordinay ordinator‘The composition of the atmosphere and atmospheric structure are described in Ch. 2. Airis never found clean in nature, due to natural and man-made pollution. Gases such as CO, SO, and HS are continually released into the atmosphere through natural activities, e.g., volcanic activity, vegetation decay and forest fires. Besides, tiny particles of solids or liquids are distributed throughout the airy winds, volcanic explosions and other similar natural disturbances. In addition to these ‘natunl pollutants’, there are man-made pollutants—gases, mists and particulates, aerosols—resulting from the chemical and biological processes used by man. The latter are present in relatively hig concentrations compared to the background values in air. These pollutants hardly exist beyond 200) feet above ground level. Air pollutants are present in the atmosphere in concentrations that disturb te dynamic equilibrium in the atmosphere and thereby affect man and his environment. Primary Pollutants—Sources There are five primary pollutants which to; i joel # a pol ich together contribute more than 90% of gl A. Carbon monoxide, CO B. Nitrogen oxides, NO, C. Hydrocarbons, HC D. Sulphur oxides, SO, E. Particulates Each of these pri . . ted? this section with referee? Pollutants will be discussed in detail. Some general features a " erm: can be much more dangerous nome does not give the correct picture since # nor a dangerous among the pri ajor pollutant. Thus, particulate pollutants "ye < compared 10 CO = | Primary polh ., » partic Pt splat450 Environmental Chemistry 10.1.3 Hydrocarbons and Photochemical Smog Natural sources, particularly trees, emit large quantities of Dee in the atmosphere, is the major naturally ‘occurring hydrocarbon emitted into the atmosp! ere. I iss Produced an conse quantities by bacteria in the ‘anaerobic decomposition of organic matter in water, sediments ang a 2(CH,0) PCO, + CHa " Domesticated animals contribute about 85 million tonnes of CH, to the atmosphere each year a has a mean residence time of about 3 to 7 years in the atmosphere. / i It has been estimated that anthropogenic sources (human activities) contribute about 15% of te hydrocarbons ‘emitted to the atmosphere each year. ‘Automobiles are the major source in this respea ‘An approximate break-up of global hydrocarbon emissions (about 570 x 10° tonnes per year) is givy below: petroleum 55%; coal evaporation 11.3%. ; . Hydrocarbons from human activities are generally found in areas of high population deny where the maximum damage to human beings and plants can occur. In USA, the Los Angeles bain has been extensively investigated for hydrocarbon pollutants since it has heavy vehicular traffic, Furthermore, its topography and climate contribute to a high load of ambient hydrocarbons. About 2) different hydrocarbons were identified and analysed. Among them, mention may be made of: ethane fand ethylene (102 ppb total), acetylene and propane (76 ppb total), n-butane (46 ppb), isopentane (35 ppb), toluene (30 ppb), n-pentane (21 ppb), m-xylene (12 ppb) and isobutane (12 ppb). Tr concentrations of these hydrocarbons varied with traffic density as function of the hour of day (se under Photochemical Smog in this section). Hydrocarbons are removed from the atmosphere by several chemical and photochemical reaction. They are thermodynamically unstable towards oxidation and tend to be oxidised through a series steps. The end products are CO, and solid organic particulate matter that settle from the Atmospher or water-soluble products, ¢.g., acids and aldehydes, which are washed by rain. 1 3.3%: wood 2.2%; incinerators and refuse burning 28.3%; solvey Photochemical Smog Majority of the harmful effects of hydrocarbon pollution are not due to the hydrocat themselves but the products of photochemical reactions in which they are involved. Hy cel not react readily with sunlight, but they are reactive towards other substances pros photochemically. An important characteristic of atmosphere which is loaded with Targe quant automobile exhausts, trapped by an inversion layer (stagnant air masses) and at the SL ve exposed to intense sunlight, is the formation of photochemical oxidants in the atmosphere: TY fy rise to the phenomenon of photochemical smog which is observed in localities like Los aneee Denver, USA. It may be mentioned that ‘smog’ originally means an odd combination of sme fog prevalent in London. This is, however, chemically reducing with high levels of SOz (82 ©, i $0,) and is called reducing smog, whereas photochemical smog is an oxidising S08 havin’ i? concentration of oxidants. Photochemical. smog is characterised by brown, hazy MUN i an the eyes and lungs, and also leads to the cracking of rubber and extensive fe.pie mechanism of smog-forming reactions is illustrated in the flow charts (Fig. 10.6 ™ me Reactive hydrocarbon BF le +02 RCH} ron NO, + HO" \ no _ —— HO} Ko RCHO (A) (Stable aldehyde) (B) Route to PAN formation RCHO aera Rez? radical Peroxyacyl nitrate (PAN) Fig. 10.6(A) Smog-formation reactions (B) PAN formation reactions (0) Reactive hydrocarbons (those with C = C groups) from auto-exhaust interact with O, to form 7 ape radical RCH}. Fh peg aPidly reacts with O, to form another free radical RCH,O}- in) net2O> feats with NO to produce NO, and the free radical RCH,” ane Ee radical next interacts with O, to yield a stable aldehyde, RCHO, and hydroperoxyl Hos t% wee Teacts with another molecule of NO to give NO, and HO’. fen ee, reactive and rapidly reacts with a stable hydrocarbon RCH, to yield H,O and BW achain 1¢ hydrocarbon-free radical RCH3, thereby completing cycle. This goes on and on RcHo.” faction. One complete cycle yields two molecules of NO;, one molecule of aldehyde tuiig.¢ 204 regenerates the free radical RCH; to start all over again. Very soon there is a rapid “P of smog products.by interaction with the HO" Tadical k » (oii) The aldehyde RCHO may INH, “peroxyacyl radical RCOO2 (by reaction ‘ys, Formation of an cyl ical ROT aon with NO3). PAN is one of the vit 0) finally peroxyacyl nitrate, PAN (OY Pty ivitants found 18 SM paractristc variation of the parameters (smog in in Photochemical sg on level is maximum daring early moming tafe yp hon pee ee the remaining daylight hours as it is eerie mae iE formaton ee decreases dur an ion has a peak vi and the i i yncentration oe ‘ len fi described ea there is a rise in the concentration of oxi dans f°, PAN, which are active oxidising agents and contain the INiAUAE “Herlents of smog Sk concentration profile of smog-forming chemicals in Los Angeles air in USA is shown in fig 17 Hydrocarbons Concentration (ppb) Ae inna 6 Time a.m.a.m.noon p.m. p.m. Fig. 10.7 Concentration profiles of smog-forming chemical in Los Angeles air (Source: J.A. Kerr, .G. Calvert and K.L. Demerjian, Chem, B., 8(1971): p. 253.) Control of Hydrocarbons and Photochemical Pollutants ___O3and PAN are secondary pollutants, so their control ultimately depends on the control of tet Primary precursors, hydrocarbons and nitrogen oxides. The control of NO, has been earlier and that of HC in connection with the control of auto-exhaust emissions.10.1.5 Acid Rain It has been mentioned in the preceding section that much of the NO, and SO, entry {mosphere are converted into HNO; and H,SO, respectively. The detailed Photochemical rage the atmosphere are summarized: NO + 0; > NO, + 0, NO, + 0 > NO; + 0, NO, + NO; N,O, N,0; + H,0 — 2HNO, HNO; is removed as a Precipitate or as particulate nitrates after reaction with bases (wi, particulate lime). 1 (HC, NO,) SO, + 72 +H,O See H,SO, (5) The presence of hydrocarbons and NO, step: droplets, ions such as Mn(ID, Fe(II), Ni(I}) and are also known to be strongly involved in catalysing the oxidation of SO,. HINO, and HSO, combine with HCl from HCl emission (both by natural and anthropogett sources) to generate acidic precipitation which is widely known se acid rain, Acid rain is 00¥* major pollution problem in some areas. a ‘Acid rain causes extensive damage to buildi up the oxidation rate of the reaction, In watt Cu(II) catalyse the oxidation reaction, Soot particles ee weakened mechanically as the soluble sulph® by rainwater. are Ieached ou Cc ‘ACO; + H,SO, — Caso, Limestone ) 4 + CO, + H,0 os= Greece and Italy, invaluable stone staty faces the same fat have been : uti is : s © at present NY dissolved by acid rain ( Fig. 10.8 Acid precipitation causes severe damage in some areas. Priceless stone statues have been partially dissolved by “acid rain” in Greece and laly, (Reprinted by permission of Brooks/ Cole Publishing Company, Monterey, California 93940, USA from Environmental Chemistry 3rd edn. S.E. Manahan, p. 326, 1979, Willard Grant Press, Statler Office Building, Boston. Massachusetts) : : In 1958, rain in Europe showed a pH of 5.0, but by 1962 it was 4.5 in the Netherlands. Sweden experienced rainfall at pH 4.5 in 1966. The acid rain damaged leaves of trees and plants and retarded the growth of Swedish forests. It may be noted that these forests are important natural resources for production of wood pulp, paper and board. In 1979, it was estimated that 20,000 lakes of Sweden were suffering loss of flora and fauna—the fish mortality was increasing. The pollution sources were emission from UK, the Ruhr and Germany. The sulphur emission rate for Europe was up to 70 metric tonnes per year. H,SO, and particles of Cd and Pb are deposited on the winter snows and when these melt, the pollutants enter the rivers and lakes. This occurs at a time when fish spawning and hatching occur thereby destroying the fish eggs. Itis intriguing that while 33-Nation UN Conference on acid rain was in session at Stockholm (July, 1982), the venue received heavy downpour of acid rain for the entire week. The conference was designed to focus world attention on acid rain, the most potent ecological threat to Scandinavia ‘nd Canada, for which UK and USA are responsible. The acid rain that fell during the conference was depositing Sulphur at the rate of 3.5 ani every year (safe level is 0.5 gm? per year). An estimated 25% of this rain came from UK eta sted on Sweden in the year 40,000 tonnes of Sulphur in smoke from heavy industry carried by Prevailing winds across the North Sea. : Elsewhere Sweden's 85,000 lakes were slowly being % damaged and 4000 lakes were completely dead. ' a a Canada, trees and Takes are also being killed by acid rain, 60% of which originates from Killed by the deluge—plant and fish life Typical analytical data of acid rain is shown in Table 10.3.Table 10.3 Analysis of typical acid rain sample (pH = 4.25) Cation Concentration Anion Concentrat molell x 10° Mole x 196 Ht 56 NH 10 51 soy 2 2 NO; 20 6 cr R | Mg? 3 Total = 83 | « 2 ! Total = The actual values, however, are subjected to variation depending on the time and location gf collection of the acid-rainwater sample. The trend, however, remains the same—H,SO, ii contributor to acid precipitation, HNO, ranks second and HCI the third in this respect. Acid precipitation shows a correlation with the prior movement of the airmass Over major Sources of anthropogenic sulphur and nitrogen oxide emissions. This has been demonstrated « southem Norway and Sweden, which receive a heavy load of air pollution from densely- popu, industrial areas of Europe, including UK. 8 the major 10.1.6 Particulates areas the particulate mass level may range that the total particulate matter burden 0! ze of the particles, Sources of, Particulates There are numerous natural processes injectin 2 ii ee Scene eae anic eruptions, blowing of dust and soil 5) Sana raa icin ati the seas and oceans, etc, The contributions ‘ ston pean atom Power plants, smelters and minin tions, and smoke incomplete combustion processes, 8 operations, sources a eee tua sae Particulate pollution indicates that fuel combustions from sion fires, structural fires, coal refuse tarneet iMaUstial processes, and miscellaneous sources ( struct iires, coal re 'use burning and agricultural bumin, ) share almost equally (0n¢" cach) the total particulate emission (200-45 sun pia z i eee tonnes per . In developed countries - USA, the annual particulate emission Per year). In fie particles (less than 3p), 1s about 20 x 10¢ tonnes, including 5 x 10° tonnes ® id particles by| sects on Humans ‘Airborne asbestos and toxic metals, e.g., Be, have caused much concern as they : : wer ona ry are all ic. Asbestos workers in construction jobs for high-rise office building suffer from lung disorders. Asbestos is a fibrous silicate mineral which may persist for long periods of time in the eavironment. The fine particles (less than 31) are the worst causes of lung damage due to their ability to penetrate into the deep air passages. Larger particles (greater than 31) are trapped in the nose and tiroat from which they are easily eliminated, but finer particles can stay intact for years in the imermost regions of the lungs which have no effective mechanism for particle removal. The lodged particles in the Iungs can cause severe breathing trouble by physical blockage and iniation of the lung capillaries. Coal miners’ ‘black-lung’ disease, asbestos workers’ pulmonary frosis, and emphysema of urban people are all associated with the accumulation of such small Particles. Effects of Particulates on Materials Air-bone particles including soot, dust, Taterils. The extent and type of damage depends of the pollutant. Extensive chemical ee i ces along with them. ase eric D the soil within a 16 km radios frocy ue dust as a eeult of methyl isocyanate (MIC) leakage, and its ferity i Particulates accelerate corrosion of metals, which is maximum in urban They cause damage to buildings, sculptures, paints etc. fumes and mist are potentially harmful for a variety of ‘upon the chemical composition and physical sate when the particulates themselves are corrosive of hopal was coated with for the next ten years. industrial atmospheres.Particulates and Climate Particulates in the atmosphere reduce visibility by scattering and absorption of solar radiation ‘They influence the climate through the formation of clouds, rain and snow, by acting as nuclei ype which water condensation can take place. Atmospheric particulate levels can be correlated with t extent of precipitation over cities and their suburbs. |t 10.1.9. Effects of Atmospheric Pollution baz opleee siatien ic pollutants are present largely in the troposphere and lows ‘atosphere, The of aa 1-100 m high, is generally very much polluted in cee and indy sites, Some pollutants are absorbed into vegetation, building and water sul faces. The next layer of si, 100-2000 m high, contains pollutants which are well mixed by the turbulent air Currents and pan which is washed out by drizzle, rain and fog. The third layer extending up to the tropopause conn, major amount of water vapour and clouds, Some pollutants may be dissolved or turn into nuclei iy the cloud water droplets. Subsequently, they are eliminated as rain or discharged again into te atmosphere on evaporation of water. The lower stratosphere contains low concentration of pollutants, dust by direct injection fox volcanic eruptions, ground and air nuclear explosion and also the products of photochemical reactions involving CH, and SO. The pollutants, however, stay in the stratosphere for a long period due to very little movement of airmass in this region. _ Particulate effects—The large concentration of particulates in the atmosphere over large cities and industrial areas Produces some general effects. Smoke and fumes tend to increase the atmosphett turbidity reducing visibility and the quantum of solar radiation reaching the earth’s surface. During more mist, fog and smog relative to nl large sized particulates on the ground. This metals and also damage to plants. S discharged into the atmosphere suffer chemi of sunlight to form secondary pollutants. So™ areas. These processes combine to increase the deposi leads to erosion and corrosion of building materials, sinet Effects in the biosphere—The pris e Primary pollu changes in presence of HO, O, and ultraviolet = such chemical reactions are summarized: ™ Primary pollutants Reactions Secondary pollutants co, He, « 0, ig ‘a : = a NO, he, (48) HF ae @n * SiFs