The problem of acid rain has attracted worldwide attention only since 1980s. However, the term ‘acid rain’ was first used by first Alkali Inspector of Britain,, Robert Angus in 1872. His work largely remained ignored until 1950s when Canadian ecologist Dr. Eville Gorham undertook detailed studies of rainwater quality and its control in Lake District in north-west England. By mid 1960s, early damage symptoms of acid rains begun to appear in Scandinavia and Swedish worker Svente Oden begain a concerted scientific effort in 1967 to bring awareness about acid rain problem. He is considered to be the father of modern acid rain studies.
GEOGRAPHY OF ACID RAIN
Primary pollutants causing acid rain problem are blown over long distances by the wind and thus spreading the problem over whole of the Earth’s surface. However, till now most of pollutants responsible for acid rain problem are produced in the highly industrialized nations, the areas of the impact of acid rains are few, noticeable, few and predictable. Common properties observed in areas affected seriously by acid rain problem are:
Heavy concentration of industries producing pollutants responsible for acid rain problem.
Downwards flow of winds from pollutant-producing areas.
Upland-mountainous position of pollutant-producing areas having thin glaciated bedrock and high rainfall-snowfall.
Numerous lakes and streams and rich forest cover in pollutant-producing area.
Areas sharing the above common properties are termed acid rain hot spots and include many parts of Scandinavia, upland Britain, West Germany and many parts of Northern Europe. Across Atlantic, such areas include Nova Scotia, Canadian Shield around southern Ontario and Quebec, Adriaondack Mountains, Great Smoky Mountains, parts of Wisconsin and Minnesota, Pacific Northwest U.S.A., Colorado Rockies and Pine Barrens of New Jersey. Japanese islands are also included in this category.
Areas having severest acid rain damage are glaciated Pre-Cambrian shield areas of Scandinavia, glaciated parts of upland Britain having thin soils, eastern Canada and resistant Canadian Shield and northwest U.S.A. Problems of acidification develop much acutely on granite and similar other resistant rocks.
Acid rain as global problem
Though at present acid rain problem is mainly concentrated in highly industrialized areas, the long-range transport of concerned air pollutants results in gradual globalization of the problem. As a result of slow transport of acid rain causing pollutants from heavily industrialized areas to areas till now free from this problem, the latter areas are also beginning to show acidification damage. Such damage has been reported from many developing nations like Zambia, South Africa, Malaysia, Venezuela, India and China. Most productive farmlands of China and India, paddy fields of South-east Asia and forests of Amazon in South America have soils which are highly susceptible to acidification.
Global dimension of acid rain problem was established beyond doubt in 1981 with discovery of Arctic haze. It is bluish-gray haze developing in Arctic areas similar to that frequently found over and downwind of large industrial areas in western Europe and eastern North America. Haze layers often cover a horizontal area of upto 1000 km and are caused by scattering of solar radiation by minute suspended particles in the atmosphere. These particles vary in the size range of 0.1-1.0 micrometer and mostly comprise of sulphate aerosols. These aerosols are transported by jet streams in upper atmosphere and may reach upto 8000 km away from their industrial sources. Hazes are found to be thickest in Alaska’s North Slope extending atleast to Norway. Hazes mainly affect visibility and are not as damaging as the smog.
CAUSE AND FORMATION OF ACID RAIN
SO2 and oxides of nitrogen (NOx) emitted into the atmosphere due to industrial, commercial and other anthropogenic activities are the basic cause of acid rain formation. Therefore, the problem of acid rains has accompanied the rise of emission of these gases into the atmosphere.
SO2 is emitted from three principal man-made sources:
Combustion of coal produces about 60% of total SO2 emitted into atmosphere.
Combustion of petroleum products which adds 30% of total emission.
Industrial activities like smelting of iron, zinc, nickel, copper ores, manufacture of sulphuric acid and operation of acid concentrators in petroleum industry. These produce the remaining 10% of this gas.
Overall emission of oxides of nitrogen is small in comparison with SO2, their importance in formation of acid rains is very high. Most of the oxides of nitrogen (NO3, NO2, NO etc.) are produced from:
Combustion of fossil fuels.
Industrial chimneys and thermal power stations.
Motor vehicles in urban areas.
Man-made sources of SO2 and NOx emission are point sources (e.g. thermal power stations and industrial chimneys) and the emission from these occurs as a plume of gases. The plume of gases emitted from high stacks usually travels downwind for about 12 km as a straight line without much dispersion. Afterwards, its shape evolves by diffusion and changes progressively downwind into a widening cone. The direction, speed, distance of travel of the plume and its dispersal and diffusion depend upon meteorological conditions such as direction, velocity and pattern of propelling wind, air temperature (especially the vertical temperature gradient), air turbulence and atmospheric stability. Under stable atmospheric conditions, for example, at night over land and during day over snow covered ground, there is very little vertical dispersal for very long distance and the acidification may occur at quite far away place from the source of emission.
Dispersal of the plume of SO2 and NOx occurs in the mixing layer of atmosphere that extends from ground level upto 1-2 km altitude. The dispersal is triggered by diffusion and atmospheric turbulence, normally between 5 to 25 km from the point of source. The rate of diffusion and mixing of oxides into air is faster when flow of air is turbulent. The lower portion of the dispersing cone of oxide plume first touches the ground level at about 5 km distance form the point source while middle and upper portions are thoroughly dispersed in the air leading to dilution and chemical transformation.
The deposition of pollutant oxides from the plume onto the ground is of two types: dry deposition and wet deposition.
Dry deposition: The acidic oxides deposited from the bottom of the plume between 5-25 km from the source in the form of gases and particles constitute the dry deposition. Though such deposition is not acid rain in strict sense, it produces acidification of soils and surface water bodies similar to acid rain. This dry deposition also causes direct SO2 and NOxpoisoning of the vegetation. Dry deposition of sulphur and nitrogen oxides and undissolved acids on lakes and steams straightaway dissolve in the water and acidify the water bodies. Such dry deposition on land and on vegetation remains inactive till dew or rainfall when these dry deposited acids dissolve in the dew or rain water and form active acids. Such sudden addition of high concentration of acids into an otherwise stable environment causes acid shocks, acid flushes or acid surges. These terms indicate increasing levels of acidification and decreasing time period in which such acidification takes place. During winters, SO2 and NOx pollutants are dry-deposited on snow and ice in the catchment areas of many lakes and rivers. In the following spring season, when this snow and ice melt, the acids accumulated in the snow and ice over long period are suddenly released over a period of few days to a week causing acid surges in the lakes and streams.
Wet deposition: It is the deposition of acidic oxides of the plume over land or vegetation after being dissolved in the rainwater, snow or ice forming acid rains, acid snow, acid mistor acid fog. Today’s industrial chimneys are normally 100-300 meters high and, therefore, such wet deposition normally occurs beyond 25 km from the point source. The prevailing wind pattern and the length of time over which oxides are transported in the wind system is of great importance in the geographical distribution of acid rains. Longer the SO2 and NOxremain in the atmosphere, greater is the possibility of their transformation to produce sulphuric and nitric acids.
The practice of increasing the height of chimneys and installation of electrostatic precipitators to reduce the air pollution appears to have magnified the problem of acid deposition in two ways. Firstly, tall stacks of pollutant-emitting units now emit pollutant gases at much greater heights so that these gases are now dispersed over much wider areas increasing the geographical extent of acid deposition. Secondly, installation of electrostatic precipitators and other mechanisms to remove alkaline particulates in chimneys has resulted in increased emission of acidic gases. It is because prior to installation of such mechanisms, acidic gases were neutralized to a large extent by alkaline particulates being emitted alongwith them.
The complex pattern of acid deposition has following six stages:
The atmosphere receives SO2and NOx from natural and man-made sources.
Some of these oxides fall on the ground as dry deposition within 5-25 km from their parent sources.
Formation of photo-oxidants like ozone, is stimulated in the atmosphere.
The photo-oxidants interact with SO2 and NOx to produce acids (H2SO4 and HNO3) by oxidation.
The oxides of sulphur and nitrogen, photo-oxidants and other gases (including NH3) dissolve in the cloud and rain-droplets to produce acids (H+and NH4+) and sulphates (SO42-) and nitrates (NO3-).
Acid rain containing ions of sulphate, nitrate ammonium and hydrogen falls as wet deposition.
The most important step in this chain of reactions is the catalytic conversion of SO2 and NOx. This may take from a few hours to a few days in the atmosphere and can not occur without photo-oxidants (precurssors). Ozone is the most readily available and abundant photo-oxidant in the atmosphere . Hydrocarbons and NO added to the atmosphere as pollutants are the two main precurssors of ozone. The acid rain is the final product of the loading of SO2 and NOx coupled with photochemistry and physical dynamics of stratosphere.
Chemistry of acid fog
More recently, measurements at sites in parts of Europe, California and eastern U.S.A. have shown that in most circumstances, acid fog and water in low clouds has a lower pH value than equivalent acidic rainwater. Average pH values of acid fog in areas of heavy air pollution are about 3.4 and range from 2.8 to over 5.0 On average, mean concentrations of H+ and acid ions are 3 to 7 times higher in fog-water than in equivalent rainwater. Acid fog-water also has higher concentration of anions and cations. There are following five main reasons for the above describe differences:
Fog being located nearer to the ground, is often exposed to higher pollutant concentrations for longer periods of time than the rainwater during below-cloud scavenging. This exposure allows more time for extensive aqueous-phase chemical processes to take place.
Smaller fog and mist particles saturate with gaseous pollutants more quickly than the larger raindrops, allowing greater aqueous ion production.
The smaller droplets in fog and mist have a greater combined surface area compared to raindrops. As a result, acid gas diffusion is enhanced and higher concentrations of the resultant ions are produced.
The fog remains in the air mass in which it is formed while precipitation is often associated with changing air masses in frontal situations when much of the gaseous and aerosol material in the atmosphere is removed.
Pollutant aerosols originating several hundred kilometers away often act as nuclei for fog or cloud droplets and enhance aqueous chemical processes. The size and number of water droplets formed and the resultant chemistry depend on the number of aerosol nuclei available in the cloud. Greater number of these generally produce smaller and more numerous fog droplets. Ion concentrations in mist tend to be lower than in fog because mist contains a lesser number of droplets and this limits the chemical reactions.
However, fog-water shows wide variations in ion concentrations between sites and events. In stable atmosphere, low altitude fog masses are more likely to interact with pollutant emissions near the surface e.g. NOx from automobiles. On the other hand, mountain fogs occurring in a well mixed atmosphere and at times, isolated from low-altitude pollutant emissions due to inversions, tend to be cleaner having pH values of 5.0 and above. On minor scale, dew from polluted atmosphere can also be acidic with free H+ comprising about 80% of acidity while species of sulphur and nitrogen may contribute about 60% and 30% respectively to the acidity.
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In conditions of sufficient moisture, two climatic factors i.e. photosynthetically active radiation and temperature are particularly important in relation to productivity of plant cover.
The influence of radiation and temperature on productivity of plant cover is quite complex. In real natural situations, radiation is always a factor whose value is a ‘minimum’ because radiation available to leaves in lower layers of canopy is always insufficient. Therefore, increase in radiation flux always results in increased productivity of plant cover.
With increase in temperature, the productivity of plant cover increases initially. After attaining a certain maximum value that depends on the value of radiation flux, productivity begins to decrease with further increase in temperature. Thus productivity of plant cover substantially decreases above a certain threshold value of temperature which is determined by the radiation flux.
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Plants can effectively be used as cheap and naturally available monitoring systems or bioassays of the level and type of air, soil and water pollution in an area. The type and concentration of a pollutant can be reliably found out by various characteristics damage symptoms produced in the plants because such damage symptoms are pollutant specific as well as concentration specific. For example, in young needles of Pinus, chlorois indicates SO2pollution, necrosis indicates HF pollution, beaching indicates NO2 pollution while chlorotic mottle indicates Cl2pollution in the atmosphere. These characteristic symptoms of damage in young pine needles appear only when concentration is 0.3 ppm for SO2, 0.07 ppm for HF and 1.0 ppm for Cl2. Similarly, browning in moss leaves due to fluoride accumulation is 5% in 65 ppm dry weight accumulation but rises to 90% in 4500 ppm dry weight accumulation. However, certain precautions have to be taken while using plants as pollution indicators...
Leaves of sensitive species generally produce highly specific and characteristic visible injury symptoms in response to pollutants. The study of such symptoms can reliably indicate the type and level of pollutant(s) present in the environment. For such analysis, leaves of same age are collected at same time of the day and at different localities in the area from plants of a particular sensitive species. Most common symptoms studied are chlorosis, necrosis, discolouration, tip-burn, bleaching, bronzing, stipples and mottles in the leaves. Characteristic colours and patterns of these symptoms in particular plant species indicate the type and level of pollutant present.
I also recommend this comprehensive section on the chemical formation of tropospheric ozone.