ENVIRONMENTAL ENGINEERING II

UnitI: Air Pollution sources of pollution classification - effects on human beings Global effects of Air pollution

1.1 AIR POLLUTION: Air pollution is basically the presence of foreign substances in air in excessive concentration which adversely affects the well being of the individual or cause damage to property and environment.

Definitions Air pollution may be described as the imbalance in quality of air so as to cause adverse effects on the living organisms existing on earth. According to World Health Organizations, air pollution is defined as, substances put into air by the activity of mankind into concentration sufficient to cause harmful effect to his health, vegetables, property or to interfere with the enjoyment of his property. Indian Standards Institute define air pollution as, Air pollution is the presence in ambient atmosphere or substances, generally resulting from the activity of man, in sufficient concentration, present for a sufficient time and under circumstances which interfere significantly with the comfort, health or welfare of persons or with the full use or enjoyment of property.

Structure of Atmosphere:

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Chemical composition of atmospheric air:

Average composition of clean dry air near sea level (PPM by volume) Components Concentration in Average conc. ppm Major Nitrogen N2 Oxygen O2 Minor Argon Ar Carbon dioxide CO2 Trace Neon Ne Helium He Methane CH4 Kyrpton Kr Hydrogen H2 Carbon monoxide CO Ozone O3 Ammonia NH3 Nitrogen Dioxide NO2 Slufur Dioxide SO2 Hydrogen Sulfide H2S Xenon Xe Historical Overview: The first incidence of air pollution gets lost in unrecorded history, but it certainly goes back to the discovery of fire. However, notable air pollution episodes are: (i) London Smog: In 1661 John Evelyn in his famous pamphlet Fumifugium, recommended the removal of all smoke producing plants from London. But London did little about it, until the famous London Smog of Dec. 1952, truly a major air pollution disaster, occurred. Coal induced smog is formed by interaction of sulphur dioxide, smoke and water to form sulphuric acid mist. It lasted for five days and caused 4000 deaths. Thereafter, London experienced many air pollution disasters causing many excess deaths; In January 1956 December 1957 January 1959 December 1962 January 1963 (ii) 1000 deaths 700 deaths 200 deaths 700 deaths 700 deaths 78.09 x 104 20.94 x 104 93 x 102 32 x 102 18 5.2 1.3 1.0 0.5 0.1 0.02 0.01 0.001 0.0002 0.002 0.081 Volume present 78.09 20.94 0.93 0.0318 0.0018 0.00052 0.00013 0.0001 0.00005 0.00001 0.000002 0.000001 0.0000001 0.0000002 0.0000002 Continuous Continuous Continuous 2 to 4 years Continuous ~ 2 million years 4 to 7 years Continuous Little is known about residence time 0.5 year ~ 60 days 7 days 5 days 4 days 2 days Continuous Estimated residence time

Meuse Valley Belgium: A strong atmospheric inversion got settled over the Meuse Valley on Dec. 1, 1930. Effluents from several factories in the valley, like So x and soot were trapped in the stable atmosphere, 63 persons died and several hundred others became ill.

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(iii)

Donora, Pennsylvania (USA): In October 1948, similar conditions led to one of the first major air pollution disasters in USA. Seventeen people died and 43% of the population became ill.

(iv)

Pittsburgh: Prior to 1948 the nickname of Pittsburgh was Smokey City, and it seemed to be appropriate as a black pall of smoke and soot often turned day into night, and blackened the brightest buildings in a few months.

(v)

Los Angeles, California: In early 1950s due to large volume of traffic on Los Angeles streets, photochemical smog is formed by the interaction of HCs and oxidants (like NOx, CO, O3) in the presence of sunlight to form toxic PAN and ozone, causing eye irritation, visibility reduction and damage to crops and rubber cracking.

(vi)

Bhopal Gas Tragedy: The methyl isocynate (MIC) gas leak in Bhopal in December, 1984 has been regarded as the worst industrial accident related to air pollution. At least 5000 people were killed and some 50,000 people have been seriously affected by the leak of poisonous MIC gas from the Union Carbide Pesticide Plant.

1.2 Sources of Air Pollutants: The sources may be natural or anthropogenic (man-made). Natural Sources include volcanic eruptions, forest fires, cosmic dust, pollen grains. Emission Sources of Air Pollutants

Natural Sources

Man-Made Sources

Volcanoes Forest fires Sulphur springs Spray from the oceans Natural geysers Dispersion of sands and dust Natural organic & inorganic decays Vegetative decays Marsh gases Extra-terrestrial bodies Cosmic dust Pollen grains of flowers Soil debris Fungal spores Photochemical reactions

Domestic burning of wood Burning of fossil fuels Industrialization Agricultural activities Vehicular emissions Aircraft Wars Nuclear tests Deforestation Incineration Power generation Mining Metallurgy Waste treatment plants Refrigeration industries Page 3 of 37

Anthropogenic or man-made air pollution sources

Source type Combustion Category Stationary Important Sources Power plants, industrial boilers, diesel generators, municipal or industrial incineration Trace metal oxides Motor, vehicles, aircraft Roasting, smelting refining operations and Typical pollutants SOx, NOx, CO, smoke, fly ash

Roasting and heating processes

Refuse burning Mobile Non-ferrous metallurgical Ferrous metallurgical Non-metallic minerals

Food and agriculture

Food processing Crop spraying and dusting Field burning

Material handling, ore sintering, and pelletising, coke ovens, blast furnaces, steel furnaces Crushed stone, cement glass, refractories, ceramic manufacture, coal cleaning Drying, preserving, packaging Pest and Weed control Refuse burning Boilers, process heaters, catalyst regenerators, flares, storage tanks, compressor engines Sulphuric acid plants, fertilizer manufacture, nitric acid and ammonia plants, phosphoric acid manufacture Plastics, paint and varnish manufacture, synthetic rubbers, rayon, insecticides, soap and detergent manufacture, Methanol, phenol, etc Digester blow oxidation towers

CO, HC, NOx, SOx, particulates Dust, smoke, metal fumes (Cu, Zn, and Pb), oxides of sulphur Smoke, fumes, CO, odours, H2S, organic vapour, fluorides Mineral and particulates organic

Vapour, odour and dust organic phosphates, chlorinated HC, organic, lead Smoke, fly ash and soot SOX, HC, NOx particulate matter, CO, aldehyde, ammonia, odours SOx, HF, H2S, NOx, NH3, particulate matter, H3PO4, etc Particulate matter, odours, SO2, CO, organic intermediates, solvent vapours

Petroleum industries Inorganic chemical industries Chemical industries

Petroleum refining

Inorganic chemicals

Organic chemicals

Paper industries

Pulp manufacture

Mercaptans, sulphide, SO2

dimethyl

Among the emission sources, some are stationary point sources while others are moving point sources. The pollution from industries is almost continuous. The vehicular pollution waxes and wanes according to the peak hour traffic during the day and night. The common air pollutants, their sources and pathogenic effects are given in table below. Common air pollutants, their sources and pathological effects on man Pollutant Sulphur dioxide Source Colourless gas produced by coal and Pathological effects on man Respiratory irritant, aggravate

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Nitrogen oxides Hydrogen sulphide Carbon monoxide Hydrogen cyanide Ammonia Phosgene or carbonyl chloride Aldehydes Arsines Suspended particles (ash, soot, smoke, etc)

oil combustion and certain industrial sources Brownish orange gas produced by motor vehicles and combustion at major industrial sources Refineries, chemical industries and bituminous fuels Burning of coal, gasoline, motor exhausts Blast furnace, fumigation, chemical manufacturing, metal plating, etc Explosives, dye making, plants and lacquers Chemical and dye making fertilizer

Thermal decomposition of oils, fats, or gylcerols Processes involving metal or acids containing arseic, soldering Solid or liquid particles produced by combustion and other processes at major industrial sources (e.g. steel mills, power plants, chemical plants, incinerators and almost every manufacturing process)

Lead

Very small particles emitted from motor vehicles and smelters A colourless gas formed from reactions between motor vehicle emissions and sunlight. It is the major component of smog.

Ozone

asthma and other lung and heart diseases, reduces lung function Inhibits cilia action so that soot and dust penetrate far into the lungs Causes nausea, irritates eyes and throat Reduces oxygen carrying capacity of blood Interferes with nerve cells, produces dry throat, indistinct vision, headache, etc. Inflames upper respiratory passages Induces coughing, irritation and fatal pulmonary edema Irritate nasal and respiratory tracts Damage red cells in blood, kidneys and cause jaundice Respiratory irritants, aggravate asthma and other ling and heart diseases (especially in combination with sulphur dioxide); many are known as carcinogens. Toxic gases and heavy metals absorb onto these particulates and are commonly carried deep into the lungs. Cause emphysema, eye irritation and possibly cancer Toxic to nervous and bloodforming systems. in high concentrations can cause brain and organ damage Respiratory irritant, aggravates asthma and other lung and heart diseases, impairs lung functions. Ozone is toxic to plants and corrodes materials.

1.3 Classifications of Air pollutants: Air pollutants may be classified according to origin, chemical composition and state of matter. 1. According to Origin: On the basis of origin, air pollutants can be divided into two categories Primary and Secondary air pollutants. Primary air pollutants are those which are emitted directly to the atmosphere and found there in the form in which they are emitted. For example, particulates, carbon monoxide (CO), oxides of sulphur (Sox), oxides of nitrogen (NOx), hydrocarbons (HCs), radioactive compounds, particles of metal, pollen, bacteria, etc. The five main primary

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air pollutants (viz particulates CO, SOx, NOx and HCs) contribute more than 90% of global air pollution. Secondary air pollutants are those which are produced in the air by the interaction among two or more primary air pollutants, or by reaction with normal atmospheric constituents, with or without photoactivation. For example, ozone (O 3), peroxyacetyl nitrate (PAN), formaldehyde, formation of acid mists, smog (coal induced and photochemical smog), etc. 2. According to Chemical Composition On the basis of chemical composition, air pollutants can be divided as organic and inorganic air pollutants. Organic compounds contain carbon and hydrogen, and many also contain certain elements such as oxygen, nitrogen, sulphur and phosphorous. Examples of organic air pollutants are hydrocarbons, aldehydes, ketones, carboxylic acids, organic sulphur compounds, etc. Inorganic air pollutants include compounds, such as CO, CO2, SOx, NOx, O3, NH3, CL2, HF, H2S etc. 3. According to State of Matter: On this basis, air pollutants are classified as particulate and gaseous air pollutants. particulate air pollutants include finely divided solids and liquids dispersed in gaseous media. Dust, smoke, fly ash, flumes, etc., are examples of solid particulates; while mist, spray, fog etc., are liquid particulate air pollutants. Gaseous air pollutants are organic gases like benzene, methane, butane, aldehydes, ketones, etc. as well as inorganic gases like CO2, SOx, CO, NH3, H2S, NOx etc. Aerosols which may be solid particles (dust, smoke) and liquid particles (fumes, oil mists, polymeric reaction products) 4. According to Mobility: These are large stationary sources, such as, Point Sources industries, These Area Sources as, etc. Line Sources Mobile Sources Area Sources These are highways, railway tracks, navigation routes, etc. These are airports, railway stations, ports, etc. are power small plants, municipal sources and and incinerators, etc. Stationary Sources stationary mobiles sources with indefinite routes. Such residential heating, commercial institutional heating, open burning city traffic,

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1.4 Effects of Air pollution on Human Health The air we breathe has not only life sustaining properties, but also life damaging properties. An average man breathes 22,000 times a day and takes in 16kg of air each day. The impurities in the inhaled air can affect human health in a number of ways, depending upon the nature and concentration of the pollutants, duration of exposure, and age group of the receptor. Depending upon the chemical nature of the pollutants, some pollutants may be harmful when present in small concentrations and others only if they are present in high concentrations. The duration of exposure to polluted air is also an important factor. The infants, elders and those with chronic diseases of the lungs or heart are more susceptible to the effects of air pollution. It has also been observed that the effect of air pollution on human health is worst or maximum during winter season, when pollution levels reach a climax. The various health effects are as under: i) Eye irritation can be caused by many air pollutants such as NO x, O3, PAN, smog, particulates. ii) Nose and throat irritation can be caused by SOx, NOx insecticides, pesticides etc. iii) Gaseous pollutants like H2S, SO2, NO2 and hydrocarbons can cause odour nuisance even at low concentrations. iv) Irritation of the respiratory tract can be caused by SOx, NOx, O3, CO, etc. v) Increase in mortality and morbidity rate. vi) A variety of particulates, particularly pollens, can initiate asthmatic attacks. vii) High concentrations of SO2, NO2, SPM (suspended particulates matter) and photochemical smog can aggravate chronic pulmonary diseases like bronchitis and asthma. viii) Carbon monoxide, which is two hundred times more reactive than oxygen, combines with haemoglobin in the blood and consequently increases stress on those suffering from cardiovascular and pulmonary diseases. Similarly, nitric oxide (NO) can react with haemoglobin and reduce the oxygen carrying capacity of the blood. ix) Hydrogen fluoride can cause flurosis and mottling of teeth. x) Air pollutants such as polycyclic organic compounds, aliphatic hydrocarbons, etc. can cause cancer. xi) Dust particles can cause dust specific respiratory diseases, such as, silicosis (associated with silica dust), asbestos (associated with asbestos dust), etc. xii) Heavy metals, like lead (emitted from vehicles), may enter the body through the lungs and can cause poisoning. Its high concentration can damage liver and kidney, and can cause abnormality in fertility and pregnancy, and mental development of children gets affected. xiii) Exposure to radioactive isotopes like Iodine 131, Phosphorous 32, cobalt 60, Radium 226, etc can cause anaemia (iron deficiency, Ieukaemia (RBC deficiency), cancer and genetic defects.

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1.5 Effects of Air Pollution on Plants: The primary factor that governs the gas absorption by the plant leaves is the degree of opening of the stomata. The stomata are the openings in the leaf, generally in the bottom of the leaf, through which CO2 enters to play its role in photosynthesis. When the stomata are wide open (day time), the absorption is maximum and vice-versa. As a result, the same conditions that enhance the absorption of CO2, also expose the plant to injury by absorbing a pollutant gas. Most of the plants close their stomata during night and are, therefore, much more resistant at night. The effects of some of the important air pollutants on plants are given in table 1.2. The air pollutants that affect plants include SO2, O3, fluorides, NOx, Pan, ethylene, NH3, mercury, smog, herbicides, etc. Effects of Air Pollutants on Plants S. No 1. 2. 3. 4. 5. Pollutant SO2 O3 NO2 Fluorides Ethylene Effects on plants Bleaching of leaves, necrosis (killing of tissues) Premature aging, suppressed growth, necrosis, bleaching, collapse of leaf Suppressed growth, bleaching Necrosis at leaf tip. Leaf abscission (dropping of leaves), leaf epinasty (downward curvature of leaf) 6. PAN Suppressed growth, silvering of lower leaf surface.

These pollutants interfere with plant growth / yield, and the phenomenon of photosynthesis. dust, smog, etc. reduce the amount of light reaching the leaf, and also by clogging the stomata may reduce the intake of carbon dioxide. Plant response to air pollutants varies from species to species, for example, some plants are sensitive to fluoride but resistant to sulphur dioxide. The sensitivity of plants to air pollutants depends on many factors, such as, climatic conditions (that include duration of light, temperature, humidity, and light intensity), soil, water and fertility. 1.6 Effects of Air pollution on Animals: The process by which the animals get poisoned is entirely different from that by which human beings exposed to air pollutants are poisoned. In case of animals, it is a two-setp process: (i) Accumulation of air pollutants in the vegetation and forage; and forage. (ii) Subsequent poisoning of the animals, when they eat the contaminated vegetation /

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The pollutants mainly responsible for most livestock damage are: Fluorine: Of all the farm animals, cattle and sheep are the most susceptible to fluorine toxicity. Horses are quite resistant, while poultry are probably the most resistant to fluorine of all the farm animals. Fluorine is a cumulative poison under conditions of continuous exposure to subacute doses. Its effects are lack of appetite, rapid loss of weight lameness, periodic diarrhoea, muscular weakness, wearing of teeth, and death. Lead: chronic lead poisoning has been observed frequently in animals that have been grazing near smelters and lead mines. It causes paralysis and difficulty in breathing. In case of acute lead poisoning, the onset is sudden and the course is relatively short. There is complete loss of appetite, paralysis and diarrhea. Arsenic: In acute cases, it can cause severe salivation, thirst, vomiting, irregular pulse and respiration, abnormal body temperature, and death in few hours. Chronic arsenic poisoning causes cough, diarrhea, anaemia, abortion, paralysis and death. 1.7 Effects of Air Pollution on Materials: Air pollution damage to property / material is a very important economic aspect of pollution, and it covers a wide range: (i) Corrosion: Air pollution damages materials chiefly by corrosion of metals. The prime air pollutant responsible for metallic corrosion is SO2. In the presence of oxygen and moisture, it is converted to sulphuric acid. Deposition of this acid on metal parts of building roofs, railway tracks, overhead wires, metal on bridges, and other structures cause enormous loss due to corrosion. (ii) Damage to building materials: The acid deposition reacts with lime stone, marble, and other building materials to cause deterioration and disfigured the building materials. (iii) (iv) (v) (vi) Damage to paints and protective covering: Pollutants like SO2, O3, H2S, and aerosols damage protective coating and paints of the surface. Damage of textile dyes and textile fibres: The fading of textile dyes and deterioration of natural and synthetic textile fibres is caused by SOx, NOx and O3. Rubber Cracking: Rubber cracking of tyres and various forms of electrical insulation is caused by ozone and PAN. Deterioration of leather and paper: Sulphur dioxide causes leather to lose much of its strength and ultimately disintegrate; which has posed a serious problem of storage of leather bound books in libraries. The impurities in paper absorb SO2 and convert it into H2SO4 in the presence of moisture, which makes the paper extremely brittle and decreases its folding resistance.

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Effect on glasses and ceramics: Although glasses and ceramics are especially resistant to the chemical action of air pollutants, but long exposure for years showed a change in their surface appearance.

(viii)

Damage to objects of art and architecture: Acid rains cause intangible loss to objects to art and architecture throughout the world. For example, effects on the Taj Mahal, Belur Temple, Cleopatras needle (a stone structure in London), Statue of Liberty, and many more monuments, paintings (such as Ajanta frescos), antique costumes and other art objects.

(ix) (x) (xi) (xii)

Increased transportation costs in period of smog. Loss due to reduction in tourists traffic due to effects to air pollutants on art treasures and tourist centres. Expenditures due to the adoption of technical measures for the reduction of smoke or other emission from factories. Expenditures in connection with the administrative organization of pollution control.

1.8 Primary air pollutants 1.8.1 Particulate pollutants Airborne small, solid particles and liquid droplets are commonly known as particulates. When present in air in excess, they pose a serious pollution threat. The life period of particulates varies from a few seconds to several months; it depends on the settling rate, size, and density of particles and turbulence. Particulates can be inert or extremely reactive materials ranging in size from 100m down to 0.1m and less. The inert materials do not react readily with the environment nor do they exhibit any morphological changes as a result of combustion or any other process, whereas reactive materials could be further oxidized or may react chemically with the environment. Classification of Particulates: Dust: Particulates of size 1-200m belong to this category and are formed by the natural disintegration of rocks and soil or by mechanical processes like grinding and spraying. They are removed from the air by gravity and other inertial processes by large settling velocities and also act as centres of catalysis for many of the chemical reactions taking place in the atmosphere. Smoke: Particles of size 0.01-1m constitute smoke which can be either in the liquid or solid form and is formed by combustion or other chemical processes. Smoke may have different color depending o the nature of materials burnt. Fumes: Solid particles of size 0.1-1m which are normally released from chemical or metallurgical processes belong to this category.

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Mists: Liquid droplets generally smaller than 10m which are formed by condensation un the atmosphere or released from industrial operations represent mist. Fog: It is the mist in which the liquid is water and is sufficiently dense to observe vision. Aerosols: All airborne suspensions, either solid or liquid belong to this category and these are generally smaller than 1m. Particles of size 1-10m have measurable settling velocities but are readily stirred by air movements, whereas particles of size 0.1-1m have small settling velocities. Particles below 0.1m, as submicroscopic size found in urban air, undergo random Brownian motion resulting from collision among individual molecules. Effects of particulate pollutants on human health: The effects of particulate pollutants are largely dependent on the particle size. Airborne particles, i.e. dust, soot, fumes, and mists are potentially dangerous to human health. The nasal system prevents coarser particulates bigger than 5 microns from entering the respiratory system. Soluble aerosols will be absorbed into the blood from the alveoli while the insoluble aerosols are carried to the lymphatic stream and get deposited in pulmonary lymphatic depot points or in the lymph glands, where they create toxicity in the respiratory system. Lead interferes with the development and maturation of red blood cells. It is respond that a smoker can easily develop symptoms of asthma which is also due to a concentration of lead greater than in non-smokers. Effects of particulate pollutants on materials: Particulates affect a variety of materials in various ways. They cause damage to buildings, paints, furniture, etc. Painted surfaces are very susceptible to damage in wet conditions. 1.8.2 Sulphur oxides: SO2 is an unpleasant and highly irritating gas, when it is present in concentration greater than 1 ppm and adversely affects men, animals, plants and materials. It is perhaps the most damaging among the various gaseous air pollutants. Along with SO 2, SO3 is discharged, at about 1-5 percent of the SO2 concentration, and it combines rapidly with moisture in the atmosphere to form Sulphuric acid which has a low dew point. Both these oxides are rapidly removed from the atmosphere by rain or settle out as aerosol due to which their concentration is less compared to their emissions from human activities. Sources of Emission of Sulphur oxides: The global sulphur fluxes per year into the atmosphere by anthropogenic and natural sources are shown in fig.

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Sulphur dioxide is one of the principal constituents of air pollutants. It is a colourless, non-flammable and non-explosive gas with a suffocating pungent odour. It has an odour threshold of 0.5ppm, and a taste threshold of 0.3ppm. It is highly soluble in water, and is about twice as heavy as air. SO2 remains airborne for an average period of 2-4 days, during which time it may be transported as far as 1000km. Therefore, the problem of SO2 pollution is an international one. The background level for sulphur dioxide in ambient air ranges from 0 to 0.02ppm. It is produced from the combustion of sulphur-bearing materials. S + O2 SO2 Sinks: Sulphur dioxide is relatively stable in atmosphere, and acts either as a reducing or an oxidizing agent. Reacting photochemically or catalytically with other components in the atmosphere, it produces sulphur trioxide (SO3), Sulphurous acid (H2SO3), Sulphuric Acid (H2SO4). SO2

The end product (i.e., H2SO4 or its salts) reaches the earths surface either as wet deposits or dry deposits, and forms sulphates.

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Effects: The oxides of sulphur have pronounced effects not only on human health but also an plants and materials. Sulphuric acid, Sulphur dioxide and sulphate slats tend to irritate the mucous membranes of the respiratory tract and fasten the development of chronic respiratory diseases, particularly bronchitis and pulmonary emphysema. The most widespread disaster due to SO2 occurs when it is

Concentration ppm 0 to 1.0 1.0 to 2.0 2.0 to 5.0 5.0 to 10.0 10.0 to 20.0 > 20.0 400 to 500

Effects No detectable response Cardio respiratory response in healthy persons Detectable responses, tightness in chest Choking and increased lung resistance to air flow Severe distress, some nose-bleeding Digestive tract affected, eye irritation Fatal

The effects of SO2 concentration in ambient air depend on the exposure time, age group and health of the receptor. Accompanied by smoke, i.e. during smog formation with fine particulates. SO2 is particularly harmful because both sulphur dioxide and sulphuric acid molecules paralyse the hair like cilia which line the respiratory tract. Without the regular sweeping action of the cilia, particulates are able to penetrate to the lungs and settle there. These particulates usually carry with them concentrated amounts of sulphuric acid and SO 2, thus bringing these irritants into direct and prolonged contact with the delicate lung tissues. The SO2 particulate combination (smog) has been cited as cause of death in several air pollution tragedies, like Meuse Valley episode (1930), Donora Pennsylvania tragedy (1942), London episode (1952), and many more. Effects on Plants or Vegetation: Effects on plants can be classified as acute or chronic. The SO2 concentration in acute exposure is high for a short period, resulting in the damage characterized by clearly marked dead tissues between the veins or on the margins of the leaves (called leaf necrosis); chronic injury comes from exposure to low concentration for long periods of time, which causes brownish-red or bleached white areas on the blade of the leaf. The plant injury threshold for SO2 is about 0.3 to 0.4 ppm exposure for eight hours. Plants are particularly sensitive to SO2 during day periods of intense light, high relative humidity, adequate moisture and moderate temperature. They are generally more sensitive during growing seasons, regardless of climate conditions. Plants vary widely in their vegetables such as beans, spinach and lettuce, and trees such as apple, mulberry and pine are particularly sensitive to sulphur dioxide. While potatoes, onions and corn are more resistant to sulphur dioxide.

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Effects on Materials: Sulphur dioxides effect on materials is quite significant. Paper absorbs SO 2, the sulphur dioxide is oxidized to H2SO4, and the paper yellows and becomes brittle. Similarly, leather also weakens and disintegrates in the present of SO2. Due to these reasons, libraries store leather bound books and historical documents in carefully controlled environments. Excess exposure to SO2 accelerates corrosion rates of many metals (such as iron, steel, zinc, copper and nickel) at higher relative humidities. The accelerated corrosion is particularly noticeable in winters when more fuel is burned. Corrosion rates are about 1.5 to 5.0 times more in polluted urban areas than in clean air areas. Sulphuric acid aerosols readily attack building materials, especially those containing carbonates (such as marble, limestone, slate and mortar).

The carbonates are replaced by sulphates which are water soluble. 1.8.3 Oxides of Nitrogen (NOx): On the seven oxides of nitrogen, viz, nitrous oxide (N 2O), nitric oxide (NO), nitrogen dioxide(NO2), nitrogen trioxide (NO3), nitrogen sesquioxide (N2O3), nitrogen tetraoxide (N2O4) and nitrogen pentaoxide (N2O5), that exist in ambient air, only two oxides of nitrogen (NO and NO2) are primarily involved in air pollution. Nitric oxide (NO) is a colourless and odourless gas; while nitrogen dioxide is a reddish-brown gas having a pungent suffocating odour. Nitric oxide is emitted to the atmosphere in much larger quantities than nitrogen dioxide, Typical background levels of NO are about 2 to 3 ppb, and for NO 2 about 4.0 to 5.0 ppb. Nitric oxide is formed in high temperature combustion processes when atmospheric oxygen and nitrogen combine according to the following reaction.

The major process by which NO2 is formed in the atmosphere is NO + O3 NO2 + O2

Nitric oxide and nitrogen dioxide remain airborne for average residence period of about 4 days and 3 days respectively. Sources and sinks: Some oxides of nitrogen are produced naturally, while others are anthropogenically produced. Bacterial decomposition of organic matter releases NOx into the atmosphere, mainly in the form of nitric oxide. Small concentrations on NOx produced in the upper atmosphere by solar radiation reach the lower atmosphere through downward diffusion. NO x are also produced by lightning and forest fires. In fact, naturally occurring sources of NO x produce about ten times as much of NOx as do the anthropogenic sources. The natural sources of NOx are more or less uniformly distributed on global basis, while anthropogenic sources are concentrated in urban

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areas. Primary origins of human induced NOx are from fuel combustion in transportation and in stationary sources (power and heating), industrial processes in which nitric acid is used, emissions from electric utilities, mining and electric arc welding. Nitrogen dioxide, which is heavier than air, is readily soluble in water forming nitrous or nitric acid. There are various photochemical reactions which take care of NO x and give nitric acid as the end product as indicated in the following reactions: 2NO2 + H2O 3NO2 + H2O 2NO + O2 NO2 + O3 NO3 + NO2 N2O5 + H2O HNO3 + HNO2 2HNO3 + NO 2NO2 NO3 + O2 N2O5 2HNO3

Both nitrous and nitric acid will fall out in the rain or combine with ammonia (NH 3) in the atmosphere to form ammonium nitrate (NH4NO3). In this instance, the nitrogen oxides will produce a plant nutrient. Health effects of NO2 on humans Concentration ppm 0.12 0.7 to 2.0 5 to 20 20 to 50 50 to 100 100 to 150 >150 Effects: Oxides of nitrogen are the second most abundant (next to SO x) air pollutants in many cities. Like SOx they too have effects on human health, plants and materials. Nitrogen dioxide has more harmful effects in human health as compared to nitric oxide. Table () indicates the health effects of NO 2 on humans. Exposure to NO2, even at low concentrations, can lead to increased resistance of the lungs airways to air movement, increased frequency of acute bronchitis among infants and older persons, increased incidence of respiratory illness, and irritation to the alveoli of the lungs. Nitric oxide (NO) is a relatively inert gas and moderately toxic. Nitric oxide, like carbon monoxide, can combine with hemoglobin to reduce oxygen carrying capacity of the blood. NO concentrations are generally less than 1.0 ppm in the ambient air and are, thus, not considered health hazards. Effect Odour threshold Increased resistance of the lungs airways Eye and nasal irritation Pulmonary discomfort Inflammation of lung tissues Bronchiolitis fibrosa obligerans Fatal

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There is no evidence that NO cause damaging effects on plants while NO2 can cause some injury to vegetation. Infact, secondary pollutants produced during photochemical reactions involving NOx, such as PAN and O3, are far more likely to be damaging to plants. Effect on materials includes fading of textile dyes, yellowing of white fabric and oxidation of metals when exposed to high levels of NO2. Nitrous oxide (N2O) or laughing gas, which is often used as a dental anesthetic, is an important greenhouse gas. It is not believed to have any harmful effects as an air pollutant except in its role as a greenhouse gas (refer Art.6.7) One N 2O molecule is about 200 times as effective as one CO2 molecule, as a greenhouse gas. 1.8.4 Carbon Monoxide (CO): It is a colourless, tasteless and odourless gas. It is slightly lighter than air (0.965 times as heavy as air) and is insoluble in water. It is chemically inert under normal conditions and has an estimated atmospheric life of about two and a half months. It is a poisonous gas and is generally classified as an asphyxiant. The atmospheric background of CO is 0.1 ppm. It is produced by (i) (ii) Incomplete burning of the carbon in fossil fuels 2C + O2 2CO Reaction between carbon dioxide and carbon containing materials at very high temperatures in industrial processes, such as in electric and blast furnaces. CO2 + C (iii) 2CO And by dissociation of carbon dioxide at higher temperatures

Sources and Sinks: Carbon monoxide sources are both natural and anthropogenic. The natural sources are volcanic eruptions, natural gas emissions, forest fires, oxidation of methane gas from decaying vegetation, electrical discharge during storms, etc. The anthropogenic sources are motor vehicles, aircrafts, railways, industries (such as iron and steel, petroleum and paper industries, electrical and blast furnaces, etc.), fuel combustion in stationary sources for power and heating, agricultural burning, solid waste disposal, etc. The major carbon monoxide sink is some soil micro organisms. These soil sinks can take care of atmospheric carbon monoxide, but neither CO nor the sinks are distributed uniformly. In fact, the highly populated urban areas having the highest ambient CO concentration often have the least amount of available soil sinks.

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Health effects of COHb at various levels in the blood COHb level % <1.0 1 to 2 >5 10 to 25 25 to 40 40 to 60 >65 Effects: At present ambient levels, carbon monoxide has little, if any, effect on property, vegetation or materials. But it can seriously affect human aerobic metabolism, due to its high affinity for hemoglobin (Hb). It reacts with the hemoglobin of blood and displaces oxygen to form carboxy hemoglobin (COHb), thus, reducing the capability of the blood to carry oxygen. CO level ppm <5 5 to 10 >302 30 to 200 200 400 400 750 >1000 Effects No apparent effect Central nervous system affects impairment of time interval discrimation, visual perception brightness discrimination, and psychomotor functionary fs. Cardiac and pulmonary functional changes Headaches and dizziness Loss of consciousness Respiratory failure, coma, death after several hours Rapid death

Since the affinity of hemoglobin for CO is about 200 times more than for oxygen, therefore carbon monoxide can seriously impair the transport of oxygen even when present at low concentrations. The health effects observed in persons exposed to CO are indicated in Table (). As COHb levels increase, effects become more and more severe. It must be kept in mind that the absorption of CO by the body increases with the performed. Carbon monoxide is believed to impose an extra burden on those already suffering from anemia, disease of heart and blood vessels, chronic lung disease, overactive thyroid or even fever. It also affects central nervous system, and is responsible for heart attack and high mortality rate. However, the carbon monoxide poisoning can be cured by exposing the effete person to fresh oxygen. The following reverse reaction takes place:

1.8.5 Ozone (O3): Ozone is a bluish gas with a pungent odour. It can be created by passing a high voltage through dry atmospheric air between two stationary electrodes. It is unstable and breaks down to normal oxygen and nascent oxygen (which is a powerful oxidizing agent). Natural ozone mainly occurs in the stratosphere (between 16 to 40km), where it serves a vital biological role in absorbing high energy photons of ultraviolet radiation from sun and hazardous effects of UV-B radiations*. Natural ozone is also present in troposphere, where it has a background concentration of about 0.02ppm. Some of this tropospheric ozone has

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diffused down from stratosphere, while the remainder is formed photochemically from the action of UV photons on natural NOx. Though only about 10% of atmospheric ozone occurs in the troposphere (remaining 90% occurs in the stratosphere), but due to its strong oxidizing nature it has harmful effects on plants, animals, human beings and materials. Thus we can say that Ozone is a life savior, if present in stratosphere; but a pollutant, if present in troposphere. Sources and Sinks: Ozone is a major concern in air pollution. Mainly it is produced in the stratosphere, but a small concentration diffused downwards. Also small amount is produced by lighting and forest fires. The emission of precursors hydrocarbons, CO and NOx, mainly from vehicles, is responsible for higher ozone concentrations in the troposphere. Nitric oxide (NO) present in atmosphere reacts with ozone and is thus, responsible for the elimination of ozone. Effects: Ozone is a smelly and poisonous (at higher concentration) gas. Ozone, which is a major component of photochemical smog along with PAN, has an irritant action in the respiratory track reaching much deeper into lungs than oxides of sulphur. It can cause coughing, shortness of breath, air-way constriction, headache, chest tightness, altered red blood cells and eye, nose and throat irritation. The effects of ozone on plants include premature aging, suppressed growth, necrosis (killing of tissues), bleaching and collapse of leaf. Being an extremely active compound, ozone readily oxidizes paints, textile fibres, dye and elastomers (such as rubber). In fact, the cracking of tyres has become a serious economic problem. Though, technology is available to protect elastomers but only at significantly high cost. 1.8.6 Fluorides: HF is a highly corrosive and irritant gas. A typical fluoride concentration in the atmosphere is 0.05mg/m3. Because of its extreme toxicity, HF is a problem wherever processed involving fluorides take place, such as in the production of phosphate fertilizers, smelting of certain iron ores, and manufacturing of aluminium.

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Emission sources: Fluorine is a gas so reactive that it does not occur naturally in elemental form. However, many fluoride-containing minerals such as fluorspar, cyrolite, and certain appetites and used by industry. Some industries also produce HF either as a byproduct or to form various useful fluoro derivatives. Industrial and commercial processes involving fluorine compounds which may release fluoride and HF Emission processes Aluminium smelting Steel production Phosphate fertilizers Enamel and pottery manufacture Brick making Missile Propulsion Beryllium, zirconium, tantalum and niobium purification Cleanings of castings Welding Sandstone and marble cleaning Crolite, fluorspar and apatite mining Processes using large amounts of fluorine-derivates Clouding of electric bulbs Cut glass finishing Aviation fuel production Insecticides and rodenticides Separation of uranium isotopes Synthesis of plastics Aerosol, refrigerant and lubricant manufacture Wood preservation Cement reinforcing Furniture cane bleaching Water supplementation

Industrial emissions are superimposed upon significant natural background sources. Consequently, levels in both air and water supplies vary widely. The majority or rural and urban air monitoring sites record very low levels of atmospheric fluoride measured as total dissolved fluoride. Near phosphate fertilizer plants, aluminium smelters, or volcanoes, however levels may rise above 200 ppm. Water supplies around these areas may also show elevated levels, well above the 1 ppm recommended as an optimum to provide an acceptable incidence of dental cares and at the same time allow for the correct bone growth of children. Hydrogen fluoride and fluoride ions effects on animals and human ubiquitous by product: Food and drinks are the most important sources of human fluoride intake. Normally, these contain below 1 mg 1-1 of fluoride. Tea, fish and other sea foods are heavily laden exceptions. Other vegetables and cereals grown in areas subjected to high fluoride emissions may also be enriched in fluoride. The various physiological effects of fluoride in animals and humans are shown in table below. Physiological effects of fluoride in animals and humans Process Carbohydrate metabolism Lipid metabolism Disturbance Glycogen levels depleted glycogen turnover depressed phosphorylase activity reduced Activation of acetate inhibited liver lipases activated certain esterases inhibited

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Mineral metabolism

Interference in iron uptake sulphite and phosphate counteract the inhibiting effect of Ca2+ upon intestinal absorption Hormonal balances Effect on parathyroid function a * Calcium levels are influenced by parathyroid hormone produced by the parathyroid and a hormonal derivative of vitamin D (called 1,25 dihydroxyl cholecacalciferol) found in the liver and kidneys both of which raise blood serum levels of calcium. Release of calcitonin from the thyroid, however, causes enhanced calcification of the bone tissues which then reduces blood calcium levels again. Effects on plants Fluoride deposition on plants not only causes them damage but may result in a second untoward effect. Grazing animals may accumulate an excess of fluoride, which mottles their teeth and ultimately causes to fall out. Problems associated with fluoride in plants are well known in relationship to fluorosis in farm animals. Animals grazing on pasture very close to brick works, smelters and phosphate fertilizer factories, or fed forage gathered from such area, may shoe fluorosis, a condition also occasionally found in humans. The major recommendation has been to ensure that the yearly average fluoride content of herbage does not exceed 40 mg 1-1a-1. Application of lime to crops and herbage has long been known to be a practical means of reducing the effects of fluoride injury. Originally, it was thought the lime caused the immobilization of the fluoride on the surfaces of the leaves as insoluble calcium fluoride. However, calcium chloride spraying has a similar alleviating effect to lime and recent studies have shown that the remedy actually relies upon additional calcium entering the leaves to interact with the fluoride inside and redress any calcium imbalances in the regulatory processes. Accumulation by plants: Crop less in the USA due to fluoride is ranked fourth in importance after O3, SO2 and nitrogen based air pollutants. However, on a weight for weight basis, fluoride is the most phytotoxid of all atmospheric pollutants. Injuries to the most susceptible plants occur at concentrations between 10 and 1000 times lower than those of other air pollutants. Rates of uptake of fluoride into leaves are also faster than those of any other pollutant and go on to cause problems to animals feeding upon these plants. Both gaseous and particulate fluorides are deposited on plant surfaces and some penetrate directly if the leaf is old or weathered. Nevertheless, the main access into a plant is by HF entering through the stomata. An important feature of fluoride uptake and transport in plants is that it is later carried in the transpiration stream towards the leaf tips or margins where it accumulates and phytotoxid effects usually develop. Plant species show wide ranges of susceptibilities to fluoride but environmental factors, such as light, temperature, humidity,

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water stress, etc., all influence plant response. Young conifers, gladioli, peaches and vines are especially sensitive while tea and cotton are very resistant. There are several mechanisms, which reduce fluoride levels in plants. These include shedding of individual leaves or surface waxes, leaching by rain, or voltalization. Fluoride levels are often lowest during summer months because of more favourable meteorological conditions for better dispersal of fluoride pollution and greater turnover of leaves in grass swards during summer. There are many reports of changes in photosynthesis, respiration or metabolism of amino acids, proteins, fatty acids, lipids and carbohydrates in plants due to fluoride. Certain enzymes are modulated by the presence or absence of fluoride but these do not explain the wide range of metabolic changes known to occur. These are due to interactions between fluoride and calcium or magnesium. Calcium and fluoride together for example, stimulate phosphate uptake which means that calcium adsorption sites on cell membranes are involved in response to fluoride. Cytoplasmic calcium is a ubiquitous regulator of cell metabolism and many, but not all, of its effects ae mediated by a calcium-binding protein calmodulin, which in turn stimulates a variety or enzymes. Moreover, calcium ions are known to affect the transport selectivity of membranes with respect to other substances. Because of this, fluoride exerts an effect in various regulatory activities (table ()) and this probably explains why it is so phytotoxic at such low concentration. Fluoride also forms magnesium-fluorophosphate complexes and, consequently

manyenzyme pathways are adversely affected by fluoride. Most reactions involving ATP, for example, require additional magnesium complexes to function correctly. If these natural complexes are also disturbed by the presence of additional fluoride then key reactions are inhibited. Normally, soils contain between 20 and 500mgg-1 fluoride but, because it has limited solubility in soil water, uptake by roots is relatively low, and there is little relationship between soil fluoride and total plant fluoride content. Consequently, atmosphere sources of fluoride are more important than fluoride in groundwater in determining the amount of fluoride in or on a crop. Physiological effects on fluoride on plants Process Respiration and Carbohydrate Metabolism Disturbance Glycolysis inhibited Pentose phosphate pathway Enhanced Unusual mitochondrial swelling Oxidative phosphorylation reduced Unusual chloroplast structure Inhibited pigment synthesis Increased PEPCa activity Likely cation interaction Mg2+ Mg2+ Mg2+ Mg2+ Mg2+ Mg2+ Mg2+

Photosynthesis

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Amino acid and Protein metabolism Nucleic acid Metabolism Fatty acid and lipid Metabolism Other metabolic a Changes Transport and Translocation Fruit development

Reduce electron flow Increases in free amino acids And asparagines Decrease in ribosome sizes Changes in transportation and Translation Increased esterase activities Decreased unsaturated / saturated ratios Increase in peroxidase activities Decrease in acid phosphatase Activity Altered plasma membrane ATPases Poor fertilization and seed Germination Reduced pollen tube growth Reduced seed number and fruit size

Ca2+ Ca2+/Mg2+ Ca2+/Mg2+

Ca2+

/Mg2+ Ca /Mg2+
2+

Ca2+/Mg2+ Ca2+/Mg2+ Ca2+/Mg2+ Ca2+

Ca2+ Ca2+ Ca2+

1.8.7 Hydrocarbons (HCs): Hydrocarbons are those organic compounds which contain only carbon and hydrogen. Like CO, they represent unburned and wasted fuel. Most of the major chemicals in gasoline and other petroleum products are hydrocarbons, which are divided into two categories aliphatic and aromatic. Aliphatic hydrocarbons group contains alkanes, alkenes and alkynes. The alkane are saturated bydrocarbons (i.e., methane) and are fairly inert, and generally not active in atmospheric photochemical reactions. The alkenes, generally called olefins, are unsaturated and highly reactive in atmosphere, The alkenes (such as ethylene), in the presence of sunlight, react with nitrogen dioxide at high concentrations to form secondary pollutants such as PAN (peroxyxcetyl nitrate) and ozone, The alkynes, through highly reactive, are relatively rare and thus not of major concern in air pollution. Aromatic hydrocarbons are biochemically and biologically active, and some are potentially carcinogenic. They are derived from or related to benzene. Though aromatics do not display the reactivity characteristics of unsaturated aliphatic hydrocarbons, but the polynuclear group of aromatic hydrocarbons is carcinogenic. Sources and sinks: Hydro carbons present in the atmosphere are from both natural and anthropogenic sources. Most of the natural hydrocarbons are from biological sources, though some amounts come from geothermal areas, coal fields, natural gas from petroleum fields and natural fires. The more complex naturally produced HCs found in the atmosphere (such as volatile terpenes and isoprene) are produced by plants and trees. The terpene molecules combine to form aerosols that produce the blue-haze over forested areas. The estimated natural emission of

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hydrocarbons in atmosphere is about 7.4 x 108 tons per year, which is about 85% of the total estimated emissions of HCs. Methane (CH 4) is the major naturally occurring hydrocarbons emitted in the atmosphere. It is produced in the anaerobic decomposition of organic matter in water or soil. Natural background levels of methane in the atmosphere range from 1.2 to 1.5 ppm on global basis. The average residence time of CH 4 is about 3 to 7 years in the atmosphere. The anthropogenic sources contribute about 15% of the total estimated emission of HCs in the atmosphere. The major anthropogenic sources of hydrocarbons are industrial sources (notably refineries) and transportation (particularly automobiles). The maximum concentration as well as emissions of hydrocarbons from human activities are generally found in areas of high population density (due to high traffic density). Some of the important HCs emitted from these sources are ethane, propane, n-butane, isopentane, n-pentane, isobutene, ethylene, acetylene, toluene, xylene, etc. Hydrocarbon emissions from solid waste disposal agricultural burning and coal waste fires also contribute to anthropogenic sources. Several chemicals and photochemical reactions are responsible for the removal of HCs from the atmosphere. As they are thermodynamically unstable towards oxidation, therefore, they tend to be oxidized through a series of steps. The end products of oxidation are CO2, solid organic particulate matter or water soluble products, which are removed from atmosphere by dry or wet deposition. Effects: Hydrocarbons are generally not toxic at concentrations normally found in the atmosphere, but they are major pollutants because of their role in the formation of photochemical smog. Experimental tests on humans and animals with aliphatic hydrocarbon concentrations of 500 ppm produce no harmful effects. But plynuclear group of aromatic hydrocarbons from automotive exhaust emissions are carcinogenic in nature. Ethylene, produced in automobile exhaust, is one of the very few hydrocarbons that can cause plant damage even at low concentrations. Tomato and pepper plants and orchids can be severely damaged if they are exposed to ethylene (0.01 to 0.3 ppm) for longer duration. 1.8.8 Ammonia: Ammonia (NH3), which is a pungent gas, is used as a raw material in large quantities used by industries for the synthesis of ammonium nitrate, plastics, explosives, dyes and drugs. Further it is also used as a refrigerant.

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Emission sources: Emission of NH3 from the biological degradation of proteins on soil surfaces into the atmosphere occurs in a very large scale which is known as NH 3 volatilization and compared to this the industrial contribution is negligible. Atmospheric concentrations of NH 3 in temperate rural regions range from 5 to 10 ppm but are much higher near the equator. In urban regions, higher levels of NH3 upto 280ppm are recorded which may be found in increasing levels close to industrial and intensive agricultural sources. In some developed countries, atmospheric levels of NH3 are still rising with accelerated use of artificial fertilizers and higher stocking rates of farm animals. NH3 readily forms cations or complexes of varying stability which effects the rate of volatilization. Most important among these is the affinity of NH3 with H2O to from ammonium ions which is strongly enhanced by increased alkalinity (as shown below). This means that there is an increased likelihood of NH3 volatilization at high pH.

Variation of CO2 level or changes in temperature will have a marked influence on the NH 3 NH4+ relationship as both ionization of H2O and the dissociation of NH3 are temperature dependent. Furthermore, exchange of NH3 between solution and the air above varies markedly with temperature. In soils, NH3 may be either adsorbed onto clay or organic particles and react with carbonyl and other acidic groups to from exchangeable salts, or it may combine with other organic components to form non-exchangeable products. In view of this different soils have different rates of NH3 volatilization and these, inturn, are affected by their water contents. As OH- ions are removed in process of conversion on NH4+ to NH3-. As NH3 is volatilized from the soil surface to the atmosphere, the soil solution becomes acidified at rates which depend on the soil buffer capacity. In view of this volatilization of NH3 is more likely from soils where the acidity produced can be neutralized by high levels of carbonate or other forms of alkalinity which explains why larger emissions of NH3 occur from natural calcareous soils or after liming. The anions present in applied fertilizers also effect the rate of NH 3 volatilization from soils. Urea is frequently uses as an alternative fertilizer because the enzyme urease, which is widely distributed in plants, microbes and soils, catalyses the hydrolysis of urea to bicarbonate and NH4+. As urease activity tends to be greater in soils with large organic contents and rather less in calcareous soils, the usual increase of NH3 volatilization form alkaline soils and decrease from acid soils is reversed when urea is used as fertilizer.

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NH3 volatilization also takes place with the higher rate from stored animal manures in stock-yards or from sewage works. The factors involved are similar to those of applied slurries on fields. Periodic addition of fresh material to the tops of piles of manure or the agitation of sewage ponds, therefore, greatly accelerates rates of NH3 volatilization. Most NH3 in the atmosphere arises from the directly hydrolysis of the urea in animal urine, other contributions being of less importance. In Europe, as much as 10% of useful N is lost directly by NH 3 volatilization and, in warmer climates, this can rise to as much as 30%. The amounts of N released into the atmosphere globally by NH3 volatilization are very large-between 115 and 245 millions of tons of nitrogen oxide. Background atmospheric levels of NH3 over Belgium, Denmark, and the Netherlands, which are intensive arable and livestock-raising countries, are often around 25ppm with peaks up to 75ppm NH3. Estimates of total N released into the atmosphere from these countries are especially high. The large releases of NH3 to the atmosphere over the last three decreases are due to (a) increased animal stocking levels, (b) increased human population, (c) increased use of artificial fertilizers, in the form of either NH4+ nitrate or urea, and (d) decreased, sinks for NH3 or NH4+ uptake. The first three go hand in hand. As material standards improve, humans move from plant-orientated to animal-based diets. This means more food has to be grown to feed animals and this can only be done by using more artificial fertilizer. Much could be done to reduce N losses associated with applications of N fertilizers due to NH3 volatilization and run-off of excess nitrate into ground waters. Direct injection of anhydrous NH3 or urea at the right depth into soil has not yet been extensively exploited. Even substituting urea for NH4+ in irrigation waters will reduce losses due to NH 3 volatilization below 2% in poorer regions where N is unduly expensive, and losses by this route tend to be greater because of higher temperatures. Removal of ammonia from the atmosphere: Once in the atmosphere, NH3 neutralizes sulphuric or nitric acids and, by decreasing acidity, promotes the oxidation of SO2 to sulphate by O3. Normally, atmospheric NH3 has an average lifetime of 0.5h before conversion to NH4+. At wind speeds of 10ms-1, therefore, a molecule of NH3 travels about 18km before it turns into NH4+. Measurement of rates of NH3 deposition is complicated because some intensively farmed lands give off more NH3 than they receive. On the other hand, fluxes towards damp acidic ecosystems are considerable and cannot be accounted for by stomatal uptake alone as they from perfect sinks for NH3. For example, the uptake rate of wet health land in the Netherlands may be as high as 100 kg N ha-1 a-1.

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In most areas where atmospheric levels of NH 3 are high, elevated concentrations of SO2 also occur. This leads to a phenomenon known as code position where fluxes are linked together. One explanation for this is that when NH3 turns into NH4+ then oxidation of SO2 into sulphate is enhanced. Removal of SO 3 from the atmosphere as ammonium sulphate at the surface then ensures that the high rates of code position of SO2 and NH3 are maintained. Similar processes occur in aerosol particles which form clouds. The hygroscopic nature of NH 4+ and sulphate causes these particles to attract more water vapour so they increase in size and eventually fall as rain, etc. Indeed, wet deposition of NH4 + as ammonium sulphate in rainfall is the major removal pathway of NH3 from the atmosphere. Effects of Ammonia: Effects on Plants: Most plants are affected visually by atmospheric NH3 when there has been an industrial spillage and high local concentrations are achieved. Generally, no visible or invisible effects are detected on even the most sensitive species at levels of 70 ppb NH 3 or below. However, there are some claims that deposition of NH3 and NH4+ on certain plants that prefer low levels of N induces leaching of potassium and magnesium which, over the long term, leads to mineral deficiencies. At higher levels of NH3 little effect on photosynthesis is detected but long-term exposures visibly injure sensitive conifers such as yew, spruces, and cypresses. However, this injury is usually associated with reduced frost hardiness and increased susceptibility to fungal attack. Vegetable and horticultural crops are generally more resistant. Cauliflowers and Brussels sprouts, however, may show characteristics black spots at levels of 0.7ppm NH 3 for 10 days as well as reduced frost hardiness. Effects of ammonia on human health: Atmospheric NH3 is not normally a hazard to health. Occasionally, industrial spillage release large amounts of NH3 which immediately react with the moist linings of the throat or the surface of the cornea to form ammonium hydroxide which then causes chemical burns. At much lower levels, the buffering of these layers is normally sufficient to absorb any NH 3 and very little penetrates to the lungs. Irritation of the eyes and throat occurs at levels of 350-700 ppm NH3 well above ambient atmospheric levels. However, physiological changes have been detected at much lower levels. For example, at 16ppm NH 3, levels of NH4+ and urea in the blood stream are increased. The TLVs vary from country to country. Most are around 25 ppm NH 3 for an 8h day. 1.8.9 Hydrogen Sulphide (H2S): Hydrogen Sulphide is well known for its rotten egg smell. It is produced by the reduction of sulphur. It is a very strong smelling substance and is gaseous at room temperature having a boiling point at -600C. It is slightly soluble in water at atmospheric conditions, but ground water

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may contain considerably higher concentration under pressure commonly found in deep aquifers. It imparts an unpleasant taste and odour to water even in small concentrations. It is not toxic in low concentrations that normally exist in the atmosphere (0.002ppm), but is toxic in high concentrations. The threshold limit value (TLV) of hydrogen sulphide is 10ppm. Sources and Sinks: Hydrogen Sulphide is a biological waste product from anaerobic bacteria decomposition of organic matter in the soil, or a by-product of reduction of sulphur from mineral deposits. It may be present in appreciable quantity in ground waters. In atmosphere, H 2S and SO2 coexist. Hydrogen sulphide is produced by the reduction of sulphate and organosulphur compounds by the bacterium Desulphovibrio desulphuricans and associated with methane thial (CH 3.S.H.). dimethyl sulphide (CH3.S.CH3) and carboxyl sulphide (C.O.S). All these species have objectionable odour, even at low concentrations. Hydrogen Sulphide is not so stable, and is readily oxidized in air. Effects: Exposure to hydrogen sulphide for short periods can result in fatigue. But high concentrations of H2S due to accidental release often cause fatalities. This occurs in the production and processing of sour gas and oil, which contain hydrogen sulphide. There are many incidences of leakages if H2S from natural gas processing plans killing hundreds of people. 1.9 Secondary air Pollutants Secondary air pollutants are chemical products that are formed from the reactions of various primary air pollutants with one another; some of the important secondary pollutants are products of photochemical reactions;

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Photo Chemical Smog formation: Coal induced smog is formed by the interaction of sulphur dioxide, smoke and water to form sulphuric acid mist. It is associated with adverse meteorological conditions (inversion conditions) when air movement is restricted during winters in industrialized areas, where fossil fuel is used, as happened during London smog episode. That is why, coal induced smog is generally referred as London smog. In fact, the world smog originally means an odd combination of smoke and fog prevalent in London. This is, however, chemically reducing with high levels of SO2 and is called reducing smog. It is also sometimes referred as classical smog. Photochemical smog, is an oxidizing smog having a high concentration of oxidant. Photochemical smog is, in fact, a mixture or reactants and products that result from the interaction between volatile organic compounds (VOCs) and oxidants (such as NOx, O3, CO etc.). The primary pollutants in photochemical smog are nitric oxide and hydrocarbons. These primary pollutants convert rapidly to the secondary pollutants like ozone, organic nitrates (e.g. PAN, peroxyacetyl nitrate), oxidized hydrocarbons and photochemical aerosols in the presence of sunlight. Photochemical smog is associated with adverse meteorological conditions (inversion conditions) when air movement is restricted in summers in highly motorized areas. The first noticed incidence of photochemical smog was in Los Angeles in USA, and thus, it is sometimes referred as Los Angeles smog. It is characterized by brown and hazy fumes, which reduce visibility, cause eye and lung irritation, damage crops, leads to the cracking of rubber, damaged of plants, etc. In a vastly oversimplified form, the production of photochemical smog can be represented by the following equation:

But in actual practice, there are many complex reactions which take place in the formation of photochemical smog. The origin of photochemical smog is the photolytic decomposition of nitrogen dioxide. Although nitric oxide is the predominant form of NOx emissions, it can react with ozone to form NO2. This nitrogen dioxide leads to subsequent reactions through its decomposition, and thus forming the NO2 photolytic cycle as represented by the following equations:

Where M is a third molecule (usually N2 or O2 in the atmosphere) that absorbs the excess energy from the reaction; without M, O 3 will possess too much energy for it to be stable and will simply dissociate back to O2 and O. It can be deduced from the above three equations, that the NO2 photolytic cycle does not produce a net increase in NO2 or ozone. Hence, if this cycle is not distributed there will be no undesirable effect (provided that the starting

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concentrations of the species are low). However, human activities emit not only No x to the atmosphere but also carbon monoxide hydrocarbons and carboxyl compounds. By their reactions with hydroxyl radicals, they disturb the NO2 photolytic cycle and, thus, not only prevent the reaction of ozone with NO but also cause the accumulation of ozone, peroxyacylnitrates (PAN), and other constituents of photochemical smog. In addition, the photolytic decomposition of carbonyl compounds also disturbs this cycle. Some of the important photochemical smog reactions that take place in the atmosphere are as under: Normal NO2 photolytic cycle:

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Production of hydroxyl radical: O3 + hv O+ + H2O O+ + O2 2OH (Hydroxyl radical)

Chain and disturbance reactions: CO + OH H + O2 HO2 + NO CO2 + H HO2 (hydroperoxyl radical) NO2 + OH

RCHO + OH (Aldehydes) RC(O) + O2 RC(O)O2 + NO2

RC(O) + H2O Acetylradical RC(O)O2 (Acetyl peroxy radical) RC(O)O2NO2 (PAN)

RC(O)O2 + NO RC(O)O + O2 RO2 + NO RNO3

NO2 + RC(O)O RO2 + CO2 (Alkyl nitrate)

RO2 + NO RO + O2 HO2 + NO RH + OH R + O 2 RCHO + hv HCO + O2

NO2 + RO RCHO (Stable aldehyde) NO2 + OH R + H2O RO2 R + HCO CO (Carbon Monoxide) + HO2 + HO2

Terminating Reactions: OH + NO2 RO2 + NO RC(O)O2 + NO2 HNO3 RNO3 RC(O)O2NO2

The end product of these photochemical reactions is photochemical smog consisting of air contaminants such as ozone, PAN, aldehyde, ketones, alky nitrates and carbon monoxide.

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1.10 Global effects of air pollution: Air pollution problems are not necessarily confined to a local or regional scale. atmospheric circulation can transport certain pollutants far away from their point of origin, expanding air pollution to continental or global scales. It can be truly be said that air quality problems know no international boundaries. Scales of pollutant transport in the atmosphere can be described as i) Local, ii) Regional, iii) Continental and iv) Global. The global effects of air pollution may be i) Global Warming (green house effect), iii) Acid rain 1.10.1 Global Warming (Green House Effect) Incident solar energy as short-wave radiations, mostly in the form of visible light, is absorbed by the earths surface and emitted into space as long -wave infrared (heat) radiations. There are several gases in the earths atmosphere, primarily water vapou r and CO2 that are transparent to the incoming short-wave radiations but are nearly opaque to the reflected longwave radiations. Thus much of the earths heat is retained, which causes a warming effect. This phenomenon is known as green house effect, and the gases that have the ability to absorb reflected long-wave radiations and produce this effect are called green-house gases. it is due to the natural occurrence of the green-house effect (i.e. presence of water vapour and CO2) that there is a higher atmosphere equilibrium temperature; otherwise the earths mean surface temperature would have been 180C instead of the present +170C. There is concern that increasing concentrations of carbon dioxide and other trace greenhouse gases due to human activities will enhance the green-house effect and causes global warming. The greenhouse gases which cause greenhouse warming of the global climate (excluding water vapour) are carbon dioxide, methane and a number of other trace gases like nitrous oxide (N2O), tropospheric ozone, chloro-fluoro carbons (CFCs), hydro-chloro-fluoro carbons (HCFCs), methychloroform (CH3CCL3), carbon tetrachloride (CCL4), sulphurdioxide, fluorine, bromine, iodine, and compounds of nitrogen and sulphur. The principal sources of green house gases are summarized. While Fig shows the estimated contributions of greenhouse gases to global warming. ii) Ozone layer depletion (ozone hole), and

Estimated contributing of greenhouse gases to global warming in 1980s

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Major sources of greenhouse gases S. No 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. Gases CO2 CH4 N2O CFC 11 O3 CFC 12 CFC 113 HCFC 22 CH3CCL3 CCL4 Major Sources Fossil fuel combustion, deforestation, respiration Wetlands, anaerobic decomposition of organic wastes, termites Natural soils, fertilizers, fossil fuel combustion Photochemical reactions in troposphere, transport (diffusion) from stratosphere Manufacturing of foams, aerosol propellant Refrigerant, aerosol propellant, manufacturing of foams Electronics solvent Refrigerant, production of fluoropolymers Industrial degreasing solvent Intermediate in production of CFC 11, CFC 12, solvent

The greenhouse effect at its natural level is very essential for life to exist on this planet (earth); but its increase (i.e. enhanced greenhouse effect), as is actually taking place, is feared to cause global climate changes of irreversible and highly destructive type. The concentrations of CO2 and other greenhouse gases in the atmosphere are rising alarmingly, and making it clear that we are going to experience a general warming-up of the atmosphere. In fact, some warming-up from 0.3 to 0.70C has already taken place during the last one century. Effects Speculated scenarios based on global warmings include the following i. ii. Increase in global mean temperature at about 0.30C per decade. There may be more warming-up in higher latitudes during late autumn and winter, than in tropics. In tropics, the expected rise would be less than the global average; and in temperature regions, more than the global average. iii. Flooding of many coastal areas (lands and islands) due to rising sea levels resulting from the thermal expansion of the oceans, the melting of glaciers and ice sheet, and probably, from the melting of polar ice caps. One set of response predicted for average global temperature and sea-level rise is shown in table 2. Rises in sea-level of this magnitude would be disastrous for low-lying areas of Netherlands, Maldives, and other such area. Prediction of a sea-level rise Year CO2 conc. (ppm) Temp. rise (0C) Sea-level rise (cm) 1990 354 2030 470 1.1 18 2060 600 2.0 38 2100 850 3.3 65

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iv.

An increase in global average temperature is predicted to increase the amount of water vapour in the atmosphere (because saturated vapour pressure increases with temperature), thereby increasing the long-wave optical depth, trapping more long-wave radiation and increasing the temperature further.

v.

Increase in global average temperature will lead to dislocation of suitable land for agriculture, and thus may adversely affect the world food production. For instance, the wheat growing areas in the northern latitude will shift towards poles, i.e. from fertile lands (in USA, Canada and Russia) to poor soils (in the north pole). In case of India, it is predicted that the wheat production will drop in the fertile northern belt.

vi.

The dislocation and possible extinction of certain biological species and ecosystems cannot be ruled out.

vii. Increase in the severity of storms viii. Other effects include more evapotranspiration in tropics, alternation in existing precipitation patterns, effect on hydrological cycle, effect on human health (like heat strokes), etc. Control Since, Co2 accounts for about half of the greenhouse gases and there is a strong evidence linking temperature and CO2 changes, therefore, the nest way to solve this problem of global warming due to increasing concentration of CO 2 is to use sources of energy that do not produce carbon dioxide such as wind, hydroelectric, geothermal, solar, tidal and nuclear energy. Similarly, the emissions of other greenhouse gases in the atmosphere should also be stopped to prevent the enhanced greenhouse effect.

1.10.2 Ozone Layer Depletion (Ozone Hole): In stratosphere, ozone is found in a concentrated thick layer at varying heights from 16km to about 40km at different latitudes. Its concentration, in ppmv (parts per million by volume), at tropopause is less than 1.0 and then starts increasing to reach a maximum value of about 8.0 at about 30km, and then again starts decreasing to a value of 2.0 at 40km. Its value reaches to zero at about 100km. In the stratosphere, O3 is formed naturally when oxygen is dissociated by ultraviolet solar radiations in the wave-lengthe region of 80 to 240nm.

Where M is any third body molecule (mostly likely N2 or O2 in the atmosphere) that remains unchanged in the reaction. The ultraviolet radiations in the region of 200 to 300 nm can also dissociate the ozone:

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In this (above) reaction, ozone portrays the absorption of ultraviolet-B radiations and hence is responsible for the removal of UV-B radiations (= 280 to 320 nm) that would otherwise reach the earths surface. The concern is that, any process that depletes stratospheric ozone will increase the UV-B radiations reaching the earths surface. Increased UV -B will be lead to increased incidence of skin cancer and could have deleterious effects on certain ecosystems. The three important areas, where human activity can influence the ozone cycle, have been the direct emission of NOx by supersonic transport flying above the tropopause, additional transport of nitrous oxide (N2O) as a result of increased use of nitrogenous fertilizers, and the formation of atomic chlorine in the stratosphere from chloro-fluoro carbons (CFCs) (used as refrigerant, aerosol propellant and industrial solvent) released in the troposphere. Another class of compounds, halons, are also ozone depleting compounds. Halons are bromo-chlorofluorocarbons or bromo-flurocarbons that are widely used in fire extinguishers. Although the emissions of halons and thus their atmospheric concentrations are much lower than the most common chloro-flurocarbons (CFCs), but they are 3 to 10 times more destructive than the CFCs. The Nox emission from supersonic transport in stratosphere or the diffusion of NO x in stratosphere from the lower atmosphere, cause ozone depletion in the following way:

The net effect on this sequence is the destruction of two molecules of ozone, since the oxygen atom (O) would have combined with oxygen molecule (O 2) to form ozone. Most significantly, the NO acts as a catalyst because it is not consumed, and therefore can participate in the reaction sequence many times. The CFCs (like chloro-fluoro methane or Freon) are inert in normal and physical reactions, but they get accumulated in greater amounts at high altitudes, and there in stratosphere, they release chlorine atoms under the influence of UV radiations (<240nm). For example, CFC-12 would photolyze forming CL and CLO radicals.

The following reactions would then occur

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In this sequence the chlorine atom acts as a catalyst, and two O3 molecules are destroyed. Before the CL is finally removed from the atmosphere (in 1-2 years) by precipitation, each CL atom will have destroyed thousands of ozone molecules. The first evidence that stratospheric ozone depletion is occurring comes from the discovery of the Antarctic ozone hole that could have been caused by human produced pollutants. This hole formation or the level of ozone depletion is increasing yearly. In the vertical profile, the most affected zones are around 40 to 50 km and the lower stratosphere below 20 km. The various studies carried out show that globally, stratospheric ozone concentrations have declined during the winter, spring and summer in both the northern and southern hemisphere at middle and high latitudes. The declines are most evident during winter months. In north Europe and America, during late winter and early spring, ozone is getting depleted and it is feared that in near future more ozone holes may develop. The studies carried out in India show that a good part of the country has low ozone belt, and further depletion could cause serious problems. Effects The thick shield (layer) of ozone present in the stratosphere is extremely useful as is prevents the UV-B radiations coming from sun to reach the earths surface; and thus the plants, animals and human beings escape from the hazardous UV-B radiations. Increase in UV-B radiations have damaging effects on the DNA of exposed cells of organisms and can cause mutation and skin cancer. Other effects are climate changes due to global warming, nonformation of stratospheric winds, and deleterious effect on certain ecosystems. Control The only practical warming solution to this problem is to accelerate the phaseout and complete elimination of the production of CFCs halons, carbon tetrachloride and methychloroform. Though such steps will stop the increase of CFCs in the atmosphere; but, because of their long life-times, the already emitted CFCs will remain in the atmosphere for centuries. 1.10.3 Acid Rain The term acid rain was first used by Robern A. Smith in 1872. Since then numerous western investigators added insight to this emerging environmental challenge. The term acid rain is used to describe all precipitation and / or deposition, which is more acidic than normal. It results, when gaseous emissions of particularly Sox and NO x interact with water vapour and sunlight, and are chemically converted to strong acidic compounds such as sulphuric, sulhurous, nitric and nitrous acids. When these compounds (acid gases or their precursors or acid particles) along with other organic and inorganic chemicals are deposited on

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the earth as aerosols and particulate, the deposition is called as Dry deposition; and when these are carried to the earths surface by precipitation. However, dry deposition is estimated to be a small fraction of total acid deposition. Generally, clean rain is slightly acidic as it dissolves varying amounts of naturally occurring carbon dioxide from the atmosphere. The lowest pH level which can be produced by carbonic acid (orCO2) is 5.6. Therefore, the precipitation or rain is said to be clean rain upto a pH of 5.6, which is the natural background pH of rain water.

Hence, acid rain, on precipitation, is defined as the one which has a pH less than 5.6. The principal species associated with dry-acid deposition are SO2(g), acid sulphate particles (H2SO4 and NH4HSO4), and HNO3(g), while the principal dissolved acids are H2SO4 and HNO3. Other acids, such as hydrochloric acid (HCL) and organic acids, usually account for only a minor part of the acidity. Although organic acids can be significant contributions in remote areas. Both acid particles and gases can be incorporated into cloud droplets. Particles are incorporated into droplets by nucleation, impaction, Brownian movement, diffusiophroesis (transport into the droplet induced by the flux of water vapour to the same surface), thermophoresis (thermally induced transport to a cooler surface), and electrostatic transport. Advective and diffusive attachment dominate all other mechanisms for pollutant gas uptake by cloud droplets. Most of the H2SO4 in precipitation is due to the diffusion of SO2 into the cloud droplets, where it is oxidized to H2SO4 by one of the several mechanisms; while most of the NHO3 in precipitation is due to the diffusion of HNO 3(g) into the droplets. The following equations summarize the reactions for sulphuric acid and nitric acid formation:

Effect: The ecological impact of acid rain is quite serious. It is likely to produce irreversible changes. The acidification of streams and lakes affects aquatic animals and plants. High acidity results in reduced fish population. Green algae and many forms of bacteria, which are essential to aquatic systems, will be killed due to acidity. Also at low pH the rate of decomposition of

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organic matter in water bodies is reduced, which increases the degree of water pollution. Acid rains can affect vegetation and soil in many ways. It adversely affects the growth of trees, and hence affects the forests that results in consequent vanishing of greenery. Due to acid rains, the plant nutrients, such as potassium, are gradually leached out of the soil; and the population of earth worms is reduced, thus affecting the fertility of soil. Acidic air pollutants have also been responsible for many other damaging effects like corrosion of metals weakening or disintegration of textiles, paper and marble, and works of art and architecture. The building and sculptural materials (e.g. marble, limestone, etc.) become pitted and weakened mechanically as a soluble sulphates are leached out by acid rain.

Acid deposition, in fact, shows a correlation with the prior movement of the air mass over major sources of Sox and NOx emissions. The acidity in Swedish lakes and rivers is due to emissions from highly industrialized areas of UK and central Europe. The British parliament building has suffered serious damage from the presence of sulphuric acid in rainfalls. The Taj Mahal is seriously affected due to pollutants released, particularly, from Mathura refinery. Similarly, in Canada trees and aquatic life in lakes are being killed by acid rain, 60% of which originates from USA. Control: One of the simplest solutions to the problem is to neutralize the acid with lime. But it is quite expensive, especially when large areas of water-bodies have to be limed. Further, large scale liming may create its own ecological problems. probably, the best way to overcome this problem is reduced emissions of Sox and Nox from anthropogenic sources. Effective air pollution prevention and control measures are required for both stationary and mobile sources of air pollution.

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