Air Pollutants

Types and Classification Air pollutants can present a real danger to living organisms as well as the wider environment. Air pollutants come in the form of gases and finely divided solid and liquid aerosols. Aerosols are loosely defined as any solid or liquid particles suspended in the air. Air pollutants can also be of primary or secondary nature. Primary air pollutants are emissions entering the atmosphere and retaining their original chemical form. Secondary air pollutants are the ones that are formed as a result of reactions, chemical and photochemical (using sunlight), between primary pollutants and other elements in the atmosphere, such as ozone. Possibly one of the most important characteristics of air pollutants is their trans-boundary nature - they can easily travel and affect the areas far away from their points of origination. Gaseous Air Pollutants Following are three main types of gaseous air pollutants:

Sulfur dioxide (SO2) Oxides of nitrogen (NOx = NO + NO2) Ozone (O3)

Sulfur dioxide and nitric oxide (NO) are the primary air pollutants, and ozone is a secondary pollutant (though there are negligible direct emissions of the gas itself). Nitrogen dioxide (NO2) is both a primary and secondary air pollutant. Other important gaseous pollutants are: ammonia, carbon monoxide, volatile organic compounds (VOCs) and persistent organic pollutants (POPs). Sulfur Dioxide (SO2) Sulfur dioxide is a colorless gas with a pungent, suffocating odor. It is a dangerous air pollutant because it is corrosive to organic materials and it irritates the eyes, nose and lungs. Anthropogenic Sources of Sulfur Dioxide Emissions Sulfur is contained within all fossil fuels, and is released in the form of sulfur dioxide (SO2) during fossil fuel combustion. Fossil fuel combustion accounts for almost all anthropogenic (human-caused) sulfur emissions. Below is a breakdown of all the significant sources of sulfur dioxide emissions:

Energy Production o Electric power generation o Petroleum refining o Other combustion Commercial and residential use Combustion for industry use Production processes Extraction and distribution of fossil fuels Transport o Road transport o Other Transport (such as aviation, ships, trains).

Currently, the most important sources of sulfur dioxide emissions (as a result of fossil fuel combustion) are electric power generating plants. Natural Sources of Sulfur Dioxide Emissions There are also significant sulfur emissions generated by natural sources. The main natural sulfur emissions come in the reduced forms of sulfur compounds such as:

hydrogen sulfide (H2S) carbon disulfide (CS2) carbonyl sulfide (COS)

and in the organic forms of:

methyl mercaptan (CH3SH) dimethyl sulfide (DMS) (CH3SCH3) dimethyl disulfide (DMDS) (CH3SSCH3)

Most of these compounds get oxidized to sulfur dioxide or to sulfate aerosols in the atmosphere. Marine phytoplankton produce dimethyl sulfide (DMS) which is then oxidized to SO2 in the atmosphere; decay processes in soil and vegetation produce H 2S (as one of sulfur compounds); and SO2 is emitted into the atmosphere by volcanoes. Around 90% of all natural sulfur emissions come in the form of DMS. Effects of Sulfur Dioxide Emissions Sulfur dioxide found in the air produces following effects:

Irritates eyes, nose, throat Damages lungs when inhaled As part of acid rain: o acidifies lakes and streams o destroys plant and fish life in lakes and streams o may deplete mineral nutrients in the soil o may cause reduction of forest and agricultural yields o corrodes metals

damages surfaces of buildings. Oxides of Nitrogen

o

Most of nitrogen oxides' production comes from the reaction of atmospheric nitrogen and oxygen within the combustion chamber. The two main nitrogen oxides are nitric oxide (NO), or nitrogen monoxide, and nitrogen dioxide (NO2) the sum of which is equal to NOx. Nitric oxide (NO) is a colorless gas. Nitrogen dioxide (NO2) is a gas of reddish-brown color with a distinct sharp, biting odor. Combustion of fuels always produces both NO 2 and NO. But almost 90% of the NO X combustion product is in the form of NO which is then oxidized to nitrogen dioxide (NO 2) in the air. Therefore, only a small percentage of NO 2 found in the atmosphere is directly emitted there in this form. The rest has been formed as a result of chemical reactions in the atmosphere itself. Anthropogenic Sources of Nitrogen Oxide Emissions Road transport (motor vehicles) is by far the largest contributor of nitrogen emissions (in contrast, it contributes a very small proportion to sulfur dioxide emissions. For example, road transport contributed nearly half of all nitrogen emissions, followed by contributions from electric power generating plants which only contributed around 20% of total nitrogen emissions. Below is a breakdown of the significant sources of emissions of nitrogen oxides:

Road transport Other Transport Energy Production o Electric power generation o Petroleum refining o Other combustion Combustion for industry use Production processes Extraction and distribution of fossil fuels.

Natural Sources of Nitrogen Oxide Emissions Nitric oxide (NO) is also emitted by soils. Some estimates suggest that the soil production of NO may be around 2 5% of its production from fossil fuel combustion. Effects of Nitrogen Dioxide (NO2) Emissions When inhaled, nitrogen dioxide becomes a serious air pollutant which may: Cause pulmonary edema (accumulation of excessive fluid in the lungs) Be part of acid rain (destroying fish and plant life in lakes, damaging surfaces of buildings etc) Contribute to photochemical smog.

Ammonia Ammonia is a colorless, pungent, hazardous caustic gas composed of nitrogen and hydrogen. Ammonia emissions are also grouped as NH y which is a sum of NH3 and NH4. Sources of Ammonia Emissions Agriculture is by far the biggest source of ammonia emissions. Livestock farming and animal waste account for the biggest percentage of total ammonia emissions which are due to the decomposition of urea from large animal wastes and uric acid from poultry wastes. Below is a breakdown of their major sources:

Livestock contributes more than 50% of all emissions Fertilizer application Oceans Vegetation Biomass burning

Effects of Ammonia Emissions Exposure to very high concentrations of gaseous ammonia in the air may result in lung damage and even death. Carbon monoxide (CO) Carbon monoxide is a colorless, odorless gas which is highly toxic to humans. The combustion of carbon-based fuels produces carbon dioxide (CO 2). But not all such combustion is complete, and this leads to the production of carbon monoxide (CO). Motor vehicles and industry are among the largest anthropogenic sources of carbon monoxide emissions. Effects of Carbon Monoxide Emissions Carbon monoxide is the most common type of fatal poisoning in many countries around the world. Exposures to carbon monoxide may lead to :

Toxicity of the central nervous system and heart Severe effects on the baby of a pregnant woman Headaches and dizziness Problems with getting oxygen supplied to some body parts which may be lifethreatening.

Volatile Organic Compounds (VOCs) Volatile organic compounds (VOCs) are defined as organic compounds which easily evaporate and enter the atmosphere. VOCs may include a wide range of organic air pollutants, from pure hydrocarbons to partially oxidized hydrocarbons to organic

compounds containing chlorine, sulfur, or nitrogen. The definition of VOCs did not include methane compounds (non-methane VOCs: NMVOCs) since the atmospheric concentration of methane was considered to be a stable natural background. But it was ultimately recognized that methane is also an anthropogenic air pollutant that comes from intensive animal and rice production. Anthropogenic Sources of Volatile Organic Compounds The major anthropogenic sources of VOCs include :

Solvent Use (including paints, adhesives, aerosols, metal cleaning and printing) Road transport (emissions from fuel / petroleum use) Production processes Extraction and distribution of fossil fuels

The substantial NMVOC emissions occur during the following processes:

Painting (evaporation of solvents) Oil production (flaring and venting of gas) Oil refining (flaring and fugitive emissions) Distribution of oil or refinery products (evaporation from storage, displacement losses when venting tanks) Dry cleaning (final drying of clothes) Production of alcoholic drinks (breweries and distilleries) Arable farming (crop growing, silage manufacture, sludge spreading)

Natural Sources of Volatile Organic Compounds Not a lot is known about the natural emissions of VOCs. The forests are the primary natural sources of VOC emissions. Tropical forests are estimated to produce about half of all global natural non-methane VOC emissions. Plants synthesize many organic molecules and release some VOCs (including a range of terpenes) into the atmosphere. Effects of Volatile Organic Compounds VOCs may produce the following effects:

Some aromatic compounds such as benzene, toluene and xylene are potential carcinogens and may cause leukemia Contribute to sick building syndrome indoors As facilitators in ozone formation, VOCs may indirectly contribute to respiratory problems and other ozone-related problems

Ozone (O3) Ozone (O3) is a colorless, poisonous gas with a sharp, cold, irritating odor. Ozone can be found in: o the stratosphere, one of the upper layers of the atmosphere, where it occurs naturally, and

the troposphere, the lowest layer of the atmosphere, where it occurs both naturally and as a result of human-generated emissions.

The natural stratospheric ozone is considered to be of beneficial nature it keeps harmful excessive ultraviolet sunlight from reaching the surface of the Earth. Ozone which is formed in the troposphere as a result of anthropogenic emissions of primary pollutants, has negative effects on humans and the natural environment. And from this point of view it is an air pollutant. This human-caused ozone in the troposphere is a secondary pollutant because it is produced by the reaction of primary pollutants, nitrogen oxides and hydrocarbons [including VOCs], in the presence of sunlight. The tropospheric ozone is the main component of the photochemical smog. A photochemical smog (of brown-yellow color) is a product of the chemical reaction between sunlight, nitrogen oxides and VOCs, which results in the formation of ozone and airborne particles. Effects of Ozone as an Air Pollutant Ozone in the troposphere can have the following negative effects on animals (including humans) and the natural environment:

Irritation of the respiratory system causing coughing, throat irritation and an uncomfortable sensation in the chest Susceptibility to respiratory infections Compromised lung function harming the breathing process which may become more rapid and more shallow than normal Inflammation and damage to the lining of the lungs Aggravation of asthma Reduction in agricultural yields

Particulate Matter : Airborne Particles Airborne particles present one more type of air pollutants. They are tiny fragments of solid or liquid nature suspended in the air (aerosols). Solid particles between 1 and 100 m (micrometres) in diameter are called dust particles, while solid particles less than 1 m in diameter are called fumes, or smoke. Anthropogenic Sources of Airborne Particles Anthropogenic particles account for around 10% of the total amount of particles in the atmosphere. Fossil fuel combustion is one of the main processes which causes vast amounts of particles to be emitted into the atmosphere. The major anthropogenic sources of airborne particles are:

Road transport Power generating plants Production processes (such as dust blown away by winds from construction sites)

Natural Sources of Airborne Particles Main natural sources of particles are :

Erosion of soil by wind which generates dust particles that travel around the globe Evaporation of droplets of sea water resulting in sea salt crystals being suspended in the air Volcanoes Forest fires Living vegetation

Effects of Airborne Particles Particles less than 10 m in diameter are of biggest concern to human and animal health as they can be easily inhaled and get trapped in the respiratory system. The particles of this size have very low gravity-related sedimentation rates and may therefore remain in the atmosphere for days before being washed out by rain or attached to vegetation or buildings. Airborne particles may cause:

Asthma Lung cancer Cardiovascular problems

Chlorofluorocarbons (CFCs) CFCs were safely used for years in cleaning products and as coolant for refrigerators. Though not toxic during initial use, CFCs dissolve into the atmosphere and destroy the upper ozone. The upper ozone protects Earth from radiation generated by the sun, and the depletion of the upper ozone can increase the risk of cancer in humans. Persistent Organic Pollutants (POPs) Persistent organic pollutants are compounds which are resistant to degradation and persistent in the environment, with half lives of more than one year in the soil or sediment and in the atmosphere. Such compounds may include dioxins, furans, polychlorinated biphenyls (PCBs) and organochlorine pesticides such as DDT. They enter the food chains via the process of biomagnification, get accumulated in human and animal tissue, and are capable of long range transport through being attached to airborne particles.

Sources of Persistent Organic Pollutants Some POPs are used as pesticides. Others are used in industrial processes as well as in the production of goods such as solvents, polyvinyl chloride and medicines. Effects of Persistent Organic Pollutants Exposure to persistent organic pollutants takes place through diet (specifically, consumption of animal fats), environmental exposure or accidents. POPs may lead to :

Death and illness including disruption of endocrine, reproductive and immune systems Neurobehavioral disorders Cancers

When POPs are present in the atmosphere in the form of aerosols, they may be classified as airborne particles rather than gaseous pollutants. Acid Rain Acid rain is any form of precipitation that is noticeably more acidic than normal rain. A pH of less than 5.6 is usually considered to indicate acid rain. The slight acidity of normal rain is the result of natural carbon dioxide dissolving in atmospheric moisture to form carbonic acid. Sulfur oxides from volcanic eruptions are other natural sources of acids in rain. Nitrogen oxides from lightning strikes and plant decay also contribute to modest pH of natural rain. The high acidity of acid rain is due to excess man-made sulfur and nitrogen oxides reacting with water in the atmosphere. Oxides of sulfur and nitrogen are released from sources such as automobiles and coal - burning power plants. Sources of Acid Rain Natural Acid Rain The phenomenon of acid rain was discovered in Great Britain in the late 1800's, but was then essentially forgotten until the 1960's. It refers to precipitation that is significantly more acidic than natural, unpolluted rain which itself is mildly acidic due to the presence of carbon dioxide dissolved in atmospheric moisture forming carbonic acid: CO2(gas) + H2O(liquid) H2CO3(aq)

The H2CO3 (aq) is a weak acid, meaning it only partially ionizes to release H +(aq), with a resultant reduction in the pH of the system. pH is the - log [H +(aq)] therefore as the concentration of the H+(aq) increases the ph decreases. This partial ionization occurs in equilibrium as carbonic acid only ionizes 1.7%: H2CO3 (aq) H+(aq) + HCO3- (aq)

Due to this source of acidity, the pH of unpolluted, natural rain is about 5.6. Only rain that is appreciably more acidic than this, with a pH of less than 5.0 is considered to be truly acid rain. Acid Rain The two predominant acids in acid rain are sulfuric acid (H 2SO4) and nitric acid (HNO3). These acids are created during the transport of the air mass that contains the primary pollutants. Generally speaking, acid rain is precipitated far downwind from the source of the primary pollutants, namely gaseous sulfur dioxide (SO 2) and nitrogen oxides such as NO2. Both nitrogen and sulfur oxides are known to react with water in the atmosphere to form acids. These reactions are the source of polluted acid rain. The formation of acid solutions by SO2 is explained as a two - step process. Assume that sulfur dioxide molecules first react with water molecules, forming molecules of sulfurous acid: SO2(gas) + H2O(liquid) H2SO3(aq)

Sulfurous acid molecules then react with water producing an equilibrium with H +(aq) and hydrogen sulfite. Sulfurous acid is considered a weak acid as it only partially ionizes into H+(aq): H2SO3(aq) + H2O(liquid) H+(aq) + HSO3- (aq)

Sulfur dioxide can also react with oxygen or ozone to form sulfur trioxide: 2SO2(gas) + O2(gas) SO2(gas) + O3(gas) 2SO3(gas) SO3(gas) + O2(gas)

The sulfur trioxide then reacts with atmospheric moisture to form sulfuric acid: SO3(gas) + H2O(liquid) H2SO4(aq)

This sulfuric acid is a strong acid that ionizes 100% in atmospheric precipitation to produce H+(aq) ions: H2SO4(aq) H+(aq) + HSO4-(aq)

These H+(aq) are responsible for the acidic effects of acid rain. Car engines burn gasoline using air as a source of oxygen. The primary component of air is nitrogen and its exposure to the high temperatures inside car engines forms the pollutant nitrogen monoxide (NO). Sunlight provides the energy that promotes a series of secondary reactions producing nitrogen dioxide and ground level ozone that both participate in acid rain reactions.

Direct scavenging of NO2 atmospheric water contributes little nitric acid (HNO 3) on account of the low solubility of NO2 in water: 2NO2(gas) + 2H2O(liquid) HNO2(aq) + HNO3(aq) Acid rain containing considerable amounts of nitric acid likely originated without water: NO2(gas) + O3(gas) NO3(gas) + O2(gas)

The gaseous NO3 then reacts with any reactive hydrogen donor ( X ) in the atmosphere: NO3(gas) + XH(gas) HNO3(aq)

Nitric acid like sulfuric acid is strong an completely ionizes into aqueous hydrogen and nitrate ions: HNO3(aq) H+(aq) + NO3- (aq)

Effect of Acid Rains on Metals Corrosion of Copper Metal In normal atmospheric exposure to carbonic acid (H 2CO3) copper and copper alloys form a layer of copper carbonate - a green substance also called patina. This patina (CuCO3) actually serves to protect the copper underneath from further corrosion. The insoluble copper carbonate tightly adheres to the surface preventing further contact with acid rain. However, the patina is a pale and unsightly green that detracts from the appearance of many copper structures and monuments. If you have ever visited Charlottetown, Prince Edward Island you may be familiar with this as the War Memorial in the downtown area is heavily coated in patina. This reaction begins with the release of gaseous carbon dioxide into the atmosphere from respiration or in the form of emissions from industrial processes. The CO2 dissolves in atmospheric moisture to form carbonic acid: CO2(gas) + H2O(liquid) H2CO3(aq)

The acidic properties of carbonic acid have no effect here as the H +(aq) do not take an active role in the reaction. The carbonate (CO32-) polyatomic ion is the reactive species that oxidizes the copper into patina and allows the hydrogen gas to escape: H2CO3(aq) + Cu(solid) Corrosion of Iron The most familiar and costly example of corrosion is the formation of rust on iron. Iron and steel structures are highly susceptible to corrosion, and their protection costs billions of dollars annually. The chemistry of corrosion under atmospheric conditions is extremely complex and is catalyzed by H+(aq) , explaining why increased acid precipitation causes CuCO3(solid) + H2(gas)

increased rates of corrosion. Oxygen gas and water must also be present for Iron to rust. Rusting is a redox reaction, involving the loss and gain of electrons between reactants. An electrochemical cell is created with impurity sites in the iron acting as cathodes for the reduction of O2 gas and a region of the metal surface serving as the anode, where the oxidation of iron occurs: 2Fe(solid) 2Fe2+(aq) + 4e-

The electrons given up by the iron reduce atmospheric oxygen to water at the cathode: O2(gas) + 4H+(aq) + 4e 2H2O(liquid)

Note this reduction half - reaction occurs in an acidic medium. The H+(aq) are provided, along with the water required, by acid rain. Therefore, as acid precipitation increases the rate of corrosion. Oxygen and water are obviously abundant therefore the rusting of iron is limited to the availability of H+(aq) from acid precipitation. The Fe2+(aq) ions formed at the anode are further oxidized by oxygen the overall redox equation: 4Fe2+(aq) + 3O2(gas) + 6H2O(liquid) 2Fe2O3 .6H2O(solid)

This hydrated form of iron(III) oxide is known as rust. Effects of Air Pollution on Agricultural Crops

Chlorosis : The loss or reduction in chlorophyll is known as chlorosis and is responsible for yellowing of the plant leaves.

Necrosis : The dead area on a leaf structure is referred to as Necrosis. The symptoms appear as flecking, bronzing or bleaching of the leaf tissues.

Epinasty : Epinasty is the downward curvature of the leaf due to higher growth rate on the upper surface.