Edited from version at http://www.aeat.co.uk/netcen/airqual/kinetics/



The Chemistry of Atmospheric Pollutants




A variety of air pollutants have known or suspected harmful effects on human health and the environment. In most areas of Europe, these pollutants are principally the products of combustion from space heating, power generation or from motor vehicle traffic. Pollutants from these sources may not only prove a problem in the immediate vicinity of these sources but can travel long distances, chemically reacting in the atmosphere to produce secondary pollutants such as acid rain or ozone.


Evolutionary Trends in Pollution Problems

In both developed and rapidly industrialising countries, the major historic air pollution problem has typically been high levels of smoke and SO2 arising from the combustion of sulphur-containing fossil fuels such as coal for domestic and industrial purposes. Smogs resulting from the combined effects of black smoke, sulphate/acid aerosol and fog have been seen throughout Northern European cities for centuries, and still occur in many parts of the developing world.

In economically developed countries, however, this problem has diminished over recent decades as a result of changing fuel-use patterns; the increasing use of cleaner fuels such as natural gas, and the implementation of effective smoke and emission control policies. These long-term changes in air pollution climate are also seen, often occurring very rapidly, in many developing countries.

In both developed and developing countries, the major threat to clean air is now posed by traffic emissions. Petrol- and diesel-engined motor vehicles emit a wide variety of pollutants, principally carbon monoxide (CO), oxides of nitrogen (NOx), volatile organic compounds (VOCs) and particulates, which have an increasing impact on urban air quality.

In addition, photochemical reactions resulting from the action of sunlight on NO2 and VOCs from vehicles leads to the formation of ozone, a secondary long-range pollutant, which impacts in rural areas often far from the original emission site. Acid rain is another long-range pollutant influenced by vehicle NOx emissions.

In all except worst-case situations, industrial and domestic pollutant sources, together with their impact on air quality, tend to be steady-state or improving over time. However, traffic pollution problems are worsening world-wide. The problem may be particularly acute in developing countries with dramatically increasing vehicle fleets, infrastructural limitations, poor engine/emission control technologies and limited provision for maintenance or vehicle regulation.

Below is an introduction to the principal pollutants produced by industrial, domestic and traffic sources.

Particulate Matter
Nitrogen Dioxide(NO2)
Ozone (O3)
Hydrocarbons
Airborne particulate matter varies widely in its physical and chemical composition, source and particle size. PM10 particles (the fraction of particulates in air of very small size (<10 µm)) are of major current concern, as they are small enough to penetrate deep into the lungs and so potentially pose significant health risks. Larger particles meanwhile, are not readily inhaled, and are removed relatively efficiently from the air by sedimentation. Particles are often classed as either primary (those emitted directly into the atmosphere) or secondary (those formed or modified in the atmosphere from condensation and growth).

A major source of fine primary particles are combustion processes, in particular diesel combustion, where transport of hot exhaust vapour into a cooler tailpipe or stack can lead to spontaneous nucleation of “carbon” particles before emission. Secondary particles are typically formed when low volatility products are generated in the atmosphere, for example the oxidation of sulphur dioxide to sulphuric acid. The atmospheric lifetime of particulate matter is strongly related to particle size, but may be as long as 10 days for particles of about 1mm in diameter.

The principal source of airbourne PM10 matter in European cities is road traffic emissions, particularly from diesel vehicles. As well as creating dirt, odour and visibility problems, PM10 particles are associated with health effects including increased risk of heart and lung disease. In addition, they may carry surface-absorbed carcinogenic compounds into the lungs.

Concern about the potential health impacts of PM10 has increased very rapidly over recent years. Increasingly, attention has been turning towards monitoring of the smaller particle fraction PM2.5 capable of penetrating deepest into the lungs, or to even smaller size fractions or total particle numbers.
Nitrogen oxides are formed during high temperature combustion processes from the oxidation of nitrogen in the air or fuel. The principal source of nitrogen oxides - nitric oxide (NO) and nitrogen dioxide (NO2), collectively known as NOx - is road traffic, which is responsible for approximately half the emissions in Europe. NO and NO2 concentrations are therefore greatest in urban areas where traffic is heaviest. Other important sources are power stations, heating plants and industrial processes.

Nitrogen oxides are released into the atmosphere mainly in the form of NO, which is then readily oxidised to NO2 by reaction with ozone. Elevated levels of NOx occur in urban environments under stable meteorological conditions, when the airmass is unable to disperse.

Nitrogen dioxide has a variety of environmental and health impacts. It is a respiratory irritant, may exacerbate asthma and possibly increase susceptibility to infections. In the presence of sunlight, it reacts with hydrocarbons to produce photochemical pollutants such as ozone (see below). In addition, nitrogen oxides have a lifetime of approximately 1 day with respect to conversion to nitric acid. This nitric acid is in turn removed from the atmosphere by direct deposition to the ground, or transfer to aqueous droplets (e.g. cloud or rainwater), thereby contributing to acid deposition.


Ground-level ozone (O3), unlike other primary pollutants mentioned above, is not emitted directly into the atmosphere, but is a secondary pollutant produced by reaction between nitrogen dioxide (NO2), hydrocarbons and sunlight. Ozone can irritate the eyes and air passages causing breathing difficulties and may increase susceptibility to infection. It is a highly reactive chemical, capable of attacking surfaces, fabrics and rubber materials. Ozone is also toxic to some crops, vegetation and trees.

Whereas nitrogen dioxide (NO2) participates in the formation of ozone, nitrogen oxide (NO) destroys ozone to form oxygen (O2) and nitrogen dioxide (NO2). For this reason, ozone levels are not as high in urban areas (where high levels of NO are emitted from vehicles) as in rural areas. As the nitrogen oxides and hydrocarbons are transported out of urban areas, the ozone-destroying NO is oxidised to NO2, which participates in ozone formation.

Sunlight provides the energy to initiate ozone formation; near-ultra-violet radiation dissociates stable molecules to form reactive species known as free radicals. In the presence of nitrogen oxides these free radicals catalyse the oxidation of hydrocarbons to carbon dioxide and water vapour. Partially oxidised organic species such as aldehydes, ketones and carbon monoxide are intermediate products, with ozone being generated as a by-product.

Since ozone itself is photodissociated (split up by sunlight) to form free radicals, it promotes the oxidation chemistry, and so catalyses its own formation (ie. it is an autocatalyst). Consequently, high levels of ozone are generally observed during hot, still sunny, summertime weather in locations where the airmass has previously collected emissions of hydrocarbons and nitrogen oxides (e.g. urban areas with traffic). Because of the time required for chemical processing, ozone formation tends to be downwind of pollution centres. The resulting ozone pollution or “summertime smog”may persist for several days and be transported over long distances.

Hydrocarbons

There are two main groups of hydrocarbons of concern: volatile organic compounds (VOCs) and polycyclic aromatic hydrocarbons (PAHs - see section below on TOMPs). VOCs are released in vehicle exhaust gases either as unburned fuels or as combustion products, and are also emitted by the evaporation of solvents and motor fuels. Benzene and 1,3-butadiene are of particular concern as they are known carcinogens. Other VOCs are important because of the role they play in the photochemical formation of ozone in the atmosphere.




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AEA Technology
Last updated 23 May 1997
Author: Jim McGinlay