Measurement and modelling of air pollution and atmospheric chemistry in the U.K. West Midlands conurbation: overview of the PUMA Consortium project.

The PUMA (Pollution of the Urban Midlands Atmosphere) Consortium project involved intensive measurement campaigns in the Summer of 1999 and Winter of 1999/2000, respectively, in which a wide variety of air pollutants were measured in the UK West Midlands conurbation including detailed speciation of VOCs and major component analysis of aerosol. Measurements of the OH and HO2 free radicals by the FAGE technique demonstrated that winter concentrations of OH were approximately half of those measured during the summer despite a factor of 15 reduction in production through the photolysis of ozone. Detailed box modelling of the fast reaction chemistry revealed the decomposition of Criegee intermediates formed from ozone-alkene reactions to be responsible for the majority of the formation of hydroxyl in both the summer and winter campaigns, in contrast to earlier rural measurements in which ozone photolysis was predominant. The main sinks for hydroxyl are reactions with NO2, alkenes and oxygenates. Concentrations of the more stable hydrocarbons were found to be relatively invariant across the conurbation, but the impacts of photochemistry were evident through analyses of formaldehyde which showed the majority to be photochemical in origin as opposed to emitted from road traffic. Measurements on the upwind and downwind boundaries of the conurbation revealed substantial enhancements in NOx as a result of emissions within the conurbation, especially during westerly winds which carried relatively clean air. Using calcium as a tracer for crustal particles, it proved possible to reconstruct aerosol mass from the major chemical components with a fairly high degree of success. The organic to elemental carbon ratios showed a far greater influence of photochemistry in summer than winter, presumably resulting mainly from the greater availability of biogenic precursors during the summer campaign. Two urban airshed models were developed and applied to the conurbation, one Eulerian, the other Lagrangian. Both were able to give a good simulation of concentrations of both primary and secondary pollutants at urban background locations.

The long range transport of ozone within Europe and its control.

It is widely accepted that the ozone concentrations experienced during photochemical episodes over large areas of Europe may exceed levels at which adverse environmental effects could be expected. These peak ozone concentrations can be reduced by controlling atmospheric emissions of the hydrocarbon and nitrogen oxide precursors. For ozone control to be successful over the spatial scale of Europe, long term international cooperation is required in the formulation of emission abatement strategies. A significant barrier to rapid progress has been the complexity of the processes that describe ozone formation. Highly sophisticated computer models of chemistry and transport have, up to now, been the only means to study the impact of abatement strategies. An alternative approach has been adopted here involving the development of a simplified long range transport model for ozone based on the analysis of over 60 experimental runs of a photochemical trajectory model applied to a wide range of hydrocarbon-nitrogen oxide emission combinations. Using the ozone-precursor relationship obtained, it has been possible to examine various policy options in the European context. Although taken together, three illustrative emission control scenarios reduce NO(x) and hydrocarbon emissions substantially through controls on motor vehicle exhaust, large combustion plant and solvent usage, a significant potential for photochemical ozone formation and long range transport may still remain after their implementation. The extents of precursor emission abatement that will be required, if the potential for ozone formation is to be reduced below published air quality criteria guidelines or critical levels, have been determined for each European country. The implied reductions in NO(x) and hydrocarbons relative to current levels amount to between 50 and 90%.

The impact of motor vehicle control technologies on future photochemical ozone formation in the United Kingdom.

Legislation to control motor vehicle exhaust emissions has been introduced in the United Kingdom in stages since the early 1970s. Recently, a further step has been taken towards reducing future exhaust emissions of carbon monoxide, unburnt hydrocarbons and oxides of nitrogen in the 'Luxembourg agreement' (Lubinska, 1985). In this paper, the possible impact of these proposed controls on photochemical air pollution formation in the United Kingdom is investigated, including an evaluation of the relative merits of the two principal emission control options for petrol-driven cars: 'Lean Burn' engines and 'Catalyst' exhaust gas treatment.

Factors influencing the ground level distribution of ozone in Europe.

Ozone is a widely distributed pollutant in the atmospheric boundary layer over north west Europe. Three main sources have been identified: the stratosphere, the free troposphere and boundary layer photochemical production. The pattern of ground level ozone concentrations resulting from these three sources cannot be accurately specified. Ozone shows significant variations in space and time but because of the high cost of continuous monitoring equipment, spatial variations on a national and international basis have not been studied in detail. Variations in ozone concentrations at individual monitoring sites have been given a great deal of attention and experience gained from United Kingdom monitoring sites is described in some detail. The averaging time statistical model of Larsen is employed to relate the exposure levels measured over different averaging periods. Diurnal variations have a major influence on exposure levels at sites nominally exposed to the same regional ozone distribution. The physical and chemical mechanisms which give rise to diurnal variations are detailed so that sites can be screened for different diurnal behaviour characteristics.

Measurements of gaseous hydrogen peroxide in southern England during a photochemical episode.

Simultaneous measurements of gaseous hydrogen peroxide and ozone made in southern England are reported. The hydrogen peroxide measurements are the first reported for the United Kingdom and show clear diurnal trends and correlate with ozone measurements. Measurements were made during a photochemical episode when a peak hydrogen peroxide concentration of 2.5 microg m(-3) was recorded with a simultaneous peak of 168 microg m(-3) in the ozone concentration. From observations on the rate of decay in the measured concentrations, an evening-time deposition velocity of 0.28 cm s(-1) was derived for hydrogen peroxide.

Modelling photochemical oxidant formation, transport, deposition and exposure of terrestrial ecosystems.

The chemical processes responsible for production of photochemical oxidants within the troposphere have been the subject of laboratory and field study throughout the last three decades. During the same period, models to simulate the atmospheric chemistry, transport and deposition of ozone (O(3)) from individual urban sources and from regions have been developed. The models differ greatly in the complexity of chemical schemes, in the underlying meteorology and in spatial and temporal resolution. Input information from land use, spatial and temporally disaggregated emission inventories and meteorology have all improved considerably in recent years and are not fully implemented in current models. The development of control strategies in both North America and Europe to close the gaps between current exceedances of environmental limits, guide values, critical levels or loads and full compliance with these limits provides the focus for policy makers and the support agencies for the research. The models represent the only method of testing a range of control options in advance of implementation. This paper describes currently applied models of photochemical oxidant production and transport at global and regional scales and their ability to simulate individual episodes as well as photochemical oxidant climatology. The success of current models in quantifying the exposure of terrestrial surfaces and the population to potentially damaging O(3) concentrations (and dose) is examined. The analysis shows the degree to which the underlying processes and their application within the models limit the quality of the model products.

Characterization of the reactivities of volatile organic compounds using a master chemical mechanism.

A comprehensive description of the ozone-forming potentials of 101 organic compounds has been constructed under North American urban "averaged conditions" using a detailed master chemical mechanism and a simple air parcel trajectory model. This chemical mechanism describes the reactions of 3603 chemical species taking part in more than 10,500 chemical reactions. An index value has been calculated for each organic compound, which describes the increment in ozone concentrations found downwind of an urban area following the emission of a fixed increment in the mass emission of each organic compound. These indices, termed photochemical ozone creation potentials (POCPs), have been expressed on a scale relative to ethylene (ethene) = 100, and, a reactivity scale has been generated for alkanes, alkenes, and oxygenated and halogenated organic compounds. A high degree of correlation (R2 = 0.9) was found between these POCP values and the most widely accepted urban reactivity scale. While the reactivities of most of the 86 organic compounds compared fell within a consistent range, significant discrepancies were found for only 5 compounds. Single-day or multiday conditions appear to be important in establishing quantitative reactivity scales for the less reactive organic compounds.

Assessment of uncertainties in a long range atmospheric transport model: Methodology, application and implications in a UK context.

Acid deposition models are inherently simplified representations of real world behaviour and their performance is best evaluated by comparison with observations. National and international acid rain policy assessments handle observed and modelled deposition fields in different ways. Here, both the observed and modelled deposition fields are seen as uncertain and the Generalised Likelihood Uncertainty Estimation (GLUE) framework is used to choose acceptable sets of model input parameters that minimise the differences between them. These acceptable sets of model parameters are then used to estimate deposition budgets to the UK and to provide a probabilistic treatment of excess deposition over environmental quality standards (critical loads).

Analysis of a petrol plume over England: 18-19 January 1997.

OBJECTIVES: About 7000 tonnes of unleaded petrol were discharged into the English Channel after a tanker collision off Ostend on Saturday 18 January 1997. The petrol evaporated and the vapour plume was carried across the central part of England to Wales, resulting in reports of unidentified odours, and irritation of the eyes, skin, and upper respiratory tract. This work uses this incident to show how marine and atmospheric dispersion modelling together with routine air quality monitoring can assist in identifying hazards to the population at risk from chemical incidents. METHODS: Public health surveillance and results from environmental sampling were compared with the behaviour of the plume as predicted by computer modelling. RESULTS: The predicted plume path and dispersion were shown to correlate well with the results from surveillance and environmental analysis. CONCLUSIONS: There is a need for public health professionals to interact with medical toxicologists, atmospheric and marine scientists and engineers, and other environmental experts in managing events of this nature.