Ambient concentrations of 1,3-butadiene in the UK.

This paper assesses the current knowledge of 1,3-butadiene as an atmospheric pollutant, considers measurement techniques and reviews available data on 1,3-butadiene monitoring and emissions estimates. Atmospheric chemistry, sources of emission, current legislation, measurement techniques and monitoring programmes for 1,3-butadiene are reviewed. There have been comparatively few studies of the products of oxidation of 1,3-butadiene in the atmosphere. However, on the basis of the available information, and by analogy with the oxidation mechanism for the widely-studied and structurally similar natural hydrocarbon isoprene (2-methyl-1,3-butadiene), it is possible to define some features of the likely oxidation pathways for 1,3-butadiene. The total UK 1,3-butadiene emission to the atmosphere for 1996 has been estimated at 10.60 kTonnes. 1,3-Butadiene is a product of petrol and diesel combustion; consequently this total is dominated by road transport exhaust emissions (accounting for some 68% of the total). Off-road vehicles and machinery are responsible for 14% of the total UK emission. 1,3-Butadiene is used in the manufacture of numerous rubber compounds, and consequently emissions arise from both the manufacture and use of 1,3-butadiene in industrial processes. Emissions from the chemical industry account for 18% of the UK total emission- 8% from 1,3-butadiene manufacture and 10% from 1,3-butadiene use. The United Kingdom Expert Panel on Air Quality Standards (EPAQS) has published a report on 1,3-butadiene, and recommended a national air quality standard of 1.0 ppb (expressed as an annual rolling mean). This was adopted by the Government as part of the National Air Quality Strategy (NAQS) in 1997, and a target of compliance by 2005 was set. Work conducted for the review of the NAQS (1999) indicated that it was likely that all locations would be compliant with the national standard by the end of 2003. As a result, the review updated the air quality objective for 1,3-butadiene, with the deadline for compliance being brought forward to 31/12/2003. The UK Hydrocarbon Monitoring Network provides continuous hourly measurements of 1,3-butadiene at 13 sites, and has been operational since 1993. The dataset that is available allows spatial and temporal trends to be evaluated, and has proved to be invaluable in characterising the current ambient levels of 1,3-butadiene in the UK. Hourly maximum concentrations of 1,3-butadiene of up to 10 ppb (1 ppb=1 ppb, i.e. 1 vol. of 1,3-butadiene in 1,000,000,000 vol. of air. 1 ppb of 1,3-butadiene is ca. equal to 2.25 microg m(-3) at 20 degrees C) may be measured for several hours at the sites. Monthly mean concentrations are typically 0.1-0.4 ppbv. At most sites, these levels are driven by emissions from motor vehicles. Occasionally emissions of 1,3-butadiene from industrial sources may elevate 1,3-butadiene concentrations to several tens of ppb. Trend analysis of the data suggests that ambient concentrations of 1,3-butadiene in the UK are declining at about 10% per year.

Uncertainties in current estimates of emissions of ammonia in the United Kingdom.

Estimates of the emissions of ammonia have previously concentrated on animal husbandry sources from agricultural systems. Animal husbandry sources still constitute the major fraction of emissions of ammonia, but we have also considered the potential magnitude of other 'minor' sources, which may include coal combustion, waste incineration, road vehicles, sewage treatment plants, fertiliser manufacture and application, vegetation senescence and crop emissions, domestic pets, and human sources. Where possible, a provisional estimate of UK emissions from each of these sources is given. It is concluded that the potential magnitude of emissions from these 'minor' sources may make a significant contribution to the total emissions of ammonia to the atmosphere. On the basis of the available data, and the application of a range of emission factors to the UK situation, an additional annual emission potential lying in the range of approximately 80-140 ktonne year(-1) over and above that from animal husbandry has been calculated. The uncertainties in the emission estimates and instances in which a better resolution of sources is required are discussed. The emission factors used for animals in various inventories are reviewed and applied to the main UK agricultural animal populations. By using this approach, estimates of emissions from these sources range between 113 and 647 ktonne year(-1), which illustrates the uncertainties involved. It is suggested that our knowledge of the sources of ammonia, and their distribution, is far from complete.

Observations of H2O2 and PAN in a rural atmosphere.

Measurements of gaseous H2O2 and peroxyacetyl nitrate (PAN) concentrations in air are given for a site in rural southern England over an approximately 4-year period. In both cases the data show both diurnal and seasonal patterns. Temperature and wind direction had clear influences on the recorded concentrations of both species. There was an indication of increasing H2O2 concentrations with time. The use of a two-dimensional global model confirmed that this would be expected to occur alongside growth in ozone formation. It is suggested that, during photochemical episodes, the sequential build-up of ozone, PAN and H2O2 could be important in influencing the ability of vegetation to resist the effects of aggressive pollutants.

A field study of the generation of nitrate in a hill cap cloud.

A field experiment to investigate the formation of nitrate as an airstream passes through a hill cap cloud has been performed at the UMIST field station on Great Dun Fell. It has been shown that the aerosol nitrate concentration increased by about 0.5 microg m(-3) as the airstream passed through the cloud during the night. At sunrise the nitrate production disappeared. It is suggested that the most likely mechanism for this nitrate production was due to the solution of N2O5 and NO3 formed from the reaction of NO2 with O3. These higher oxides build up overnight in the absence of short wave radiation to photolyse them. Other possible mechanisms of nitrate production are also discussed.

Measurements of ammonia emission from grazed grassland.

Some of the factors influencing NH(3) emission from grazed grassland were examined. The large day-to-day variation in rates of loss were only partially explained by variation in the measured environmental factors (wind speed, soil and air temperature, soil moisture status, relative humidity, rainfall and potential evapotranspiration). Of the measured variables, wind speed had the largest effect but the best multiple linear regression model of daily NH(3) loss had an adjusted R(2) value of only 0.406. The mechanisms controlling NH(3) flux were therefore unclear. There were marked diurnal rhythms in NH(3) loss and the concentration gradients above the sward were strongest during the period which included the 3 h each side of midday. This pattern of NH(3) release has important implications in relation to atmospheric mixing processes and chemical reactions. A comparison of two means of determining NH(3) concentrations, i.e. a bubbler collection system or denuder tubes, indicated that different forms were collected which could be related to the environmental conditions. Such differences and effects should be considered when models are developed to describe the behaviour of nitrogenous and other species in the atmosphere.

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.

Emission of NOx from urine-treated pasture.

Emission of NO(x) from urine-treated pasture was determined using a system of enclosures coupled to a chemiluminescence NO(x) analyser. Rates of emission ranged from 0 to 190 microg NO(x) - Nm(-2)h(-1), with a mean of 43 microg N m(-2) h(-1). The lowest rates were associated with periods of heavy or persistent rain. On average, NO comprised 68% of the NO(x) produced. Emissions of NO(x) were apparently associated with the nitrification of ammonium N derived from hydrolysis of organic N constituents in the urine applied. Emissions from untreated pasture occurred at a mean rate of 1.7 microg NO(x) -N m(-2) h(-1). NO(x) comprised only a small proportion (<0.1%) of the emission of other nitrogenous gases (NH(3), N(2) and N(2)O) following application of urine. The mean rate of NO(x) emission suggested a total release to the atmosphere of 2.3 x 10(-8) g N year(-1) from urine returned to pasture in the UK. This loss is not significant in agronomic terms and is equivalent to only 0.04% of the estimated anthropogenic emissions for the UK.

Studies on the behaviour of lead in wood binding of free and complexed 210Pb to xylem tissue.

The binding of lead to xylem tissue has been studied using an isolated segmentperfusion technique. The results show that free lead ions bind more readily to xylem tissue than does lead in the form of a lead-glycine complex. A small, but significant proportion of the applied lead moves laterally from wood to bark. Both binding and lateral movement of lead are shown to be time-dependant. The results are discussed in terms of using trees and the chemical analysis of their annual growth rings to date heavy metal pollution histories.

Studies on lateral movement of 210Pb in woody stems : Patterns observed in dormant and non-dormant stems.

Evidence has been obtained for lateral transport of bark applied 210Pb from bark to wood in a range of tree species. This lateral redistribution was found to be independant of cambial reactivation, Lead being recovered from bark and wood in the same proportions from dormant and non-dormant shoots. The results are discussed in relationship to naturally-occurring uptake of Lead by stems.