Alkyl nitrate photochemistry during the tropospheric organic chemistry experiment

Alkyl nitrates (C₁–C₅) were measured at two sites (near urban and rural) in southeast England during the Tropospheric Organic Chemistry Experiment (TORCH). Methyl nitrate was the dominant species during both campaigns accounting for on average about one third of the total measured alkyl nitrates. High mixing ratios (>50 pptv) and variability of methyl nitrate were observed at the near urban site (TORCH1) that were not seen at the rural site (TORCH2) and which could not be explained by local photochemical production or direct emissions. The diurnal variation of methyl nitrate during TORCH1 showed a morning maximum that would be consistent with nighttime chemistry followed by transport to the surface by boundary layer dynamics. Similarly, elevated morning mixing ratios were also observed during TORCH2 although the magnitudes were much smaller. As a result, methyl nitrate could represent a tracer for nighttime chemistry seen at the ground the following day. At both campaigns, the dominant source of short chain alkyl nitrates and carbonyl precursor radicals (≤C₄) were from decomposition of larger compounds. The magnitude of the source increased with decreasing carbon number consistent with increasing total precursor abundance. Non-photochemical emissions of acetaldehyde and acetone could not be accounted for by automobile exhaust emissions alone and indicated that other direct sources are likely important in this environment.     

Environmental forensics: an emerging discipline within UK higher education?

Environmental forensics is an established discipline in North America, but has yet to make an impact within Europe and more specifically within the UK. In this paper we explore the reasons for this and explore the nature and fundamental philosophy that underlies this discipline. Case studies can be used to explore the complexity that can be associated with an environmental forensic investigation and we argue that there is a demand for professionals with skills in forensic practice within the environmental sector today. The paper finishes by suggesting that environmental forensics is a discipline of its moment within Europe for which the Higher Education sector must now cater.     

Bioaccumulation of trace elements in omnivorous amphibian larvae: implications for amphibian health and contaminant transport

Despite the influence that amphibians have on the flow of energy and nutrients in ecological systems, the role that amphibians play in transporting contaminants through food webs has received very little attention. This study was undertaken to investigate bioaccumulation of trace elements in amphibians relative to other small aquatic organisms in a contaminated wetland. We collected bullfrog larvae (Rana catesbeiana) along with three other species of small vertebrates and four species of invertebrates from a site contaminated with a wide array of trace elements and analyzed them for trace element concentrations and stable nitrogen and carbon isotope composition. We found that amphibian larvae accumulated the highest concentrations of most trace elements, possibly due to their feeding ecology. These results suggest that omnivorous amphibian larvae can serve as a critical link for trace element trophic transfer. Their propensity to accumulate trace elements may have important implications for amphibian health in contaminated environments and should be further investigated.     

Cadmium availability to wheat grain in soils treated with sewage sludge or metal salts

Grain Cd concentrations were determined in wheat (Triticum aestivum L.) grown in 1999, 2001 and 2003, at six sludge cake field experiments. Three of these sites also had comparisons with Cd availability from metal amended liquid sludge and metal salts. Grain Cd concentrations in all years and at all sites were significantly linearly correlated with NH4NO3 extractable Cd and soil total Cd (P<0.001). Soil extractability was greater in the liquid sludge and metal salt experiments than in the cake experiments, as were grain Cd concentrations. Across all the sites, NH4NO3 extractable soil Cd was no better at predicting grain Cd than soil total Cd. Stepwise multiple linear regression analysis showed that soil total Cd, pH and organic carbon were the only significant (P<0.001) variables influencing wheat grain Cd concentrations, explaining 78% of the variance across all field experiments (1408 plots). This regression predicted that the current UK soil total Cd limit of 3 mg kg(-1) was not sufficiently protective against producing grain above the European Union (EU) grain Cd Maximum Permissible Concentration (MPC) of 0.235 mg Cd kg(-1) dry weight, unless the soil pH was > 6.8. Our predictions show that grain would be below the MPC with > 95% confidence with the proposed new EU draft regulations permitting maximum total Cd concentrations in soils receiving sludge of 0.5 mg kg(-1) for soils of pH 5-6, 1 mg kg(-1) for soils of pH 6-7, and 1.5 mg kg(-1) for soils of pH > or = 7.     

The Applicability of National Critical Loads Data in Assessing Designated Sites

Critical loads have been successfully used within Europe in the development of effects-based policies for pollution abatement, including the Second Sulphur Protocol and the Protocol to abate acidification, eutrophication and ground-level ozone (CLRTAP, 1979). This success has encouraged the UK Environment Agency and Conservation Agencies to use the national critical load maps as a screening tool in assessing the threats from acidification and eutrophication to designated (Natura 2000) sites. The UK maps of critical loads are based on national-scale data sets appropriate for national-scale assessments, and were never intended for use at the site-specific level. Site-based assessments are often targeted at Special Areas of Conservation, a sub-set of the UK Natura 2000 sites. The spatial data available includes the boundaries of the sites but not the location of the designated features. Ancillary data is variable from one site to another; habitat types may be described in detail with cross-reference to classes of the National Vegetation Classification (NVC: Rodwell, 1991 et seq), but information available on soils and geology is generalised and has not been related to the habitats or species being protected. Hence it can be difficult to relate the individual sites to the national maps, even where appropriate to do so. This paper examines the underlying uncertainties in the national critical load maps showing how the maps could give misleading results if used for site-specific assessments. It also includes advice on how to determine when the national data may be appropriate as a policy-tool at the site-level.     

Arsenic sequestration by nitrate respiring microbial communities in urban lake sediments

Changes in microbial community composition and activity were related to geochemical conditions favoring arsenic sequestration in sediments collected from the urban, arsenic-contaminated Upper Mystic Lake. After amendment with nitrate, >94% total soluble arsenic is sequestered by Fe(III)-(oxy)hydroxides generated in live sediments. Of this sequestered arsenic, >75% existed as As(III), indicating As redox state alone is not responsible for changes in mobility. Arsenic sequestration was concurrent with the microbial respiration of nitrate as indicated by steady state hydrogen concentration and the presence of organisms similar to nitrate-reducing, iron-oxidizing bacteria belonging to the genus Dechloromonas in 16S rDNA clone libraries.     

Recovery of benthic invertebrate communities from acidification in Killarney Park lakes

Using a reference-condition comparison, recovery of benthic invertebrate communities from acidification was assessed in three lakes in Killarney Wilderness Park approximately 40–60 km from the massive metal smelters in Sudbury, Canada. Test site analyses (TSAs) were used to compare the park lakes to 20 reference lakes near Dorset Ontario, 200 km to the east. An extension of a previous survey (1997–2001) of two sensitive mayfly species (Stenonema femoratum and Stenacron interpunctatum) was conducted in one of the lakes. TSA results indicate that the three Killarney lakes remain significantly different from reference condition due primarily to higher abundances of a few acid-tolerant families and the presence of some less abundant sensitive families. Colonization rates differ greatly between the two mayfly species presumably because of competition for available habitat. Overall, this study suggests that early colonizers will gain an advantage to out-compete subsequent arrivals, and these competitive interactions will delay the return of communities to reference condition.     

PFOS or PreFOS? Are perfluorooctane sulfonate precursors (PreFOS) important determinants of human and environmental perfluorooctane sulfonate (PFOS) exposure?

The extent to which perfluorooctanesulfonate precursors (PreFOS) play a role in human or environmental exposure to perfluorooctanesulfonate (PFOS) is not well characterized. The diversity of manufactured PreFOS and its degradation products (e.g. C(8)F(17)SO(2)R and C(8)F(17)SO(2)NR'R', where R is H or F, and R' and R' are various) has made it difficult to track their fate. Temporal trends of PFOS in both humans and wildlife are discrepant, thus it is difficult to predict future exposure, and hypotheses about the role of PreFOS have been raised. Although abiotic degradation of commercially important PreFOS materials requires further research, current data suggest that the yield of PFOS is negligible or minor. On the other hand, in vivo biotransformation of PreFOS yields PFOS as the major metabolite, and >32% yields have been observed. In Canadians, exposure to PreFOS was equivalent or greater than direct PFOS exposure prior to 2002. In most ocean water, PFOS is dominant to PreFOS, but in the oceans east of Greenland there may be more PreFOS than PFOS, consistent with the fact that whales and humans in this region also show evidence of substantial PreFOS exposure. Quantitative assessments of PFOS body-burdens coming from PreFOS are complicated by the fact that PreFOS partitions to the cellular fraction of blood, thus biomonitoring in serum under predicts PreFOS relative to PFOS. Many unknowns exist that prevent accurate modelling, thus analytical methods that can distinguish directly manufactured PFOS, from PFOS that has been biotransformed from PreFOS, should be applied in future human and environmental monitoring. Two new source tracking principles are presented and applied to human serum.     

Evaluation of the best compromise between the urban air quality monitoring resolution by diffusive sampling and resource requirements

The need to collect data representative of overall urban pollution is all-important in order to monitor the population exposure. High spatial resolution monitoring using diffusive samplers allows studying of the urban pollutant distribution, thus enabling deeper investigation of their generation and diffusion mechanisms. Nevertheless, such a monitoring campaign has a certain cost. In this study we point out how to find the best compromise between the number of necessary measurements and the affordable costs for monitoring campaigns. We also describe an innovative method for the proper design of a fixed urban monitoring network by means of preliminary high spatial resolution campaigns using diffusive samplers. Four European capital cities (Dublin, Madrid, Paris and Rome) were monitored six times, each time for seven days. Benzene, toluene, ethylbenzene, xylenes (BTEX) and NO(2) concentrations were measured at 146 sites in Dublin, 293 in Madrid, 339 in Paris and 290 in Rome. Multiscale grids have been drawn which ranged in mesh size from 500 m to 2 km. The statistical processing of data produced a twofold result: the creation of isoconcentration maps with geostatistical procedures, and an algorithm aimed at locating the minimum number of sampling sites where the fixed monitoring stations should be placed. Average urban levels estimated on the basis of these selected sites differ by less than 8% from those calculated on the whole populations of the sampled points. The aim of this work is to investigate how far the resolution of a monitoring campaign of urban pollution by diffusive sampling can be reduced, thus making the monitoring less expensive in terms of human and financial resources, while preserving the same quality of the results that could be achieved with a higher resolution. We found that there is no significant loss of information when the resolution of the monitoring grid for BTEX is lowered to a mesh size of 1.85 km, that is a sampling site each 3.4 km(2), and that the minimum number of sampling sites to be used is N = 0.29 A, where A is the urban surface to be monitored (in km(2)). As the spatial distribution of NO(2) is less sensitive to the distance from the emission source than that of BTEX, this relationship could be retained as a valid lower limit for the mesh grid size also for NO(2) monitoring.