Effects of broadleaf woodland cover on streamwater chemistry and risk assessments of streamwater acidification in acid-sensitive catchments in the UK

Streamwater was sampled at high flows from 14 catchments with different (0-78%) percentages of broadleaf woodland cover in acid-sensitive areas in the UK to investigate whether woodland cover affects streamwater acidification. Significant positive correlations were found between broadleaf woodland cover and streamwater NO3 and Al concentrations. Streamwater NO3 concentrations exceeded non-marine SO4 in three catchments with broadleaf woodland cover>or=50% indicating that NO3 was the principal excess acidifying ion in the catchments dominated by woodland. Comparison of calculated streamwater critical loads with acid deposition totals showed that 11 of the study catchments were not subject to acidification by acidic deposition. Critical loads were exceeded in three catchments, two of which were due to high NO3 concentrations in drainage from areas with large proportions of broadleaved woodland. The results suggest that the current risk assessment methodology should protect acid-sensitive catchments from potential acidification associated with broadleaf woodland expansion.     

Using Archive Data to Investigate Trends in the Sources and Composition of Urban PM10 Particulate Matter: Application to Edinburgh (U.K.) Between 1992 and 1997

By extending the method of Stedman (1998), daily dataof atmospheric concentrations of gravimetricPM₁₀, black smoke (BS) and sulphate aerosol (SA)from national networks were analysed to determine thetrends in time of the contribution of different sources of particulate matter to total PM₁₀ measured in central Edinburgh. Since BS is an indicator of combustion-related primary sources of particulate matter, the quantity obtained by subtraction of daily BS from daily PM₁₀ is indicative of the contribution to total PM₁₀ from other primary sources and from secondary aerosol. This PM₁₀-BS statistic was regressed on SA, since SA is an indicator of variation in secondary aerosol source. For Edinburgh, SA is a considerably better indicator of PM₁₀-BS during summer than winter (reflecting the much greater photochemical generation of secondary aerosol in summer) and there is evidence that the contribution of other secondary aerosol (presumably nitrate aerosol) has increased relative to SA between 1992 and 1997. The concentration of non-combustion primary particulate material (marine aerosol, suspended dust) to PM₁₀ in Edinburgh has not changed over this period but is about twice that calculated as the U.K. national average. The increasing input to PM₁₀ from secondary aerosol sources at regional rather than urban scale has important implications for ensuring local air quality compliance. The method should have general applicability to other locations.     

Identification and quantification of methyl halide sources in a lowland tropical rainforest

In conjunction with the OP3 campaign in Danum Valley, Malaysian Borneo, flux measurements of methyl chloride (CH₃Cl) and methyl bromide (CH₃Br) were performed from both tropical plant branches and leaf litter in June and July 2008. Live plants were mainly from the Dipterocarpaceae family whilst leaf litter samples were representative mixtures of different plant species. Environmental parameters, including photosynthetically-active radiation, total solar radiation and air temperature, were also recorded. The dominant factor determining magnitude of methyl halide fluxes from living plants was plant species, with specimens of the genus Shorea showing persistent high emissions of both gases, e.g. Shorea pilosa: 65 ± 17 ng CH₃Cl h^?1 g^?1 (dry weight foliage) and 2.7 ± 0.6 ng CH₃Br h^?1 g^?1 (dry weight foliage). Mean CH₃Cl and CH₃Br emissions across 18 species of plant were 19 (range, <LOD ?76) and 0.4 (<LOD ?2.9) ng h^?1 g^?1 respectively; fluxes from leaf litter were 1–2 orders of magnitude smaller per dry mass. CH₃Cl and CH₃Br fluxes were weakly correlated. Overall, the findings suggest that tropical rainforests make an important contribution to global terrestrial emissions of CH₃Cl, but less so for CH₃Br.     

Reactive uptake of ozone at simulated leaf surfaces: Implications for ‘non-stomatal’ ozone flux

The reaction of ozone (O₃) with α-pinene has been studied as a function of temperature and relative humidity and in the presence of wax surfaces that simulate a leaf surface. The objective was to determine whether the presence of a wax surface, in which α-pinene could dissolve and form a high surface concentration, would lead to enhanced reaction with O₃. The reaction of O₃ itself with the empty stainless steel reactor and with aluminium and wax surfaces demonstrated an apparent activation energy of around 30 kJ mol^?1 for all the surfaces, similar to that observed in long-term field measurements of O₃ fluxes to vegetation. However, the absolute reaction rate was 14 times greater for aluminium foil and saturated hydrocarbon wax surfaces than for stainless steel, and a further 5 times greater for beeswax than hydrocarbon wax. There was no systematic dependence on either relative or absolute humidity for these surface reactions over the range studied (20–100% RH). Reaction of O₃ with α-pinene occurred at rates close to those predicted for the homogeneous gas-phase reaction, and was similar for both the empty reactor and in the presence of wax surfaces. The hypothesis of enhanced reaction at leaf surfaces caused by enhanced surface concentrations of α-pinene was therefore rejected. Comparison of surface decomposition reactions on different surfaces as reported in the literature with the results obtained here demonstrates that the loss of ozone at the earth's surface by decomposition to molecular oxygen (i.e. without oxidative reaction with a substrate) can account for measured ‘non-stomatal’ deposition velocities of a few mm s^?1. In order to quantify such removal, the effective molecular surface area of the vegetation/soil canopy must be known. Such knowledge, combined with the observed temperature-dependence, provides necessary input to global-scale models of O₃ removal from the troposphere at the earth's surface.     

A new method for the determination of trichloroacetic acid in spruce foliage and other environmental media

Trichloroacetic acid (TCAA) is a phytotoxic chemical, present throughout the environment. The majority of methods for analysis of TCAA require chemical derivatisation and multiple extraction steps prior to analysis by gas-chromatography. Here, a new analytical method for TCAA determination in environmental matrices is reported. The method is based on a modified Nielsen-Kryger steam distillation that combines into one 1 h reflux the thermal decarboxylation of TCAA to CHCl3 and the partitioning and concentration of the CHCl3 into 5 ml of hexane, which is analysed by GC. Sample preparation is minimal and no matrix standard additions are required. The background CHCl3 in the sample is removed prior to extraction by degassing the solution for 1 h with nitrogen. Optimisation of the method gave recoveries from three separate solutions of 0.31 ppb aqueous TCAA standards of 93 +/- 15% (n = 9), 110 +/- 9% (n = 9) and 105 +/- 11% (n = 6). The extraction method has been compared with a decarboxylation and headspace GC method for determination of TCAA in Sitka spruce needles. No significant difference in TCAA concentration or replicate precision between the two methods was observed.