Current issues and uncertainties in the measurement and modelling of air-vegetation exchange and within-plant processing of POPs

Air-vegetation exchange of POPs is an important process controlling the entry of POPs into terrestrial food chains, and may also have a significant effect on the global movement of these compounds. Many factors affect the air-vegetation transfer including: the physicochemical properties of the compounds of interest; environmental factors such as temperature, wind speed, humidity and light conditions; and plant characteristics such as functional type, leaf surface area, cuticular structure, and leaf longevity. The purpose of this review is to quantify the effects these differences might have on air/plant exchange of POPs, and to point out the major gaps in the knowledge of this subject that require further research. Uptake mechanisms are complicated, with the role of each factor in controlling partitioning, fate and behaviour process still not fully understood. Consequently, current models of air-vegetation exchange do not incorporate variability in these factors, with the exception of temperature. These models instead rely on using average values for a number of environmental factors (e.g. plant lipid content, surface area), ignoring the large variations in these values. The available models suggest that boundary layer conductance is of key importance in the uptake of POPs, although large uncertainties in the cuticular pathway prevents confirmation of this with any degree of certainty, and experimental data seems to show plant-side resistance to be important. Models are usually based on the assumption that POP uptake occurs through the lipophilic cuticle which covers aerial surfaces of plants. However, some authors have recently attached greater importance to the stomatal route of entry into the leaf for gas phase compounds. There is a need for greater mechanistic understanding of air-plant exchange and the 'scaling' of factors affecting it. The review also suggests a number of key variables that researchers should measure in their experiments to allow comparisons to be made between studies in order to improve our understanding of what causes any differences in measured data between sites.     

Resolving Chernobyl vs. global fallout contributions in soils from Poland using Plutonium atom ratios measured by inductively coupled plasma mass spectrometry

Plutonium in Polish forest soils and the Bór za Lasem peat bog is resolved between Chernobyl and global fallout contributions via inductively coupled plasma mass spectrometric measurements of 240Pu/230Pu and 241Pu/239Pu atom ratios in previously prepared NdF3 alpha spectrometric sources. Compared to global fallout, Chernobyl Pu exhibits higher abundances of 240Pu and 241Pu. The ratios 240Pu/230Pu and 241Pu/239Pu co-vary and range from 0.186 to 0.348 and 0.0029 to 0.0412, respectively, in forest soils (241Pu/239Pu = 0.2407 x [240Pu/239Pu] - 0.0413; r2 = 0.9924). Two-component mixing models are developed to apportion 239+240Pu and 241Pu activities; various estimates of the percentage of Chernobyl-derived 239+240Pu activity in forest soils range from < 10% to > 90% for the sample set. The 240Pu/230Pu - 241Pu/239Pu atom ratio mixing line extrapolates to estimate 241Pu/239Pu and the 241Pu/239+240Pu activity ratio for the Chernobyl source term (0.123 +/- 0.0007; 83 +/- 5; 1 May 1986). Sample 241Pu activities, calculated using existing alpha spectrometric 239+240Pu activities, and the 240Pu/230Pu and 241Pu/239Pu atom ratios, agree relatively well with previous liquid scintillation spectrometry measurements. Chernobyl Pu is most evident in locations from northeastern Poland. The 241Pu activities and/or the 241Pu/239Pu atom ratios are more sensitive than 240Pu/239Pu or 238Pu/239+240Pu activity ratios at detecting small Chernobyl 239+240Pu inputs, found in southern Poland. The mass spectrometric data show that the 241Pu activity is 40-62% Chernobyl-derived in southern Poland, and 58-96% Chernobyl in northeastern Poland. The Bór za Lasem peat bog (49.42 degrees N, 19.75 degrees E), located in the Orawsko-Nowotarska valley of southern Poland, consists of global fallout Pu.     

Evaluating factors influencing groundwater vulnerability to nitrate pollution: developing the potential of GIS

The 1991 EU Nitrate Directive was designed to reduce water pollution from agriculturally derived nitrates. England and Wales implemented this Directive by controlling agricultural activities within their most vulnerable areas termed Nitrate Vulnerable Zones. These were designated by identifying drinking water catchments (surface and groundwater), at risk from nitrate pollution. However, this method contravened the Nitrate Directive because it only protected drinking water and not all waters. In this paper, a GIS was used to identify all areas of groundwater vulnerable to nitrate pollution. This was achieved by constructing a model containing data on four characteristics: the quality of the water leaving the root zone of a piece of land; soil information; presence of low permeability superficial (drift) material; and aquifer properties. These were combined in a GIS and the various combinations converted into a measure of vulnerability using expert knowledge. Several model variants were produced using different estimates of the quality of the water leaving the root zone and contrasting methods of weighting the input data. When the final models were assessed all produced similar spatial patterns and, when verified by comparison with trend data derived from monitored nitrate concentrations, all the models were statistically significant predictors of groundwater nitrate concentrations. The best predictive model contained a model of nitrate leaching but no land use information, implying that changes in land use will not affect designations based upon this model. The relationship between nitrate levels and borehole intake depths was investigated since there was concern that the observed contrasts in nitrate levels between vulnerability categories might be reflecting differences in borehole intake depths and not actual vulnerability. However, this was not found to be statistically important. Our preferred model provides the basis for developing a new set of groundwater Nitrate Vulnerable Zones that should help England and Wales to comply with the EU Nitrate Directive.     

Sediment and porewater geochemistry in a metal contaminated estuary,Dulas Bay,Anglesey

Remobilisation of contaminant metals from sediments can occur by chemical, biological or physical changes. This in turn can lead to contaminant fluxes to the porewaters and ultimately the water column. The aim of the research presented here is to document post-depositional controls on metal mobility and fluxes in a heavily metal-contaminated estuary. This will allow for an improved understanding of the impact of contaminated sediments on water quality from both a short-term and long-term perspective. Dulas Bay is situated on the east coast of Anglesey, North Wales, and receives polluted waters from Parys Mountain. Metals within Dulas Bay sediments show surface enrichment and variations in mineralogical form. Diagenesis clearly plays a role in post-depositional behaviour of the metals, forming sulphides and potentially carbonates. The presence of a dominant exchangeable/carbonate fraction, and elevated porewater metals, in this sulphidic system is significant and could indicate the presence of freshwater diagenesis, or, reflect the high levels of metals in the sediment.     

CH4/CO2 ratios indicate highly efficient methane oxidation by a pumice landfill cover-soil

Landfills that generate too little biogas for economic energy recovery can potentially offset methane (CH₄) emissions through biological oxidation by methanotrophic bacteria in cover soils. This study reports on the CH₄ oxidation efficiency of a 10-year old landfill cap comprising a volcanic pumice soil. Surface CH₄ and CO₂ fluxes were measured using field chambers during three sampling intervals over winter and summer. Methane fluxes were temporally and spatially variable (?0.36 to 3044 mg CH₄ m^?2 h^?1); but were at least 15 times lower than typical literature CH₄ fluxes reported for older landfills in 45 of the 46 chambers tested. Exposure of soil from this landfill cover to variable CH₄ fluxes in laboratory microcosms revealed a very strong correlation between CH₄ oxidation efficiency and CH₄/CO₂ ratios, confirming the utility of this relationship for approximating CH₄ oxidation efficiency. CH₄/CO₂ ratios were applied to gas concentrations from the surface flux chambers and indicated a mean CH₄ oxidation efficiency of 72%. To examine CH₄ oxidation with soil depth, we collected 10 soil depth profiles at random locations across the landfill. Seven profiles exhibited CH₄ removal rates of 70–100% at depths <60 cm, supporting the high oxidation rates observed in the chambers. Based on a conservative 70% CH₄ oxidation efficiency occurring at the site, this cover soil is clearly offsetting far greater CH₄ quantities than the 10% default value currently adopted by the IPCC.     

The effect of metal catalysts on the formation of polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran precursors

The catalytic effects of copper and iron compounds were examined for their behavior in promoting formation of chlorine (Cl₂), the major chlorinating agent of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), in an environment simulating that of municipal waste fly ash. Formation of Cl₂ occurred as a result of a metal-catalyzed reaction of HCl with O₂. Catalytic activity was greatest at a temperature of approximately 400 °C, supporting a theory of de novo synthesis of PCDDs and PCDFs on fly ash particles downstream of waste combustion.     

Sedimentary Pigments and Organic Matter in Relation to Benthic Fauna in the Tan-Shui Estuary, Taiwan

The benthic ecological structure of the Tan-Shui estuary, Taiwan is changed due to long term effects of dumping of urban wastewater and of engineering actions. to monitor these changes, we sampled and analyzed benthos and sediment from 12 stations on the estuary.

The composition of the dominant species of benthos varied seasonally, with molluscan and crustacean species having greater numbers and higher frequencies of occurrence than other species. the dominant taxa during winter were Nassarius sp. and Maldanidae at two stations. Analysis using Simpson's index and Shannon's index showed the benthic community varied more in coastal areas than in offshore areas.

Physicochemical analysis showed that most of the Tan-Shui estuary consisted of sandy sediment. the variations in concentrations of organic carbon and total nitrogen at each station were small. Although the concentrations of chlorophyll-a and carotenoid at all stations were generally low, the two stations had the highest concentrations, and we concluded that the concentration of pigments in these sediments was related to the abundance of benthos. the community structure of the benthos reflected the characteristics of the sediments, and benthic species exhibited selection of and adaptation to specific sedimentary environments.