Contrasting arsenic cycling in strongly and weakly stratified contaminated lakes: Evidence for temperature control on sediment-water arsenic fluxes.

Arsenic contamination of lakebed sediments is widespread due to a range of human activities, including herbicide application, waste disposal, mining, and smelter operations. The threat to aquatic ecosystems and human health is dependent on the degree of mobilization from sediments into overlying water columns and exposure of aquatic organisms. We undertook a mechanistic investigation of arsenic cycling in two impacted lakes within the Puget Sound region, a shallow weakly-stratified lake and a deep seasonally-stratified lake, with similar levels of lakebed arsenic contamination. We found that the processes that cycle arsenic between sediments and the water column differed greatly in shallow and deep lakes. In the shallow lake, seasonal temperature increases at the lakebed surface resulted in high porewater arsenic concentrations that drove larger diffusive fluxes of arsenic across the sediment-water interface compared to the deep, stratified lake where the lakebed remained ~10#x00B0;C cooler. Plankton in the shallow lake accumulated up to an order of magnitude more arsenic than plankton in the deep lake due to elevated aqueous arsenic concentrations in oxygenated waters and low phosphate: arsenate ratios in the shallow lake. As a result, strong arsenic mobilization from sediments in the shallow lake was countered by large arsenic sedimentation rates out of the water column driven by plankton settling.

Sediment organic carbon and temperature effects on methylmercury concentration: A mesocosm experiment.

The fate and mobility of mercury, and its bioaccumulation primarily as methylmercury (MeHg), in marine ecosystems are influenced by climate related environmental factors, including increased temperature and carbon loading. To investigate the interactions between sediment organic carbon and temperature MeHg bioaccumulation, mesocosm experiments were conducted examining relationships between sediment, water column and biota (sediment-dwelling amphipod and juvenile oyster) MeHg concentration. Experimental treatments consisted of a two by two design of high and low temperature (15 & 25 °C) and high and low sediment organic carbon (4-5% and 13% LOI, pre-experiment). Sediment organic carbon had significant individual effects on MeHg concentration in water and biota, with higher carbon associated with lower MeHg. Temperature individual effects were significant for sediment, water, and only amphipod MeHg concentration, with higher temperature treatments indicating higher MeHg concentration. There were significant temperature × carbon interactions observed for sediment, dissolved, and oyster MeHg concentration. Sediment carbon reduction had greater influence than temperature on increasing MeHg concentrations in both the water column and biota. MeHg concentrations in the bulk sediment were not correlated with MeHg in the water column or in the biota, indicating that even when sediments are the only source of MeHg, bulk sediment measurements do not provide a good proxy for bioaccumulation and that the concentration in bulk sediments is not the primary determinant of MeHg entry into the food web.

Organic carbon content drives methylmercury levels in the water column and in estuarine food webs across latitudes in the Northeast United States.

Estuaries are dynamic ecosystems which vary widely in loading of the contaminant methylmercury (MeHg), and in environmental factors which control MeHg exposure to the estuarine foodweb. Inputs of organic carbon and rates of primary production are important influences on MeHg loading and bioaccumulation, and are predicted to increase with changes in climate and land use pressures. To further understand these influences on MeHg levels in estuarine biota, we used a field study approach in sites across different temperature regions, and with varying organic carbon levels. In paired comparisons of sites with high vs. low organic carbon, fish had lower MeHg bioaccumulation factors (normalized to water concentrations) in high carbon sites, particularly subsites with large coastal wetlands and large variability in dissolved organic carbon levels in the water column. Across sites, MeHg level in the water column was strongly tied to dissolved organic carbon, and was the major driver of MeHg concentrations in fish and invertebrates. Higher primary productivity (chlorophyll-a) was associated with increased MeHg partitioning to suspended particulates, but not to the biota. These findings suggest that increased inputs of MeHg and loss of wetlands associated with climate change and anthropogenic land use pressure will increase MeHg concentrations in estuarine food webs.

Preliminary evaluation of (135)Cs/(137)Cs as a forensic tool for identifying source of radioactive contamination.

Ratios of the fission products (135)Cs and (137)Cs were determined in soil and sediment samples contaminated from three different sources, to assess the use of (135)Cs/(137)Cs as an indicator of source of radioactive contamination. Soil samples from the Chernobyl exclusion zone were found to have to be heavily depleted in (135)Cs ((135)Cs/(137)Cs approximately 0.45), indicative of a high thermal neutron flux at the source. Sludge samples from a nuclear waste treatment pond were found to have a (135)Cs/(137)Cs ratio of approximately 1, whereas sediment collected downstream from a nuclear reactor was highly variable in both (137)Cs activity and (135)Cs/(137)Cs ratio. Comparison of these preliminary results of variability in radiocaesium isotope ratios with reports of Pu isotope ratios suggests (135)Cs/(137)Cs similarly varies with fuel and reactor conditions, and may be used to corroborate other methods of characterizing radioactive contamination.

Determination of 90Sr in contaminated environmental samples by tuneable bandpass dynamic reaction cell ICP-MS.

A rapid method for the extraction and determination of 90Sr in natural water, plant and sediment samples was developed using extraction chromatography and dynamic reaction cell ICP-MS, with O2 as a reaction gas. While isobaric interference from the stable isotope 90Zr was efficiently removed by this method, interferences produced from in-cell reactions with Fe+ and Ni+ required suppression by tuneable bandpass, and in sediments, additional chromatographic separation. Method detection limits were 0.1 pg g-1 (0.5 Bq g-1), 0.04 pg g-1(0.2 Bq g-1), and 3 pg L-1 (5 Bq L-1) for sediments, plant and water samples, respectively, and 90Sr concentrations determined by ICP-MS were in good agreement with activities determined by Cerenkov counting and with certified reference values. While mass spectrometric determination does not rival detection limits achievable by radiometric counting, radiometric determination of 90Sr, a pure beta-emitter, is hindered by long analysis times (several weeks); the comparatively fast analysis achieved via ICP-MS enables same-day preparation and analysis of samples, making this an important technique for the environmental monitoring of areas contaminated by radioactivity.