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Differences in bioavailability among sediments are a source of variability and uncertainty in sediment quality assessment. We present three sets of studies designed to test a thin-film solid phase extraction technique for characterizing the bioavailability of organic chemicals in sediments. Laboratory studies with spiked natural sediments reveal highly reproducible thin-film extractions for chemicals with octanol-water partition coefficients between 104.5 and 108.5, with 95% equilibration times between 1 and 600 h. Studies with field-collected sediments illustrate that method detection limits are sufficiently low for field application at contaminated sites. Bioaccumulation studies with clams (Macoma balthica) show excellent correlations between thin-film and animal tissue concentrations. We conclude that thin-film extraction provides an ecologically relevant, fugacity-based measure of chemical exposure that can be expected to improve sediment quality assessments. [ABSTRACT FROM AUTHOR]

The bioavailability of four sediment-spiked hydrophobic organic contaminants (HOCs; chrysene, benzo[a]pyrene, chlordane, and Aroclor 1254) was investigated by comparing bioaccumulation by the amphipod Corophium colo with uptake into a thin film of ethylene/vinyl acetate (EVA) copolymer. The EVA thin film is a solid-phase extraction medium previously identified as effective at measuring the bioavailable contaminant fraction in sediment. The present study presents the results of 11 separate treatments in which chemical uptake into EVA closely matched uptake into lipid over 10 d. For all compounds, the concentration in EVA was a good approximation for the concentration in lipid, suggesting that this medium would be an appropriate biomimetic medium for assessing the bioaccumulation of HOCs during risk assessment of contaminated sediment. For chrysene and benzo[a]pyrene, limitations on bioaccumulation and toxicity because of low aqueous solubility were observed. The fugacity of the compounds in lipid (flip) and in the EVA thin film (fEVA) also was determined. The ratio of flip to fEVA was greater than one for all chemicals, indicating that all chemicals biomagnified over the duration of the exposure and demonstrating the potential for EVA thin-film extraction to assess trophic transfer of HOCs. [ABSTRACT FROM AUTHOR]

It is well documented that the bioavailability of hydrophobic organic chemicals (HOCs) can vary substantially among sediments. This makes risk assessments based on total sediment concentrations problematic. The present study investigates the application of thin-film solid-phase extraction to measure bioavailable concentrations of phenanthrene in estuarine sediment by comparing concentrations of phenanthrene in the amphipod Corophium colo and in thin ethylene/vinyl acetate films at different concentrations in three geochemically different sediments. For all sediment types, concentrations of phenanthrene in sediments and thin films followed linear relationships, indicating first-order exchange kinetics. Organism/thin-film concentration ratios did not vary systematically among sediment types but dropped significantly with increasing phenanthrene concentration in the sediments. While at low phenanthrene concentrations in the sediment fugacities of phenanthrene in the amphipods approached the fugacities in the thin films, they were significantly lower than those in the sediments at higher concentrations. While phenanthrene concentrations in the three sediment types were identical, biota sediment accumulation factors and concentrations in amphipods and thin films were consistently lower in sediments enriched with black carbon than in sediments with sedimentary organic matter bearing a more diagenetic organic signature. It is concluded that, for the range of concentrations tested, thin-film solid-phase extraction can be a useful tool in the characterization of differences in bioavailability of HOCs among sediment types. [ABSTRACT FROM AUTHOR]