In situ bioavailability of DDT and Hg in sediments of the Toce River (Lake Maggiore basin, Northern Italy): accumulation in benthic invertebrates and passive samplers.

DDT and mercury (Hg) contamination in the Toce River (Northern Italy) was caused by a factory producing technical DDT and using a mercury-cell chlor-alkali plant. In this study, DDT and Hg contamination and bioavailability were assessed by using different approaches: (1) direct evaluation of sediment contamination, (2) assessment of bioaccumulation in native benthic invertebrates belonging to different taxonomic/functional groups, and (3) evaluation of the in situ bioavailability of DDT and Hg using passive samplers. Sampling sites were selected upstream and downstream the industrial plant along the river axis. Benthic invertebrates (Gammaridae, Heptageniidae, and Diptera) and sediments were collected in three seasons and analyzed for DDT and Hg content and the results were used to calculate the biota sediment accumulation factor (BSAF). Polyethylene passive samplers (PEs) for DDT and diffusive gradients in thin films (DGTs) for Hg were deployed in sediments to estimate the concentration of the toxicants in pore water. Analysis for (DDx) were performed using GC-MS. Accuracy was within ±30 % of the certified values and precision was >20 % relative standard deviation (RSD). Total mercury concentrations were determined using an automated Hg mercury analyzer. Precision was >5 % and accuracy was within ±10 % of certified values. The results of all the approaches (analysis of sediment, biota, and passive samplers) showed an increasing contamination from upstream to downstream sites. BSAF values revealed the bioavailability of both contaminants in the study sites, with values up to 49 for DDx and up to 3.1 for Hg. No correlation was found between values in sediments and the organisms. Concentrations calculated using passive samplers were correlated with values in benthic invertebrates, while no correlation was found with concentrations in sediments. Thus, direct analysis of toxicant in sediments does not provide a measurement of bioavailability. On the contrary, analysis of bioaccumulation in benthic organisms provides the most realistic picture of the site-specific bioavailability of DDx and Hg, but this approach is time-consuming and not always feasible. On the other hand, the in situ deployment of passive samplers proved to be a powerful tool, providing a good surrogate measure of bioaccumulation.