Riverine sediments are important sites of mercury methylation and benthic invertebrates may be indicators of Hg exposure to higher organisms. From 2014 to 2018, sediments and invertebrates were collected along a mercury gradient in the Toce River (Northern Italy) and analyzed for THg and MeHg. Concentrations in invertebrates, separated according to taxon and to Functional Feeding Group, ranged from 20 to 253 µg kg−1 dry weight (d.w.) for THg, increasing from grazers (Leuctra, Baetis, Serratella) to predators (Perla). MeHg ranged from 3 to 88 µg kg−1 d.w. in biota, representing 6–53% of THg, while in sediments it was mostly below LOD (0.7 µg kg−1), accounting for ≤3.8% of THg. The Biota-Sediment Accumulation Factor (BSAF, ranging 0.2–4.6) showed an inverse relation to exposure concentrations (THg in sediments, ranging 0.014–0.403 µg kg−1 d.w.) and to organic carbon. THg in invertebrates (up to 73 µg kg−1 wet weight), i.e., at the basal levels of the aquatic trophic chain, exceeded the European Environmental Quality Standard for biota (20 µg kg−1 w.w.), posing potential risks for top predators. Concentrations in adult insects were close to those in aquatic stages, proving active mercury transfer even to terrestrial food chains.
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