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Earthworms and soil collected from six sites in Styria, Austria, were investigated for total arsenic concentrations by ICP-MS and for arsenic compounds by HPLC−ICP-MS. Total arsenic concentrations ranged from 3.2 to 17.9 mg/kg dry weight in the worms and from 5.0 to 79.7 mg/kg dry weight in the soil samples. There was no strict correlation between the total arsenic concentrations in the worms and soil. Arsenic compounds were extracted from soil and a freeze-dried earthworm sample with a methanol/water mixture (9:1, v/v). The extracts were evaporated to dryness, redissolved in water, and chromatographed on an anion- and a cation-exchange column. Arsenic compounds were identified by comparison of the retention times with known standards. Only traces of arsenic acid could be extracted from the soil with the methanol/water (9:1, v/v) mixture. The major arsenic compounds detected in the extracts of the earthworms were arsenous acid and arsenic acid. Arsenobetaine was present as a minor constituent, and traces of dimethylarsinic acid were also detected. Two dimethylarsinoylribosides were also identified in the extracts by co-chromatography with standard compounds. This is the first report of the presence of dimethylarsinoylribosides in a terrestrial organism. Two other minor arsenic species were present in the extract, but their retention times did not match with the retention times of the available standards.

Abstract-A wide range of human pharmaceuticals are present at low concentrations in freshwater systems, particularly in sections of polluted river. These compounds show high biological activity, often associated with a high stability. These characteristics imply a potential impact of these substances on aquatic biota even when present at low environmental concentrations. Low flow conditions in Mediterranean rivers, most of which flow through densely populated areas and are subjected to intensive water use, increase the environmental risk of these emergent compounds. Here, we studied whether pharmaceuticals in river water affect the local benthic community structure (diatoms and invertebrates). For this purpose, we analyzed the occurrence of pharmaceuticals along the Llobregat River and examined the benthic community structure (diatoms and invertebrates) of this system. Some pharmaceutical products in the Llobregat River registered concentrations greater than those cited in the literature. Multivariate analyses revealed a potential causal association between the concentrations of some anti-inflammatories and b-blockers and the abundance and biomass of several benthic invertebrates (Chironomus spp. and Tubifex tubifex). Further interpretation in terms of cause-and-effect relationships is discussed; however, it must be always taken with caution because other pollutants also may have significant contributions. Combined with further community experiments in the laboratory, our approach could be a desirable way to proceed in future risk management decisions.

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