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Fluvial sediments of the Paglia River, a tributary of Tiber River (Central Italy), are contaminated by mercury (Hg) as a consequence of past mining activity (1846-1981, with main production 1900-1970) in the Monte Amiata district (the 3rd largest Hg producer worldwide). In this study, we combine a geomorphological analysis with geochemical data to try and understand the influence of fluvial dynamics on the spatial distribution of Hg in fluvial sediments over a 43 km segment of the river. By considering the evolution of the river course between 1883 and 2013, eight different geomorphic units (GUs) were recognised, including the active channel bed (baseflow channel and bar), the floodplain, and five orders of terraces. The distribution of Hg in sediments of these GUs reflects the timing of their formation with respect to evolution of the mining activity. In GUs formed before the main peak of mining activity, or after mine closure, sediments show mean Hg contents comparable to, or slightly higher than, the local background, estimated at 2-6 mg/kg; in GUs formed during the peak production, Hg mean contents are definitely higher (up to 26 mg/kg). The current floodplain also shows high contents (mean 19 mg/kg), because of continuous reworking and transport of older contaminated sediments during major flood events. Therefore, the point contaminant sources represented by mining centres evolved into a diffuse source spread over several tens of kilometres. By combining geochemical data with calculated sediment volumes, we estimate that not less than 63 tonnes of Hg are currently contained in the sediments of the investigated river stretch. Such amount of Hg will probably limit for the near future a full land use along the Paglia-Tiber course.

The Mount Amiata mining district (southern Tuscany, Italy) was, for decades, one of the world's largest mercury (Hg) producing regions, where mining activity lasted until the 1980s. The Paglia River drains the eastern part of the district and is also the main western tributary of the Tiber River. Recent studies show that, still today, high total Hg contents severely affect the downstream ecosystems of these rivers. In November 2012, a major flood event occurred in the Paglia River basin, which drastically changed the river morphology and, possibly, the Hg concentrations. In the present work, stream sediment was sampled before and after the flood to evaluate possible changes in sediment total Hg concentrations as a consequence of this event. The comparison between pre-and post-flood Hg concentrations shows that Hg content increased up to an order of magnitude after the flood, suggesting that this event triggered Hg mobilization in the basin rather than its dilution.

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