The Mediterranean Sea is characterized by a marked mercury (Hg) geochemical anomaly, arising in part from large Hg deposits. Mercury mass loads discharged from the Monte Amiata mining district (Central Italy) to the Mediterranean Sea through the Paglia–Tiber River system were estimated. Data from two seasons showed that up to 40 kg year⁻¹ of Hg are drained to Tiber River and finally to the Mediterranean Sea. The mercury mass loads varied in different seasons, from 3 mg day⁻¹ in the upper section of Paglia River in November to 42 g day⁻¹ before the confluence with Tiber River in June. Along Tiber River, up to 15 ng L⁻¹ of the total Hg found at a site after Rome showed that Hg can be discharged to the sea. The Alviano reservoir along Tiber River acts as a temporary trap for Hg-rich particulate, while dam operations may promote Hg release (up to 223 g day⁻¹). The combination of hydrologic factors controlling Hg transport, the torrential regime in the upper catchment of Paglia River, the waterway steepness, together with Hg-contaminated legacy sediments in the Paglia River floodplain, make the Paglia–Tiber River system a long-lasting intermittent source of Hg to Tiber River and the Mediterranean Sea.

Previous studies documented the contribution of toxic elements (Hg, As, and Sb) from the dismissed Monte Amiata Mining District (Italy), the third largest Hg producer worldwide, to the Mediterranean Sea. Another highly toxic element, thallium (Tl), received less attention. Here we report a reconnaissance study of the spatial variability of Tl content in stream sediments across the Fiora River catchment, which drains part of the Hg and Sb mining districts. Thallium contents are comparatively low (≤0.4 mg/kg) in sediments of creeks directly draining the mining areas, whereas they increase up to 2 mg/kg in the catchment section that drains the Vulsini ultrapotassic volcanic province, where no known mineral deposits occur. Results suggest that Hg and Sb deposits cannot be the only Tl source in the catchment. The most likely alternative/additional candidate are the high-K volcanic rocks. Although no specific data for the Vulsini district exist, a distinct Tl geochemical anomaly linked to the Latium volcanic province is present. The total Tl mass contained in sediments discharged yearly into the Mediterranean Sea from the Fiora River is estimated in the order of 0.1 t. This reconnaissance study indicates a non-negligible potential release of Tl from the mining districts and volcanic catchments in Central Italy and suggests the opportunity of further investigation on Tl distribution and speciation in the area.