Geochemical controls on arsenic distribution in the Baccu Locci stream catchment (Sardinia,Italy) affected by past mining

The Baccu Locci stream catchment (Sardinia, Italy) is affected by serious As contamination as a consequence of past mining. The presence of both point and widespread sources of contamination (waste-rock dumps and flotation tailings, respectively) strongly affects surface water chemistry, and produces high As concentrations (hundreds of μg l^?1) in stream waters. Water chemistry of the Baccu Locci stream changes considerably over a distance of about 10 km as a consequence of various, locally concomitant, processes acting along the stream course: (1) mixing with metal-rich SO₄ waters; (2) dissolution/precipitation of metal-bearing phases; (3) mixing with HCO₃-dominated lake waters; (4) gypsum dissolution coupled with calcite precipitation; (5) mixing with dilute surface and/or ground waters. In contrast to metals (e.g. Pb, Cu, Zn and Cd), whose dissolved concentrations rapidly decrease downstream of the mined area through (co-)precipitation/adsorption mechanisms, As concentrations tend to gradually increase (up to 0.9 mg l^?1) along the stream course as far as the alluvial plain, though significant variations are locally observed. This behaviour is mainly due to the higher mobility of As than metals under the near neutral-oxidative conditions occurring in the Baccu Locci stream waters. Results of a leaching test indicate that part of the As contained in the flotation tailings occurs as As(III), which is more mobile and less strongly sorbed than As(V). The As released to the waters by various mechanisms (i.e. release/desorption from the Fe(III)-hydroxides coatings of silicate grains, oxidation of residual arsenopyrite, decomposition of scorodite) tends to remain in solution and to be transported long distances. As a consequence of the widespread presence of highly As-contaminated flotation tailings all over the medium-lower Baccu Locci stream catchment, long-term As contamination is expected.