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We investigated the fate of Sb and As downstream of the abandoned Su Suergiu mine (Sardinia, Italy) and surrounding areas. The mined area is a priority in the Sardinian remediation plan for contaminated sites due to the high concentrations of Sb and As in the mining-related wastes, which may impact the Flumendosa River that supplies water for agriculture and domestic uses. Hydrogeochemical surveys conducted from 2005 to 2015 produced time-series data and downstream profiles of water chemistry at 46 sites. Water was sampled at: springs and streams unaffected by mining; adits and streams in the mine area; drainage from the slag heaps; stream water downstream of the slag drainages; and the Flumendosa River downstream from the confluence of the contaminated waters. At specific sites, water sampling was repeated under different flow conditions, resulting in a total of 99 samples. The water samples were neutral to slightly alkaline. Elevated Sb (up to 30 mg L−\ud 1) and As (up to 16 mg L−1) concentrations were observed in water flowing from the slag materials from where the Sb ore was processed. These slag materials were the main Sb and As source at Su Suergiu. A strong base, Na-carbonate, from the foundry wastes, had a major influence on mobilizing Sb and As. Downstream contamination can be explained by considering that: (1) the predominant aqueous species, Sb(OH)6− and HAsO4−2, are not favored in sorption processes at the observed pH conditions; (2) precipitation of Sb- and As-bearing solid phases was not observed, which is consistent with modeling results indicating undersaturation; and (3) the main decrease in dissolved Sb and As concentrations was by dilution. Dissolved As concentrations in the Flumendosa River did not generally\ud exceed the EU limit of 10 μg L−1, whereas dissolved Sb in the river downstream of the contamination source always exceeded the EU limit of 5 μg L−1. Recent actions aimed at retaining runoff from the slag heaps are apparently not sufficiently mitigating contamination in the Flumendosa River

This study gives a contribution to assess the efficacy of some LDHs (layered double hydroxides) in Sb(V) uptake and understand the mechanisms involved in the removal process. Uncalcined nitrate Mg/Al LDHs and the mixed Mg-Al oxides derived from calcined carbonate Mg/Al LDHs mainly remove Sb(OH) from aqueous solution through the formation of a brandholzite-like phase (a non-LDH compound with general formula Mg[Sb(OH)]·6HO), although with a different efficiency (< 50 and 90-100% of Sb(V) removed, respectively). The formation of a brandholzite-like compound highlights the fundamental role of Mg in the removal process. The Sb(OH) removal capacity of uncalcined nitrate Mg/Al LDHs increases from 22 to 46% as the Mg/Al molar ratio decreases from 4 to 2 thanks to the increasing excess of positive charge of brucite-like sheets and the expanding interlayer thickness due to the different spatial orientations of nitrate groups (flat for Mg/Al = 4, perpendicular for Mg/Al = 2). The presence of Fe in the trivalent cationic site of carbonate LDHs (Mg/(Al + Fe) = 3/(0.5 + 0.5)) improves the Sb(OH) removal capacity of their calcined products. When Mg is replaced by Zn in the divalent cationic site of carbonate LDHs and the sorption experiments are performed using the mixed Zn-Al oxides derived from calcination, Sb(OH) is mainly removed from the solution through the reconstruction of an antimonate LDH structure (i.e., a zincalstibite-like compound with general formula ZnAl(OH)[Sb(OH)]). The removal efficiency of calcined carbonate Zn/Al LDHs is high and comparable to that of calcined carbonate Mg/Al LDHs; however, the mechanisms involved in the removal process are substantially different: entrance of Sb(OH) in the interlayer in the first case, adsorption of Sb(OH) onto the surface and formation of a new phase (a brandholzite-like compound) in the second case. In both cases, the removal processes are described with the pseudo-second-order kinetic model; the theoretical maximum adsorption capacity determined with the Langmuir isotherm results to be 4.54 and 4.37 mmol g for calcined carbonate Mg/AlFe and Zn/Al LDHs, respectively.

Four streams flowing in the Iglesiente and Arburese mine districts (SW Sardinia, Italy), exploited for zinc (Zn) and lead (Pb) extraction from sulphides and secondary non-sulphide mineralization (calamine ores), have been studied combining investigations from the macroscale (hydrologic tracer techniques) to the microscale (X-ray powder diffraction, scanning electron microscopy, X-ray absorption spectroscopy). In the investigated area, concerns arise from release of metals to water during weathering of ore minerals and mine-waste. Specifically, Zn is observed at extremely high concentrations (10s of mg/L or more) in waters in some of the investigated catchments. The results from synoptic sampling campaigns showed marked differences of Zn loads, from 6.3 kg/day (Rio San Giorgio) to 2000 kg/day (Rio Irvi). Moreover, natural attenuation of metals was found to occur i) through precipitation of Fe compounds (Fe oxy/hydroxides and "green rust"), ii) by means of the authigenic formation of metal sulphides promoted by microbial sulphate reduction, iii) by metal intake in roots and stems of plants (Phragmites australis and Juncus acutus) and by immobilization in the rhizosphere, and iv) by cyanobacterial biomineralization processes that lead to formation of Zn-rich phases (hydrozincite and amorphous Zn-silicate). The biologically mediated natural processes that lead to significant abatement and/or reduction of metal loads, are the response of environmental systems to perturbations caused from mine activities, and can be considered part of the resilience of the system itself. The aim of this study is to understand the effect of these processes on the evolution of the studied systems towards more stable and, likely, resilient conditions, e.g. by limiting metal mobility and favoring the improvement of the overall quality of water. The understanding of how ecosystems adapt and respond to contamination, and which chemical and physical factors control these natural biogeochemical barriers, can help to plan effective remediation actions.