Coupled S and Sr isotope evidences for elevated arsenic concentrations in groundwater from the world’s largest antimony mine, Central China

Abstract

The Xikuangshan(XKS) mine, the world’s largest antimony mine, was chosen for a detailed arsenic hydrogeochemical study because of the elevated arsenic in bedrock aquifers used by local residents. Hydrochemical data, δ34S values of dissolved SO42− and 87Sr/86Sr ratios have been analyzed to identify the predominant geochemical processes that control the arsenic mobilization within the aquifers. Groundwater samples can be divided into three major types: low arsenic groundwater (0–50 µg/L), high arsenic groundwater (50–1000 µg/L) and anomalous high arsenic groundwater (>1000 µg/L). Arsenic occurs under oxidizing conditions at the XKS Sb mine as the HAsO42− anion. The Ca/Na ratio correlates significantly with HCO3−/Na and Sr/Na ratios, indicating that carbonate dissolution and silicate weathering are the dominant processes controlling groundwater hydrochemistry. The δ34S values of the groundwater indicate that dissolved SO42− in groundwater is mainly sourced from the oxidation of sulfide minerals, and elevated As concentrations in groundwater are influenced by the mixing of mine water and surface water. Furthermore, the δ34S values are not correlated with dissolved As concentrations and Fe concentrations, suggesting that the reduction dissolution of Fe(III) hydroxides is not the dominant process controlling As mobilization. The 87Sr/86Sr ratios imply that elevated As concentrations in groundwater are primarily derived from the interaction with the stibnite and silicified limestone. More specifically, the excess-Na ion, the feature of Ca/Na ratio, and the spatial association of elevated As concentrations in groundwater collectively suggest that high and anomalous high arsenic groundwater are associated with smelting slags and, in particular, the arsenic alkali residue. In general, the hydrochemistry analysis, especially the S and Sr isotope evidences elucidate that elevated As concentrations and As mobilization are influenced by several geochemical processes, including: (1) bedrock weathering; (2) oxidation of arsenopyrite and the dominant sulfides in the ores; (3) mixing of mine drainage and surface water; (4) leaching of the arsenic alkali residue; and (5) sorption-desorption from Fe/Mn oxides/hydroxides.