Arsenic release from chlorine-promoted alteration of a sulfide cement horizon: Evidence from batch studies on the St. Peter Sandstone, Wisconsin, USA

Abstract

► We conducted laboratory experiments to examine chlorine-promoted sulfide oxidation. ► Chlorine increases oxidation of sulfides, releasing As. ► Chlorine increases ferrous iron oxidation, resulting in iron oxide formation to which As sorbs. ► Iron oxides can be sinks for As but can also release As if biogeochemical conditions change. ► Results have implications for aquifer storage and recovery in sulfide-bearing aquifers. Elevated As concentrations have been measured in wells in the St. Peter Sandstone aquifer of eastern Wisconsin, USA. The primary source is As-bearing sulfide minerals (pyrite and marcasite) within the aquifer. There is concern that well disinfection by chlorination may facilitate As release to groundwater by increasing the rate and extent of sulfide oxidation. The objective of this study was to examine the abiotic processes that mobilize As from the aquifer solids during controlled exposure to chlorinated solutions. Thin sections made from sulfidic aquifer material were characterized by quantitative electron probe micro-analysis before and after 24 h exposure to solutions of different Cl 2 concentrations. Batch experiments using crushed aquifer solids were also conducted to examine changes in solution chemistry over 24 h. Results of the combined experiments indicate that Cl 2 addition affects As release and uptake in two ways. First, Cl 2 increases oxidation of sulfide minerals, releasing more As from the mineral structure. Chlorine addition also increases the rate of Fe(II) oxidation and subsequent hydrous ferric oxide (HFO) precipitation, allowing for increased uptake of As onto the mineral surface. Although HFOs can act as sinks for As, they can release As if biogeochemical conditions (e.g. redox, pH) change. These results have implications not only for disinfection of drinking water wells in the study area, but also suggest that introduction of oxidants may adversely affect water quality during aquifer storage and recovery programs in aquifers containing As-bearing minerals.