Sequestration of arsenic to biogenic sulfide minerals is known from As-contaminated anoxic environments. Despite numerous successful laboratory experiments, the process remains difficult to predict in moderate arsenic conditions. We performed microcosm experiments using naturally contaminated groundwater (containing ca. 6 mg/L As) and natural organic matter (NOM) particles both collected from wetland soil. Macroscopic realgar precipitates, occasionally accompanied by bonazziite, a FeS phase, elementary S, calcite, and whewellite, appeared after 4 to 18 months. Realgar only precipitated in microcosms moderately poisoned by azide or antibiotics and those in which oxidation of hydrogen sulfide to sulfur took place. The biomineralization process was not affected by the presence of additional carbon sources or the diversity, community structure, and functional composition of the microbial community. Hydrogen sulfide concentration was greater in the realgar-free microcosms, suggesting that arsenic thiolation prevented precipitation of realgar. We compared our data to available microbial community data from soils with different rates of realgar precipitation, and found that the communities from realgar-encrusted NOM particles usually showed limited sulfate reduction and the presence of fermentative metabolisms, whereas communities from realgar-free NOM particles were strongly dominated by sulfate reducers. We argue that the limited sulfate supply and intensive fermentation amplify reducing conditions, which make arsenic sulfide precipitation plausible in high-sulfate, low-arsenic groundwaters.
Keywords: Arsenic; Arsenic thiolation; Fermentation; Microcosm; Realgar biomineralization; Sulfate reduction.