Biomineralization of arsenate to arsenic sulfides is greatly enhanced at mildly acidic conditions

•The biological reduction of AsV and SO42− resulted in arsenic sulfide precipitation.•Arsenic sulfides formed were a mixture of As2S3 and AsS.•The bioprecipitation of arsenic sulfides is enhanced at mildly-acidic pH.•A higher proportion of As2S3 over AsS is obtained at circumneutral pH.•The methanogenic inhibition by As is reversed by arsenic sulfide mineral formation.

Arsenic (As) is an important water contaminant due to its high toxicity and widespread occurrence. Arsenic-sulfide minerals (ASM) are formed during microbial reduction of arsenate (AsV) and sulfate (SO42−). The objective of this research is to study the effect of the pH on the removal of As due to the formation of ASM in an iron-poor system. A series of batch experiments was used to study the reduction of SO42− and AsV by an anaerobic biofilm mixed culture in a range of pH conditions (6.1–7.2), using ethanol as the electron donor. Total soluble concentrations and speciation of S and As were monitored. Solid phase speciation of arsenic was characterized by x-ray adsorption spectroscopy (XAS). A marked decrease of the total aqueous concentrations of As and S was observed in the inoculated treatments amended with ethanol, but not in the non-inoculated controls, indicating that the As-removal was biologically mediated. The pH dramatically affected the extent and rate of As removal, as well as the stoichiometric composition of the precipitate. The amount of As removed was 2-fold higher and the rate of the As removal was up to 17-fold greater at pH 6.1 than at pH 7.2. Stoichiometric analysis and XAS results confirmed the precipitate was composed of a mixture of orpiment and realgar, and the proportion of orpiment in the sample increased with increasing pH. The results taken as a whole suggest that ASM formation is greatly enhanced at mildly acidic pH conditions.

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