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.
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A number of colleagues helped with sample processing and analyses: Věra Vonásková and Lenka Jílková (water analyses); Jana Schweigstillová, Michaela Fridrichová, and Zuzana Korbelová (SEM, EDS). We also wish to thank Tyler Kohler and Marek Stibal for editing the English manuscript.
This study was supported by the Czech Science Foundation (GACR 16-09352S).
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A typical soil profile at the natural arsenic anomaly in Mokrsko, Czech Republic. The brown upper layers correspond to an anthropogenic backfill. The realgar-containing black layers represent the buried wetland soil with abundant vegetation. Underground water table oscillates within this reduced zone. Depth of the soil pit is approx. 95 cm. (JPG 1336 kb)
Representative XRD patterns of the precipitates scraped from NOM particle surfaces. The bottom sediment instead of NOM is displayed in I3-3 only. The red vertical lines denote the diffraction lines for realgar (PDF reference code 00-024-077). Abbreviations: Bnz: bonazziite; Cal: calcite; Dic: dickite; Rlg: realgar; S: sulfur; Qtz: quartz; Wwl: wawelite. (JPG 1127 kb)
Table S1. Phylum composition of microbial communities from the incubation experiments. Proposed supergroups of phyla are marked by color shading. Table S2. Thorough characterization of OTUs having at least 1% abundance in at least 1 microcosm. Common characterization for more OTUs is used in cases, where phylogenetic distance of OTUs enabled to asses that they share the basic properties or when more detailed information was unavailable. The included chemistry of the of I3 series input water is representative for all experiments since the pore water composition is largely constant in time. (XLS 93 kb)
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Falteisek, L., Duchoslav, V. & Drahota, P. Realgar (As4S4) bioprecipitation in microcosm fed by a natural groundwater and organic matter. Environ Sci Pollut Res 26, 18766–18776 (2019). https://doi.org/10.1007/s11356-019-05237-4
- Sulfate reduction
- Realgar biomineralization
- Arsenic thiolation