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Detrital peat (organic carbon-enriched deposit) with high arsenic (As) content is widely distributed in sediments where groundwater As contamination exists. Iron sulfides often persist in these sediments under anoxic conditions. However, the mechanisms and pathways of formation of iron sulfides and its potential contribution in controlling As mobility are still poorly understood. In this study, we examined three As-contaminated peat sediments from the Hetao Basin in China to gain better understanding of the complex interplay between iron sulfides formation and As mobility. We employed high-resolution spectroscopic techniques, including X-ray absorption spectroscopy and 57Fe Mössbauer spectroscopy, coupled with electron microscopy to determine the speciation of iron sulfides and the associated As in the peat sediments. Pyrite (FeS 2) and metastable greigite (Fe 3 S 4) persisted in peat as end-members of S and Fe diagenetic pathways. The Fe-rich phyllosilicates and decaying plant tissues provided the ideal micro-environments for pyrite and greigite nucleation. Pyrite formation most likely occurred via the polysulfides pathway in the surface water-sediments interface during early diagenetic process, while the relative enrichment of reactive Fe compared to sulfide possibly inhibited the transformation of greigite to pyrite in such Fe-rich sediments. Our results revealed that the peat sediments could act as a stable sink for As immobilization under steady groundwater anoxic conditions, with As content up to 250 mg/kg and large proportions (40 to 60 wt.% As) sequestered in pyrite and greigite. Pyrite crystallites had up to 1 wt.% As content through the replacement of the S-I sites. Greigite crystallites had a relatively constant As content ranging from ∼500 to ∼1400 mg/kg. Instead of being adsorbed or structurally incorporated, arsenic formed distinct arsenic sulfide phase in the greigite-enriched sediments, which was analogous to realgar. The transfer of As from iron sulfides to ferrihydrite temporarily retarded As release into groundwater under slightly oxic groundwater conditions. However, the reductive dissolution of ferrihydrite and potential subsequent As re-release could be a source of As in groundwater under disturbed redox conditions. [ABSTRACT FROM AUTHOR]

The formation of iron-sulfur-arsenic (Fe–S–As) minerals during biogeochemical processes in As contaminated aquifers remains poorly understood despite their importance to understanding As release and transport in such systems. In this study, X-ray absorption and Mössbauer spectroscopies complemented by electron microscopy, and chemical extractions were used to examine vertical changes of As, Fe and S speciation for the example of sediments in the Hetao Basin. Reduction of Fe(III), As(V) and SO 4 2- species were shown to co-occur in the aquifers. Iron oxides were observed to be predominantly goethite and hematite (36 – 12%) and appeared to decrease in abundance with depth. Furthermore, reduced As (including arsenite and As sulfides) and sulfur species (including S(-II), S(-I) and S0) increased from 16% to 76% and from 13% to 44%, respectively. Iron oxides were the major As carrier in the sediments, and the lower groundwater As concentration consists with less desorbable and reducible As in the sediments. The formation of As-Fe sulfides (e.g., As containing pyrite and greigite) induced by redox heterogeneities likely contribute to localized lower groundwater As concentrations. These results help to further elucidate the complex relationship between biogeochemical processes and minerals formation in As contaminated aquifers. ga1 • Speciation of As, S and Fe is mainly characterized by XAS. • Fe(III) oxides mainly include goethite and hematite, and the content decrease with depth. • The reduced As (As(III) species and As sulfides) species generally increases with depth. • Heterogenous Fe sulfides formation contributes to lower groundwater As concentration. [ABSTRACT FROM AUTHOR]