Redox Heterogeneities Promote Thioarsenate Formation and Release into Groundwater from Low Arsenic Sediments

Kumar, Naresh; Noël, Vincent; Planer-Friedrich, Britta; Besold, Johannes; Lezama-Pacheco, Juan; Bargar, John R.; Brown, Gordon E.; Fendorf, Scott; Boye, Kristin

doi:10.1021/acs.est.9b06502

Redox Heterogeneities Promote Thioarsenate Formation and Release into Groundwater from Low Arsenic Sediments

Journal Article · Tue Feb 18 00:00:00 EST 2020 · Environmental Science and Technology

DOI:https://doi.org/10.1021/acs.est.9b06502· OSTI ID:1633945

Kumar, Naresh ^[1]; ^[2]; ^[3]; Besold, Johannes ^[3]; Lezama-Pacheco, Juan ^[4]; ^[2]; Brown, Gordon E. ^[5]; ^[4]; ^[2]

Stanford Univ., CA (United States); Univ. of Vienna (Austria)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Univ. of Bayreuth (Germany)
Stanford Univ., CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., CA (United States)

Groundwater contamination by As from natural and anthropogenic sources is a worldwide concern. Redox heterogeneities over space and time are common and can influence the molecular-level speciation of As, and thus, As release/retention but are largely unexplored. Here, we present results from a dual-domain column experiment, with natural organic-rich, fine-grained, and sulfidic sediments embedded as lenses (referred to as “reducing lenses”) within natural aquifer sand. We show that redox interfaces in sulfur-rich, alkaline aquifers may release concerning levels of As, even when sediment As concentration is low (<2 mg/kg), due to the formation of mobile thioarsenates at aqueous sulfide/Fe molar ratios <1. In our experiments, this behavior occurred in the aquifer sand between reducing lenses and was attributed to the spreading of sulfidic conditions and subsequent Fe reductive dissolution. In contrast, inside reducing lenses (and some locations in the aquifer) the aqueous sulfide/Fe molar ratios exceeded 1 and aqueous sulfide/As molar ratios exceeded 100, which partitioned As(III)–S to the solid phase (associated with organics or as realgar (As₄S₄)). These results highlight the importance of thioarsenates in natural sediments and indicate that redox interfaces and sediment heterogeneities could locally degrade groundwater quality, even in aquifers with unconcerning solid-phase As concentrations.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-76SF00515; SC0020205

OSTI ID:: 1633945

Journal Information:: Environmental Science and Technology, Journal Name: Environmental Science and Technology Journal Issue: 6 Vol. 54; ISSN 0013-936X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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