Reduction of Hg(II) by Fe(II)-Bearing Smectite Clay Minerals

O’Loughlin, Edward J.; Boyanov, Maxim I.; Kemner, Kenneth M.; Thalhammer, Korbinian O.

doi:10.3390/min10121079

Title: Reduction of Hg(II) by Fe(II)-Bearing Smectite Clay Minerals

Journal Article · Tue Dec 01 00:00:00 EST 2020 · Minerals

DOI:https://doi.org/10.3390/min10121079· OSTI ID:1727382

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Argonne National Lab. (ANL), Argonne, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States); Bulgarian Academy of Sciences, Sofia (Bulgaria)
Argonne National Lab. (ANL), Argonne, IL (United States); California Institute of Technology (CalTech), Pasadena, CA (United States)

Aluminosilicate clay minerals are often a major component of soils and sediments and many of these clays contain structural Fe (e.g., smectites and illites). Structural Fe(III) in smectite clays is redox active and can be reduced to Fe(II) by biotic and abiotic processes. Fe(II)-bearing minerals such as magnetite and green rust can reduce Hg(II) to Hg(0); however, the ability of other environmentally relevant Fe(II) phases, such as structural Fe(II) in smectite clays, to reduce Hg(II) is largely undetermined. We conducted experiments examining the potential for reduction of Hg(II) by smectite clay minerals containing 0–25 wt% Fe. Fe(III) in the clays (SYn-1 synthetic mica-montmorillonite, SWy-2 montmorillonite, NAu-1 and NAu-2 nontronite, and a nontronite from Cheney, Washington (CWN)) was reduced to Fe(II) using the citrate-bicarbonate-dithionite method. Experiments were initiated by adding 500 µM Hg(II) to reduced clay suspensions (4 g clay L–1) buffered at pH 7.2 in 20 mM 3-morpholinopropane-1-sulfonic acid (MOPS). The potential for Hg(II) reduction in the presence of chloride (0–10 mM) and at pH 5–9 was examined in the presence of reduced NAu-1. Analysis of the samples by Hg LIII-edge X-ray absorption fine structure (XAFS) spectroscopy indicated little to no reduction of Hg(II) by SYn-1 (0% Fe), while reduction of Hg(II) to Hg(0) was observed in the presence of reduced SWy-2, NAu-1, NAu-2, and CWN (2.8–24.8% Fe). Hg(II) was reduced to Hg(0) by NAu-1 at all pH and chloride concentrations examined. These results suggest that Fe(II)-bearing smectite clays may contribute to Hg(II) reduction in suboxic/anoxic soils and sediments.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1727382

Journal Information:: Minerals, Vol. 10, Issue 12; ISSN 2075-163X

Publisher:: MDPICopyright Statement

Country of Publication:: United States

Language:: English

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