Chromium isotope fractionation during reduction of Chromium(VI) by Iron(II/III)-bearing clay minerals

Joe-Wong, Claresta; Weaver, Karrie L.; Brown, Shaun T.; Maher, Kate

doi:10.1016/j.gca.2020.09.034

Title: Chromium isotope fractionation during reduction of Chromium(VI) by Iron(II/III)-bearing clay minerals

Journal Article · Tue Oct 06 00:00:00 EDT 2020 · Geochimica et Cosmochimica Acta

DOI:https://doi.org/10.1016/j.gca.2020.09.034· OSTI ID:1844244

^[1]; Weaver, Karrie L. ^[1];

^[2];

^[1]

Stanford Univ., CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Chromium stable isotope ratios are used to trace the reduction of Cr(VI) to Cr(III) in both ancient and modern systems. However, quantitative interpretation of Cr isotopic signatures has been stymied by the large variability in isotopic fractionation factors for Cr(VI) reduction by different reductants. Here we determine Cr isotope fractionation factors during Cr(VI) reduction by Fe(II/III)-bearing clay minerals, which are abundant in subsurface environments. Several variables were tested: pH, total Fe content of the clay, and the fraction of reduced Fe within the clay (Fe(II)/Fe(total)). The latter controls the standard reduction potential of the clay. Our results demonstrate that neither pH nor total Fe content of the clay have major effects on isotopic fractionation. In contrast, as the effective standard reduction potential of the clay and thus the standard free energy of Cr(VI) reduction become more negative, Cr isotope fractionation factors decrease in magnitude from - 4.9 to -1.3‰ according to a linear free energy relationship. This linear free energy relationship can be predicted from Marcus electron transfer theory and allows first-order predictions of Cr isotope fractionation factors to be made from the standard reduction potential or Fe(II)/Fe(total) of a clay, potentially improving our ability to model Cr isotope signatures in geochemical systems. Chromium is the first isotope system to show such a linear free energy relationship over a diverse range of reductants, including both aqueous and solid-phase reductants, and may provide a model for determining other redox-driven kinetic isotope effects in environmentally important isotope systems.

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Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); USDOD

Grant/Contract Number:: AC02-05CH11231; EAR-1254156

OSTI ID:: 1844244

Alternate ID(s):: OSTI ID: 1775804

Journal Information:: Geochimica et Cosmochimica Acta, Vol. 292; ISSN 0016-7037

Publisher:: Elsevier; The Geochemical Society; The Meteoritical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Chromium isotope fractionation during reduction of Chromium(VI) by Iron(II/III)-bearing clay minerals

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