Redox Transformations of As and Se at the Surfaces of Natural and Synthetic Ferric Nontronites: Role of Structural and Adsorbed Fe(II)

Ilgen, Anastasia G.; Kruichak, Jessica N.; Artyushkova, Kateryna; Newville, Matt G.; Sun, Chengjun J.

doi:10.1021/acs.est.7b03058

Title: Redox Transformations of As and Se at the Surfaces of Natural and Synthetic Ferric Nontronites: Role of Structural and Adsorbed Fe(II)

Journal Article · Tue Aug 29 00:00:00 EDT 2017 · Environmental Science and Technology

DOI:https://doi.org/10.1021/acs.est.7b03058· OSTI ID:1420143

^[1]; Kruichak, Jessica N. ^[1];

^[2]; Newville, Matt G. ^[3]; Sun, Chengjun J. ^[3]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Univ. of New Mexico, Albuquerque, NM (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

Adsorption and redox transformations on clay mineral surfaces are prevalent in surface environments. We examined the redox reactivity of iron Fe(II)/Fe(III) associated with natural and synthetic ferric nontronites. Specifically, we assessed how Fe(II) residing in the octahedral sheets, or Fe(II) adsorbed at the edge sites alters redox activity of nontronites. To probe the redox activity we used arsenic (As) and selenium (Se). Activation of both synthetic and natural ferric nontronites was. observed following the introduction of Fe(II) into predominantly-Fe(III) octahedral sheets or through the adsorption of Fe(II) onto the mineral surface. The oxidation of As(III) to As(V) was observed via catalytic (oxic conditions) and, to a lesser degree, via direct (anoxic conditions) pathways. We provide experimental evidence for electron transfer from As(III) to Fe(111) at the natural and synthetic nontronite surfaces, and illustrate that only a fraction of structural Fe(III) is accessible for redox transformations. We show that As adsorbed onto natural and synthetic nontronites forms identical adsorption complexes, namely inner-sphere binuclear bidentate. In conclusion, we show that the formation of an inner-sphere adsorption complex may be a necessary step for the redox transformation via catalytic or direct oxidation pathways.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1420143

Journal Information:: Environmental Science and Technology, Vol. 51, Issue 19; ISSN 0013-936X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 23 works

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Title: Redox Transformations of As and Se at the Surfaces of Natural and Synthetic Ferric Nontronites: Role of Structural and Adsorbed Fe(II)

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