An experimental and ab initio study on the abiotic reduction of uranyl by ferrous iron

Taylor, S. D.; Marcano, M. C.; Rosso, K. M.; Becker, U.

doi:10.1016/j.gca.2015.01.021

An experimental and ab initio study on the abiotic reduction of uranyl by ferrous iron

Journal Article · Sun Feb 22 23:00:00 EST 2015 · Geochimica et Cosmochimica Acta

DOI:https://doi.org/10.1016/j.gca.2015.01.021· OSTI ID:1700520

Taylor, S. D. ^[1]; Marcano, M. C. ^[1]; Rosso, K. M. ^[2]; Becker, U. ^[1]

Univ. of Michigan, Ann Arbor, MI (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

It is important to understand the mechanisms controlling the removal of uranyl from solution from an environmental standpoint, particularly whether soluble Fe(II) is capable of reducing soluble U(VI) to insoluble U(IV). Experiments were performed to shed light into discrepancies of recent studies about precipitation of U-containing solids without changing oxidation states versus precipitation/reduction reactions, especially with respect to the kinetics of these reactions. To understand the atomistic mechanisms, thermodynamics, and kinetics of these redox processes, ab initio electron transfer (ET) calculations, using Marcus theory, were applied to study the reduction of U(VI)_aq to U(V)_aq by Fe(II)_aq (the first rate-limiting ET-step). Outer-sphere (OS) and inner-sphere (IS) Fe–U complexes were modeled to represent simple species within a homogeneous environment through which ET could occur.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1700520

Report Number(s):: PNNL-SA--153389

Journal Information:: Geochimica et Cosmochimica Acta, Journal Name: Geochimica et Cosmochimica Acta Vol. 156; ISSN 0016-7037

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

Country of Publication:: United States

Language:: English

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