Title: Surface area effects on the reduction of U^VI in the presence of synthetic montmorillonite

Abstract

Here, the redox transformations that affect the environmental mobility of metal or radionuclide contaminants typically take place in the presence of mineral or biological surfaces. Adsorption can alter the speciation and free energy of a dissolved ion and can thus change the occurrence, rate, or products of redox reactions relative to those expected in homogenous solution. Here, we investigated the effect of SYn-1, a redox-inactive synthetic montomorillonite clay mineral, on the reduction of U^VI by dihydroanthraquinone-2,6 disulfonate (AH₂QDS, the reduced form of the soluble electron shuttle AQDS). We varied the surface:U ratio in a circumneutral bicarbonate solution and measured the valence and atomic coordination of U in the solids using X-ray absorption spectroscopy (XANES and EXAFS). The spectra show that U^IV was the predominant product both in the presence or absence of the clay mineral, indicating that adsorption of U^VI to clay mineral surface sites does not affect its ability to be reduced by AH₂QDS. In the absence of the clay mineral and at low-to-intermediate surface:U ratios the predominant UIV product was nanoparticulate uraninite, UO₂. At the highest surface:U ratio tested (100 g/L clay mineral and 50 μM U) we observe a decrease in the proportion of uraninite down tomore » 50%, with the remaining U^IV present as adsorbed, non-uraninite species. These results are similar to previous findings with magnetite and rutile, where adsorbed U^IV were the predominant species below a specific surface coverage and U in excess of this coverage was precipitated as uraninite. The threshold coverage determined here for the SYn-1 clay mineral is 10-100 × lower than that determined for magnetite and rutile, suggesting that clay mineral surfaces may be less important than metal oxides for stabilizing non-uraninite U^IV species in natural sediments.« less

Authors:

Boyanov, Maxim I. ^[1]; Latta, Drew E. ^[2]; Scherer, Michelle M. ^[2]; O'Loughlin, Edward J. ^[3]; Kemner, Kenneth M. ^[3]

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+ Show Author Affiliations

1. Bulgarian Academy of Sciences, Sofia (Bulgaria); Argonne National Lab. (ANL), Argonne, IL (United States)
2. The Univ. of Iowa, Iowa City, IA (United States)
3. Argonne National Lab. (ANL), Argonne, IL (United States)

Publication Date:

Wed Dec 14 00:00:00 EST 2016

Research Org.:

Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23), Subsurface Biogeochemical Research; USDOE

OSTI Identifier:

1364633

Alternate Identifier(s):

OSTI ID: 1573101

Grant/Contract Number:  

AC02-06CH11357

Resource Type:

Accepted Manuscript

Journal Name:

Chemical Geology

Additional Journal Information:

Journal Volume: 464; Journal Issue: C; Journal ID: ISSN 0009-2541

Publisher:

Elsevier

Country of Publication:

United States

Language:

English

Subject:

36 MATERIALS SCIENCE; 58 GEOSCIENCES; AQDS; XANES/EXAFS; clay mineral; non-uraninite products; reduction; uranium