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Title: Uranium(IV) adsorption by natural organic matter in anoxic sediments

Abstract

Uranium is an important fuel source and a global environmental contaminant. It accumulates in the tetravalent state, U(IV), in anoxic sediments, including ore deposits, marine basins, and contaminated aquifers. However, very little is known about the speciation of U(IV) in low temperature geochemical environments, inhibiting the development of a conceptual model of U behavior. Until recently, U(IV) was assumed to exist predominantly as the sparingly soluble mineral uraninite (UO2) in anoxic sediments; yet studies now show that UO2 is not often dominant in these environments. However, a model of U(IV) speciation under environmentally relevant conditions has not yet been developed. Here we show that complexes of U(IV) adsorb on organic carbon and organic carbon-coated clays in an organic-rich natural substrate under field-relevant conditions. Whereas previous research assumed that the U(IV) product depended on the reduction pathway, our results demonstrate that UO2 formation can be inhibited simply by decreasing the U:solid ratio. Thus, it is the number and type of surface ligands that controls U(IV) speciation subsequent to U(VI) reduction. Projections of U transport and bioavailability, and thus its threat to human and ecosystem health, must consider retention of U(IV) ions within the local sediment environment.

Authors:
; ; ;
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1338629
Alternate Identifier(s):
OSTI ID: 1340156; OSTI ID: 1344623
Report Number(s):
SLAC-PUB-16909; PNNL-SA-119314
Journal ID: ISSN 0027-8424; /pnas/114/4/711.atom
Grant/Contract Number:  
AC02-76SF00515; AC05-76RL01830
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 114 Journal Issue: 4; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
58 GEOSCIENCES; 36 MATERIALS SCIENCE; EARTH, ENV; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Environmental Molecular Sciences Laboratory

Citation Formats

Bone, Sharon E., Dynes, James J., Cliff, John, and Bargar, John R.. Uranium(IV) adsorption by natural organic matter in anoxic sediments. United States: N. p., 2017. Web. https://doi.org/10.1073/pnas.1611918114.
Bone, Sharon E., Dynes, James J., Cliff, John, & Bargar, John R.. Uranium(IV) adsorption by natural organic matter in anoxic sediments. United States. https://doi.org/10.1073/pnas.1611918114
Bone, Sharon E., Dynes, James J., Cliff, John, and Bargar, John R.. Mon . "Uranium(IV) adsorption by natural organic matter in anoxic sediments". United States. https://doi.org/10.1073/pnas.1611918114.
@article{osti_1338629,
title = {Uranium(IV) adsorption by natural organic matter in anoxic sediments},
author = {Bone, Sharon E. and Dynes, James J. and Cliff, John and Bargar, John R.},
abstractNote = {Uranium is an important fuel source and a global environmental contaminant. It accumulates in the tetravalent state, U(IV), in anoxic sediments, including ore deposits, marine basins, and contaminated aquifers. However, very little is known about the speciation of U(IV) in low temperature geochemical environments, inhibiting the development of a conceptual model of U behavior. Until recently, U(IV) was assumed to exist predominantly as the sparingly soluble mineral uraninite (UO2) in anoxic sediments; yet studies now show that UO2 is not often dominant in these environments. However, a model of U(IV) speciation under environmentally relevant conditions has not yet been developed. Here we show that complexes of U(IV) adsorb on organic carbon and organic carbon-coated clays in an organic-rich natural substrate under field-relevant conditions. Whereas previous research assumed that the U(IV) product depended on the reduction pathway, our results demonstrate that UO2 formation can be inhibited simply by decreasing the U:solid ratio. Thus, it is the number and type of surface ligands that controls U(IV) speciation subsequent to U(VI) reduction. Projections of U transport and bioavailability, and thus its threat to human and ecosystem health, must consider retention of U(IV) ions within the local sediment environment.},
doi = {10.1073/pnas.1611918114},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 4,
volume = 114,
place = {United States},
year = {2017},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
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https://doi.org/10.1073/pnas.1611918114

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