Iron Vacancies Accommodate Uranyl Incorporation into Hematite
Abstract
Radiotoxic uranium contamination in natural systems and nuclear waste containment can be sequestered by incorporation into naturally abundant iron (oxyhydr)oxides such as hematite (α-Fe2O3) during mineral growth. The stability and properties of the resulting uranium-doped material are impacted by the local coordination environment of incorporated uranium. While measurements of uranium coordination in hematite have been attempted using extended X-ray absorption fine structure (EXAFS) analysis, traditional shell-by-shell EXAFS fitting yields ambiguous results. We used hybrid functional ab initio molecular dynamics (AIMD) simulations for various defect configurations to generate synthetic EXAFS spectra which were combined with adsorbed uranyl spectra to fit experimental U L3-edge EXAFS for U6+-doped hematite. We discovered that the hematite crystal structure accommodates a trans-dioxo uranyl-like configuration for U6+ that substitutes for structural Fe3+, which requires two partially protonated Fe vacancies situated at opposing corner-sharing sites. Surprisingly, the best match to experiment included significant proportions of vacancy configurations other than the minimum-energy configuration, pointing to the importance of incorporation mechanisms and kinetics in determining the state of an impurity incorporated into a host phase under low temperature hydrothermal conditions.
- Authors:
-
- Research Centre for Radwaste Disposal and Williamson Research Centre for Molecular Environmental Science, School of Earth, Atmospheric and Environmental Sciences, The University of Manchester, Manchester M13 9PL, United Kingdom
- Publication Date:
- Research Org.:
- Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States); Stanford Univ., CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; USDOE Office of Science (SC), Biological and Environmental Research (BER)
- OSTI Identifier:
- 1459051
- Alternate Identifier(s):
- OSTI ID: 1508821
- Grant/Contract Number:
- AC05-76RL01830; AC02-06CH11357; AC02-76SF00515
- Resource Type:
- Published Article
- Journal Name:
- Environmental Science and Technology
- Additional Journal Information:
- Journal Name: Environmental Science and Technology Journal Volume: 52 Journal Issue: 11; Journal ID: ISSN 0013-936X
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
McBriarty, Martin E., Kerisit, Sebastien, Bylaska, Eric J., Shaw, Samuel, Morris, Katherine, and Ilton, Eugene S. Iron Vacancies Accommodate Uranyl Incorporation into Hematite. United States: N. p., 2018.
Web. doi:10.1021/acs.est.8b00297.
McBriarty, Martin E., Kerisit, Sebastien, Bylaska, Eric J., Shaw, Samuel, Morris, Katherine, & Ilton, Eugene S. Iron Vacancies Accommodate Uranyl Incorporation into Hematite. United States. https://doi.org/10.1021/acs.est.8b00297
McBriarty, Martin E., Kerisit, Sebastien, Bylaska, Eric J., Shaw, Samuel, Morris, Katherine, and Ilton, Eugene S. Mon .
"Iron Vacancies Accommodate Uranyl Incorporation into Hematite". United States. https://doi.org/10.1021/acs.est.8b00297.
@article{osti_1459051,
title = {Iron Vacancies Accommodate Uranyl Incorporation into Hematite},
author = {McBriarty, Martin E. and Kerisit, Sebastien and Bylaska, Eric J. and Shaw, Samuel and Morris, Katherine and Ilton, Eugene S.},
abstractNote = {Radiotoxic uranium contamination in natural systems and nuclear waste containment can be sequestered by incorporation into naturally abundant iron (oxyhydr)oxides such as hematite (α-Fe2O3) during mineral growth. The stability and properties of the resulting uranium-doped material are impacted by the local coordination environment of incorporated uranium. While measurements of uranium coordination in hematite have been attempted using extended X-ray absorption fine structure (EXAFS) analysis, traditional shell-by-shell EXAFS fitting yields ambiguous results. We used hybrid functional ab initio molecular dynamics (AIMD) simulations for various defect configurations to generate synthetic EXAFS spectra which were combined with adsorbed uranyl spectra to fit experimental U L3-edge EXAFS for U6+-doped hematite. We discovered that the hematite crystal structure accommodates a trans-dioxo uranyl-like configuration for U6+ that substitutes for structural Fe3+, which requires two partially protonated Fe vacancies situated at opposing corner-sharing sites. Surprisingly, the best match to experiment included significant proportions of vacancy configurations other than the minimum-energy configuration, pointing to the importance of incorporation mechanisms and kinetics in determining the state of an impurity incorporated into a host phase under low temperature hydrothermal conditions.},
doi = {10.1021/acs.est.8b00297},
journal = {Environmental Science and Technology},
number = 11,
volume = 52,
place = {United States},
year = {Mon May 14 00:00:00 EDT 2018},
month = {Mon May 14 00:00:00 EDT 2018}
}
https://doi.org/10.1021/acs.est.8b00297
Web of Science
Figures / Tables:
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