Structure and thermodynamics of uranium-containing iron garnets
Abstract
Use of crystalline garnet as a waste form phase appears to be advantageous for accommodating actinides from nuclear waste. Previous studies show that large amounts of uranium (U) and its analogues such as cerium (Ce) and thorium (Th) can be incorporated into the garnet structure. In this study, we synthesized U loaded garnet phases, Ca3UxZr2–xFe3O12 (x = 0.5–0.7), along with the endmember phase, Ca3(Zr2)SiFe3+2O12, for comparison. The oxidation states of U were determined by X-ray photoelectron and absorption spectroscopies, revealing the presence of mixed pentavalent and hexavalent uranium in the phases with x = 0.6 and 0.7. The oxidation states and coordination environments of Fe were measured using transmission 57Fe-Mössbauer spectroscopy, which shows that all iron is tetrahedrally coordinated Fe3+. U substitution had a significant effect on local environments, the extent of U substitution within this range had a minimal effect on the structure, and unlike in the x = 0 sample, Fe exists in two different environments in the substituted garnets. The enthalpies of formation of garnet phases from constituent oxides and elements were first time determined by high temperature oxide melt solution calorimetry. The results indicate that these substituted garnets are thermodynamically stable under reducing conditions. Furthermore, ourmore »
- Authors:
-
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of California, Davis, CA (United States)
- Univ. of California, Davis, CA (United States)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Univ. of Chicago, Chicago, IL (United States)
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Publication Date:
- Research Org.:
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)
- OSTI Identifier:
- 1296668
- Alternate Identifier(s):
- OSTI ID: 1435357
- Report Number(s):
- LA-UR-15-27116
Journal ID: ISSN 0016-7037
- Grant/Contract Number:
- AC52-06NA25396; SC0001089; AC06-76RLO1930; FG02-94ER14466; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Geochimica et Cosmochimica Acta
- Additional Journal Information:
- Journal Volume: 189; Journal ID: ISSN 0016-7037
- Publisher:
- The Geochemical Society; The Meteoritical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE WASTES FROM NUCLEAR FACILITIES; 36 MATERIALS SCIENCE; Inorganic and Physical Chemistry
Citation Formats
Guo, Xiaofeng, Navrotsky, Alexandra, Kukkadapu, Ravi K., Engelhard, Mark H., Lanzirotti, Antonio, Newville, Matthew, Ilton, Eugene S., Sutton, Stephen R., and Xu, Hongwu. Structure and thermodynamics of uranium-containing iron garnets. United States: N. p., 2016.
Web. doi:10.1016/j.gca.2016.05.043.
Guo, Xiaofeng, Navrotsky, Alexandra, Kukkadapu, Ravi K., Engelhard, Mark H., Lanzirotti, Antonio, Newville, Matthew, Ilton, Eugene S., Sutton, Stephen R., & Xu, Hongwu. Structure and thermodynamics of uranium-containing iron garnets. United States. https://doi.org/10.1016/j.gca.2016.05.043
Guo, Xiaofeng, Navrotsky, Alexandra, Kukkadapu, Ravi K., Engelhard, Mark H., Lanzirotti, Antonio, Newville, Matthew, Ilton, Eugene S., Sutton, Stephen R., and Xu, Hongwu. Thu .
"Structure and thermodynamics of uranium-containing iron garnets". United States. https://doi.org/10.1016/j.gca.2016.05.043. https://www.osti.gov/servlets/purl/1296668.
@article{osti_1296668,
title = {Structure and thermodynamics of uranium-containing iron garnets},
author = {Guo, Xiaofeng and Navrotsky, Alexandra and Kukkadapu, Ravi K. and Engelhard, Mark H. and Lanzirotti, Antonio and Newville, Matthew and Ilton, Eugene S. and Sutton, Stephen R. and Xu, Hongwu},
abstractNote = {Use of crystalline garnet as a waste form phase appears to be advantageous for accommodating actinides from nuclear waste. Previous studies show that large amounts of uranium (U) and its analogues such as cerium (Ce) and thorium (Th) can be incorporated into the garnet structure. In this study, we synthesized U loaded garnet phases, Ca3UxZr2–xFe3O12 (x = 0.5–0.7), along with the endmember phase, Ca3(Zr2)SiFe3+2O12, for comparison. The oxidation states of U were determined by X-ray photoelectron and absorption spectroscopies, revealing the presence of mixed pentavalent and hexavalent uranium in the phases with x = 0.6 and 0.7. The oxidation states and coordination environments of Fe were measured using transmission 57Fe-Mössbauer spectroscopy, which shows that all iron is tetrahedrally coordinated Fe3+. U substitution had a significant effect on local environments, the extent of U substitution within this range had a minimal effect on the structure, and unlike in the x = 0 sample, Fe exists in two different environments in the substituted garnets. The enthalpies of formation of garnet phases from constituent oxides and elements were first time determined by high temperature oxide melt solution calorimetry. The results indicate that these substituted garnets are thermodynamically stable under reducing conditions. Furthermore, our structural and thermodynamic analysis further provides explanation for the formation of natural uranium garnet, elbrusite-(Zr), and supports the potential use of Ca3UxZr2–xFe3O12 as viable waste form phases for U and other actinides.},
doi = {10.1016/j.gca.2016.05.043},
journal = {Geochimica et Cosmochimica Acta},
number = ,
volume = 189,
place = {United States},
year = {Thu Sep 15 00:00:00 EDT 2016},
month = {Thu Sep 15 00:00:00 EDT 2016}
}
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