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Title: Structure and thermodynamics of uranium-containing iron garnets

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+ (x = 0 and substituted sample), U substitution had a significant effect on local environments, the extent of U isubstitution 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 determined by high temperature oxide melt solution calorimetry. The results indicate that these substituted garnets are thermodynamicallymore » stable under reducing conditions. 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.« less
Authors:
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Publication Date:
OSTI Identifier:
1324888
Report Number(s):
PNNL-SA-113283
Journal ID: ISSN 0016-7037; 47956; KP1704020
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Geochimica et Cosmochimica Acta; Journal Volume: 189
Publisher:
The Geochemical Society; The Meteoritical Society
Research Org:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory