Rehydration of metastudtite in the alteration kinetics of α– and β–U3O8 in dilute aqueous solutions of hydrogen peroxide

Chamberlain, Carmen E.; Spano, Tyler L.; Hunt, Rodney Dale; Burns, Peter C.; Miskowiec, Andrew

doi:10.1016/j.jnucmat.2025.155941

Rehydration of metastudtite in the alteration kinetics of α– and β–U₃O₈ in dilute aqueous solutions of hydrogen peroxide

Journal Article · Wed Jun 04 00:00:00 EDT 2025 · Journal of Nuclear Materials

DOI:https://doi.org/10.1016/j.jnucmat.2025.155941· OSTI ID:3002745

^[1]; ^[2]; ^[2]; Burns, Peter C. ^[1]; ^[2]

University of Notre Dame, IN (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

The formation of alteration phases on uranium ore concentrates and used nuclear fuels under oxidizing conditions is key to understanding the potential mobility of radionuclides in the environment and designing optimal storage conditions of materials. However, the time-dependent distribution of alteration phases on α– and β–U₃O₈ under oxidizing conditions has yet to be explored. Here, in this study, crystalline powders of α– and β–U₃O₈ were submerged in aqueous solutions of hydrogen peroxide (1.6 × 10⁻¹ to 5.4 × 10⁻⁵ M) with aliquots of solution and solid removed for analysis at 1, 8, 15, 22, 29, 36, 46, 58, 71, and 83 days. Within one day there is significant alteration of U₃O₈ to the uranyl peroxide metastudtite, [(UO₂)(O₂)(H₂O)₂], that is replaced by studtite, [(UO₂)(O₂)(H₂O)₂]·2H₂O, within a week regardless of the polymorph of U₃O₈ or the initial concentration of H₂O₂ in solution, as determined by partial least squares regression (PLSR) of Raman spectra collected from the solids. A dissolution/reprecipitation mechanism is proposed for both the alteration of U₃O₈ to metastudtite and the subsequent alteration of both U₃O₈ and metastudtite to studtite. The two polymorphs of U₃O₈ exhibit similar rates and extents of alteration over time. The rehydration of metastudtite to studtite has not been previously reported and highlights the need for future work to determine the mechanism by which metastudtite is converted to studtite and what other conditions facilitate this rehydration.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 3002745

Journal Information:: Journal of Nuclear Materials, Journal Name: Journal of Nuclear Materials Vol. 615; ISSN 0022-3115

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Rehydration of metastudtite in the alteration kinetics of α– and β–U3O8 in dilute aqueous solutions of hydrogen peroxide

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References (43)

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Rehydration of metastudtite in the alteration kinetics of α– and β–U₃O₈ in dilute aqueous solutions of hydrogen peroxide