Superoxide Radicals in Uranyl Peroxide Solids: Lasting Signatures Identified by Electron Paramagnetic Resonance Spectroscopy

Scherrer, Sarah K.; Gates, Cassandra; Rajapaksha, Harindu; Greer, Samuel M.; Stein, Benjamin W.; Forbes, Tori Z.

doi:10.1002/ange.202400379

Superoxide Radicals in Uranyl Peroxide Solids: Lasting Signatures Identified by Electron Paramagnetic Resonance Spectroscopy

Journal Article · Tue Apr 23 00:00:00 EDT 2024 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.202400379· OSTI ID:2340218

^[1]; Gates, Cassandra ^[2]; Rajapaksha, Harindu ^[1]; Greer, Samuel M. ^[2]; Stein, Benjamin W. ^[2]; ^[1]

Department of Chemistry University of Iowa Chemistry Building W374 Iowa City IA 52242 United States
Chemistry Division Los Alamos National Laboratory Los Alamos New Mexico 87545 United States

Abstract

U(VI) peroxide phases (studtite and meta‐studtite) are found throughout the nuclear fuel cycle and exist as corrosion products in high radiation fields. Peroxides are part of a family of reactive oxygen species (ROS) that include hydroperoxyl and superoxide species and are produced during alpha radiolysis of water. While U(VI) peroxides have been thoroughly investigated, the incorporation and stability of ROS species within studtite have not been validated. In the current study, electron paramagnetic resonance (EPR) spectroscopy was used to identify the presence of free radicals within a series of U(VI) peroxide samples containing depleted, highly enriched, and natural uranium. Density functional theory calculations indicated that the predicted EPR signals matched well with a superoxide (O ₂ ⁻ ⋅) species incorporated into the studtite structure, confirming the presence of ROS in the material. Further analysis of samples that were synthesized between 1945 and 2023 indicated that there is a correlation between the radical signal and the product of specific activity multiplied by age of the sample.

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Sponsoring Organization:: USDOE

OSTI ID:: 2340218

Alternate ID(s):: OSTI ID: 2340220

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 21 Vol. 136; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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