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

Sarah Scherrer; Cassandra Gates; Harindu Rajapaksha; Samuel Greer; Benjamin Stein; Tori Forbes

doi:10.1002/anie.202400379

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

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

Sarah Scherrer, Cassandra Gates, Harindu Rajapaksha, Samuel Greer, Benjamin Stein and Tori Forbes

Angewandte Chemie (International ed.), Vol.63(21), e202400379

04/23/2024

DOI: 10.1002/anie.202400379

PMID: 38530229

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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, weapons-grade, and natural uranium. Density functional theory calculations indicated that the predicted EPR signals matched well with a superoxide (O2-•) 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.

radiation

EPR

uranyl peroxide

oxygen radicals

uranyl superoxide

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Details

Title: Subtitle: Superoxide Radicals in Uranyl Peroxide Solids: Lasting Signatures Identified by Electron Paramagnetic Resonance Spectroscopy
Creators: Sarah Scherrer - The University of Iowa, Department of Chemistry, W374 Chemistry Building, 52242, Iowa City, UNITED STATES
Cassandra Gates - Los Alamos National Laboratory
Harindu Rajapaksha - University of Iowa
Samuel Greer - Los Alamos National Laboratory
Benjamin Stein - Los Alamos National Laboratory
Tori Forbes - University of Iowa
Resource Type: Journal article
Publication Details: Angewandte Chemie (International ed.), Vol.63(21), e202400379
DOI: 10.1002/anie.202400379
PMID: 38530229
NLM abbreviation: Angew Chem Int Ed Engl
eISSN: 1521-3773
Publisher: Wiley
Language: English
Electronic publication date: 03/26/2024
Date published: 04/23/2024
Academic Unit: Civil and Environmental Engineering; Core Research Facilities; Chemistry
Record Identifier: 9984577110702771

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