Complexity of Uranyl Peroxide Cluster Speciation from Alkali-Directed Oxidative Dissolution of Uranium Dioxide

Hickam, Sarah; Aksenov, Sergey M.; Dembowski, Mateusz; Perry, Samuel N.; Traustason, Hrafn; Russell, Meghan; Burns, Peter C.

doi:10.1021/acs.inorgchem.8b01299

Complexity of Uranyl Peroxide Cluster Speciation from Alkali-Directed Oxidative Dissolution of Uranium Dioxide

Journal Article · Fri Jul 13 00:00:00 EDT 2018 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.8b01299· OSTI ID:1460947

Hickam, Sarah ^[1]; ^[2]; Dembowski, Mateusz ^[3]; Perry, Samuel N. ^[2]; Traustason, Hrafn ^[3]; Russell, Meghan ^[2]; ^[4]

Univ. of Notre Dame, IN (United States). Dept. of Civil and Environmental Engineering and Earth Sciences; University of Notre Dame
Univ. of Notre Dame, IN (United States). Dept. of Civil and Environmental Engineering and Earth Sciences
Univ. of Notre Dame, IN (United States). Dept. of Chemistry and Biochemistry
Univ. of Notre Dame, IN (United States). Dept. of Civil and Environmental Engineering and Earth Sciences, and Dept. of Chemistry and Biochemistry

Solid UO₂ dissolution and uranium speciation in aqueous solutions that promote formation of uranyl peroxide macroanions was examined, focusing on the role of alkali metals. UO₂ powders were dissolved in solutions containing XOH (X = Li, Na, or K) and 30% H₂O2. Inductively coupled plasma optical emission spectroscopy (ICP-OES) measurements of solutions revealed linear trends of uranium versus alkali concentration in solutions resulting from oxidative dissolution of UO₂, with X:U molar ratios of 1.0, showing that alkali availability determines the U concentrations in solution. The maximum U concentration in solution was 4.36 x 10⁵ parts per million (ppm), which is comparable to concentrations attained by dissolving UO₂ in boiling nitric acid, and was achieved by lithium hydroxide-promoted dissolution. Lastly, Raman spectroscopy and electrospray ionization mass spectrometry (ESI-MS) of solutions indicate that dissolution is accompanied by formation of various uranyl peroxide cluster species, the identity of which is alkali concentration-dependent, revealing remarkably complex speciation at high concentrations of base.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA); Univ. of Notre Dame, IN (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: NA0003763; SC0001089

OSTI ID:: 1460947

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 15 Vol. 57; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Complexity of Uranyl Peroxide Cluster Speciation from Alkali-Directed Oxidative Dissolution of Uranium Dioxide

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