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

Abstract

Solid UO 2 dissolution and uranium speciation in aqueous solutions that promote formation of uranyl peroxide macroanions was examined, focusing on the role of alkali metals. UO 2 powders were dissolved in solutions containing XOH (X = Li, Na, or K) and 30% H 2O2. 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 UO 2, 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 10 5 parts per million (ppm), which is comparable to concentrations attained by dissolving UO 2 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.

Authors:
 [1]; ORCiD logo [1];  [2];  [1];  [2];  [1]; ORCiD logo [3]
  1. Univ. of Notre Dame, IN (United States). Dept. of Civil and Environmental Engineering and Earth Sciences
  2. Univ. of Notre Dame, IN (United States). Dept. of Chemistry and Biochemistry
  3. Univ. of Notre Dame, IN (United States). Dept. of Civil and Environmental Engineering and Earth Sciences, and Dept. of Chemistry and Biochemistry
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA); Univ. of Notre Dame, IN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1460947
Grant/Contract Number:  
NA0003763; SC0001089
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 15; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; 36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY; uranyl; peroxide; clusters; uranium dioxide

Citation Formats

Hickam, Sarah, Aksenov, Sergey M., Dembowski, Mateusz, Perry, Samuel N., Traustason, Hrafn, Russell, Meghan, and Burns, Peter C. Complexity of Uranyl Peroxide Cluster Speciation from Alkali-Directed Oxidative Dissolution of Uranium Dioxide. United States: N. p., 2018. Web. doi:10.1021/acs.inorgchem.8b01299.
Hickam, Sarah, Aksenov, Sergey M., Dembowski, Mateusz, Perry, Samuel N., Traustason, Hrafn, Russell, Meghan, & Burns, Peter C. Complexity of Uranyl Peroxide Cluster Speciation from Alkali-Directed Oxidative Dissolution of Uranium Dioxide. United States. doi:10.1021/acs.inorgchem.8b01299.
Hickam, Sarah, Aksenov, Sergey M., Dembowski, Mateusz, Perry, Samuel N., Traustason, Hrafn, Russell, Meghan, and Burns, Peter C. Fri . "Complexity of Uranyl Peroxide Cluster Speciation from Alkali-Directed Oxidative Dissolution of Uranium Dioxide". United States. doi:10.1021/acs.inorgchem.8b01299. https://www.osti.gov/servlets/purl/1460947.
@article{osti_1460947,
title = {Complexity of Uranyl Peroxide Cluster Speciation from Alkali-Directed Oxidative Dissolution of Uranium Dioxide},
author = {Hickam, Sarah and Aksenov, Sergey M. and Dembowski, Mateusz and Perry, Samuel N. and Traustason, Hrafn and Russell, Meghan and Burns, Peter C.},
abstractNote = {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.},
doi = {10.1021/acs.inorgchem.8b01299},
journal = {Inorganic Chemistry},
number = 15,
volume = 57,
place = {United States},
year = {2018},
month = {7}
}

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  • Chemistry – A European Journal, Vol. 25, Issue 24
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journal, February 2019

  • Arteaga, Ana; Zhang, Lei; Hickam, Sarah
  • Chemistry – A European Journal, Vol. 25, Issue 24
  • DOI: 10.1002/chem.201806227

An anionic manganese( ii ) metal–organic framework for uranyl adsorption
journal, January 2019

  • Zhang, Tao; Ling, Bo-Kai; Hu, Yue-Qiao
  • CrystEngComm, Vol. 21, Issue 26
  • DOI: 10.1039/c9ce00603f