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Title: Dissolution of poorly soluble uranyl phosphate phases in the Metaautunite Subgroup under uranyl peroxide cage cluster forming conditions

Abstract

Uranyl phosphate minerals are widespread in uranium deposits and usually exhibit very low solubility in aqueous systems. Uranyl phosphates of the autunite group and metaautunite subgroup impact the mobility of uranium in the environment and have inspired groundwater remediation strategies that emphasize their low solubility. The importance of soluble uranium-bearing macro-anions, including nanoscale uranyl peroxide cage clusters, is largely unexplored relative to solubilization of normally low-solubility uranium minerals. Eight synthetic analogs of metaautunite subgroup minerals have been prepared and placed in various alkaline aqueous solutions containing hydrogen peroxide and tetraethylammonium hydroxide. Each uranyl phosphate studied has a topologically identical anionic sheet of uranyl square bipyramids and phosphate tetrahedra combined with various cations (Li+, Na+, K+, Rb+, Cs+, Mg2+, Ca2+, Ba2+) and water in the interlayer. Uranyl peroxides formed under many of the experimental conditions examined, including solid studtite [(UO2)(O2)(H2O)2](H2O)2 and soluble uranyl peroxide cage clusters containing as many as 28 uranyl ions. Uranyl phosphate solids in contact with solutions in which uranyl peroxide cage clusters formed dissolved extensively or completely. The greatest dissolution of uranyl phosphates occurred in systems that contained cations with larger hydrated radii, Li+ and Na+. The details of the uranium speciation in solution depended on themore » pH and counter cations provided from the interlayers of the uranyl phosphate solids.« less

Authors:
 [1];  [2];  [3];  [1];  [1];  [1];  [1];  [1];  [1];  [1]; ORCiD logo [1]
  1. Univ. of Notre Dame, IN (United States)
  2. Univ. of Notre Dame, IN (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  3. Univ. of Notre Dame, IN (United States); Clemson Univ., SC (United States)
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Univ. of Notre Dame, IN (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1811761
Alternate Identifier(s):
OSTI ID: 1596357
Report Number(s):
LLNL-JRNL-786890
Journal ID: ISSN 0003-004X; 965811
Grant/Contract Number:  
AC52-07NA27344; NA0003763
Resource Type:
Accepted Manuscript
Journal Name:
American Mineralogist
Additional Journal Information:
Journal Volume: 105; Journal Issue: 2; Journal ID: ISSN 0003-004X
Publisher:
Mineralogical Society of America
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 77 NANOSCIENCE AND NANOTECHNOLOGY; metaautunite; dissolution; uranium; studtite; uranyl peroxide nanoclusters; peroxide; uranyl phosphate

Citation Formats

Lobeck, Haylie L., Balboni, Enrica, Parker, Connor J., Kohlgruber, Tsuyoshi A., Xu, Mengyu, Boukdad, Sara, Ridder, Henry M., Traustason, Hrafn, Isner, Jordan K., Dzik, Ewa A., and Burns, Peter C.. Dissolution of poorly soluble uranyl phosphate phases in the Metaautunite Subgroup under uranyl peroxide cage cluster forming conditions. United States: N. p., 2020. Web. https://doi.org/10.2138/am-2020-7106.
Lobeck, Haylie L., Balboni, Enrica, Parker, Connor J., Kohlgruber, Tsuyoshi A., Xu, Mengyu, Boukdad, Sara, Ridder, Henry M., Traustason, Hrafn, Isner, Jordan K., Dzik, Ewa A., & Burns, Peter C.. Dissolution of poorly soluble uranyl phosphate phases in the Metaautunite Subgroup under uranyl peroxide cage cluster forming conditions. United States. https://doi.org/10.2138/am-2020-7106
Lobeck, Haylie L., Balboni, Enrica, Parker, Connor J., Kohlgruber, Tsuyoshi A., Xu, Mengyu, Boukdad, Sara, Ridder, Henry M., Traustason, Hrafn, Isner, Jordan K., Dzik, Ewa A., and Burns, Peter C.. Thu . "Dissolution of poorly soluble uranyl phosphate phases in the Metaautunite Subgroup under uranyl peroxide cage cluster forming conditions". United States. https://doi.org/10.2138/am-2020-7106. https://www.osti.gov/servlets/purl/1811761.
@article{osti_1811761,
title = {Dissolution of poorly soluble uranyl phosphate phases in the Metaautunite Subgroup under uranyl peroxide cage cluster forming conditions},
author = {Lobeck, Haylie L. and Balboni, Enrica and Parker, Connor J. and Kohlgruber, Tsuyoshi A. and Xu, Mengyu and Boukdad, Sara and Ridder, Henry M. and Traustason, Hrafn and Isner, Jordan K. and Dzik, Ewa A. and Burns, Peter C.},
abstractNote = {Uranyl phosphate minerals are widespread in uranium deposits and usually exhibit very low solubility in aqueous systems. Uranyl phosphates of the autunite group and metaautunite subgroup impact the mobility of uranium in the environment and have inspired groundwater remediation strategies that emphasize their low solubility. The importance of soluble uranium-bearing macro-anions, including nanoscale uranyl peroxide cage clusters, is largely unexplored relative to solubilization of normally low-solubility uranium minerals. Eight synthetic analogs of metaautunite subgroup minerals have been prepared and placed in various alkaline aqueous solutions containing hydrogen peroxide and tetraethylammonium hydroxide. Each uranyl phosphate studied has a topologically identical anionic sheet of uranyl square bipyramids and phosphate tetrahedra combined with various cations (Li+, Na+, K+, Rb+, Cs+, Mg2+, Ca2+, Ba2+) and water in the interlayer. Uranyl peroxides formed under many of the experimental conditions examined, including solid studtite [(UO2)(O2)(H2O)2](H2O)2 and soluble uranyl peroxide cage clusters containing as many as 28 uranyl ions. Uranyl phosphate solids in contact with solutions in which uranyl peroxide cage clusters formed dissolved extensively or completely. The greatest dissolution of uranyl phosphates occurred in systems that contained cations with larger hydrated radii, Li+ and Na+. The details of the uranium speciation in solution depended on the pH and counter cations provided from the interlayers of the uranyl phosphate solids.},
doi = {10.2138/am-2020-7106},
journal = {American Mineralogist},
number = 2,
volume = 105,
place = {United States},
year = {2020},
month = {1}
}

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