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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; TRN: US2213197
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. doi: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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Works referenced in this record:

Uranyl peroxide enhanced nuclear fuel corrosion in seawater
journal, January 2012

  • Armstrong, C. R.; Nyman, M.; Shvareva, T.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 6
  • DOI: 10.1073/pnas.1119758109

In Situ Nanoscale Observations of Metatorbernite Surfaces Interacted with Aqueous Solutions
journal, February 2013

  • Astilleros, José Manuel; Pinto, André Jorge; Gonçalves, Mário A.
  • Environmental Science & Technology, Vol. 47, Issue 6
  • DOI: 10.1021/es302781k

On the determination of uraniumoxygen bond lengths in dioxouranium(VI) compounds by Raman spectroscopy
journal, February 1989


Contaminant Uranium Phases and Leaching at the Fernald Site in Ohio
journal, January 1996

  • Buck, Edgar C.; Brown, Neil R.; Dietz, Nancy L.
  • Environmental Science & Technology, Vol. 30, Issue 1
  • DOI: 10.1021/es9500825

U6+ Minerals and Inorganic Compounds: Insights into an Expanded Structural Hierarchy of Crystal Structures
journal, December 2005


Nanoscale uranium-based cage clusters inspired by uranium mineralogy
journal, February 2011


Studtite, [(UO 2 )(O 2 )(H 2 O) 2 ](H 2 O) 2 : The first structure of a peroxide mineral
journal, July 2003

  • Burns, Peter C.; Hughes, Karrie-Ann
  • American Mineralogist, Vol. 88, Issue 7
  • DOI: 10.2138/am-2003-0725

Captivation with encapsulation: a dozen years of exploring uranyl peroxide capsules
journal, January 2018

  • Burns, Peter C.; Nyman, May
  • Dalton Transactions, Vol. 47, Issue 17
  • DOI: 10.1039/C7DT04245K

Nuclear Fuel in a Reactor Accident
journal, March 2012

  • Burns, Peter C.; Ewing, Rodney C.; Navrotsky, Alexandra
  • Science, Vol. 335, Issue 6073
  • DOI: 10.1126/science.1211285

The oxidative dissolution of unirradiated UO2 by hydrogen peroxide as a function of pH
journal, October 2005


Study of the thermal stability of studtite by in situ Raman spectroscopy and DFT calculations
journal, March 2017

  • Colmenero, Francisco; Bonales, Laura J.; Cobos, Joaquín
  • Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 174
  • DOI: 10.1016/j.saa.2016.11.040

Crystal structure of bassetite and saléeite: new insight into autunite-group minerals [Crystal structure of bassetite and saléeite: new insight into autunite-group minerals]
journal, September 2016

  • Dal Bo, Fabrice; Hatert, Freédéric; Mees, Florias
  • European Journal of Mineralogy, Vol. 28, Issue 3
  • DOI: 10.1127/ejm/2016/0028-2527

The Propensity of Uranium-Peroxide Systems to Preserve Nanosized Assemblies
journal, July 2017


Computationally-Guided Assignment of Unexpected Signals in the Raman Spectra of Uranyl Triperoxide Complexes
journal, January 2017


Thermodynamic properties of phosphate members of the meta-autunite group: A high-temperature calorimetric study
journal, November 2017

  • Dzik, Ewa A.; Lobeck, Haylie L.; Zhang, Lei
  • The Journal of Chemical Thermodynamics, Vol. 114
  • DOI: 10.1016/j.jct.2017.07.007

Thermodynamic characterization of synthetic autunite
journal, October 2017

  • Dzik, Ewa A.; Lobeck, Haylie L.; Zhang, Lei
  • American Mineralogist, Vol. 102, Issue 10
  • DOI: 10.2138/am-2017-6109

RAMAN Spectra of Peroxides
journal, January 1975

  • Eysel, H. H.; Thym, S.
  • Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 411, Issue 2
  • DOI: 10.1002/zaac.19754110202

The Key Role of U 28 in the Aqueous Self-Assembly of Uranyl Peroxide Nanocages
journal, August 2016


Pore-scale evaluation of uranyl phosphate precipitation in a model groundwater system: PORE-SCALE URANYL PHOSPHATE PRECIPITATION
journal, February 2013

  • Fanizza, Michael F.; Yoon, Hongkyu; Zhang, Changyong
  • Water Resources Research, Vol. 49, Issue 2
  • DOI: 10.1002/wrcr.20088

Preparation of crystals of sparingly soluble salts
journal, March 1934

  • Fernelius, W. Conard; Detling, Kenneth D.
  • Journal of Chemical Education, Vol. 11, Issue 3
  • DOI: 10.1021/ed011p176

Experimental measurements of U60 nanocluster stability in aqueous solution
journal, May 2015

  • Flynn, Shannon L.; Szymanowski, Jennifer E. S.; Gao, Yunyi
  • Geochimica et Cosmochimica Acta, Vol. 156
  • DOI: 10.1016/j.gca.2015.02.021

Alteration of dehydrated schoepite and soddyite to studtite, [(UO2)(O2)(H2O)2](H2O)2
journal, December 2010

  • Forbes, T. Z.; Horan, P.; Devine, T.
  • American Mineralogist, Vol. 96, Issue 1
  • DOI: 10.2138/am.2011.3517

Mechanisms of Uranium Interactions with Hydroxyapatite:  Implications for Groundwater Remediation
journal, January 2002

  • Fuller, C. C.; Bargar, J. R.; Davis, J. A.
  • Environmental Science & Technology, Vol. 36, Issue 2
  • DOI: 10.1021/es0108483

Selective Permeability of Uranyl Peroxide Nanocages to Different Alkali Ions: Influences from Surface Pores and Hydration Shells
journal, November 2015

  • Gao, Yunyi; Haso, Fadi; Szymanowski, Jennifer E. S.
  • Chemistry - A European Journal, Vol. 21, Issue 51
  • DOI: 10.1002/chem.201503773

Remobilization of U and REE and the formation of secondary minerals in oxidized U deposits
journal, March 2013

  • Gob, S.; Guhring, J. -E.; Bau, M.
  • American Mineralogist, Vol. 98, Issue 4
  • DOI: 10.2138/am.2013.4275

Thermodynamic Properties of Autunite, Uranyl Hydrogen Phosphate, and Uranyl Orthophosphate from Solubility and Calorimetric Measurements
journal, October 2009

  • Gorman-Lewis, Drew; Shvareva, Tatiana; Kubatko, Karrie-Ann
  • Environmental Science & Technology, Vol. 43, Issue 19
  • DOI: 10.1021/es9012933

Quantification of kinetic rate law parameters for the dissolution of natural autunite in the presence of aqueous bicarbonate ions at high concentrations
journal, October 2018


Corrosion of commercial spent nuclear fuel. 1. Formation of studtite and metastudtite
journal, January 2005


Complexity of Uranyl Peroxide Cluster Speciation from Alkali-Directed Oxidative Dissolution of Uranium Dioxide
journal, July 2018


Effects of H2O2 Concentration on Formation of Uranyl Peroxide Species Probed by Dissolution of Uranium Nitride and Uranium Dioxide
journal, April 2019


Irena : tool suite for modeling and analysis of small-angle scattering
journal, February 2009


pH standardization for phosphorus-31 magnetic resonance heart spectroscopy at different temperatures
journal, June 1990


Groundwater uranium stabilization by a metastable hydroxyapatite
journal, September 2017


Transformation of Uranyl Peroxide Studtite, [(UO 2 )(O 2 )(H 2 O) 2 ](H 2 O) 2 , to Soluble Nanoscale Cage Clusters
journal, May 2019


In situ Raman spectroscopy of uranyl peroxide nanoscale cage clusters under hydrothermal conditions
journal, January 2019

  • Lobeck, Haylie L.; Traustason, Hrafn; Julien, Patrick A.
  • Dalton Transactions, Vol. 48, Issue 22
  • DOI: 10.1039/C9DT01529A

Monovalent Cations in Structures of the Meta-Autunite Group
journal, August 2004


Divalent Transition Metals and Magnesium in Structures that Contain the Autunite-Type Sheet
journal, December 2004


Oxidizing dissolution mechanism of an irradiated MOX fuel in underwater aerated conditions at slightly acidic pH
journal, July 2015


Physical Characterization and Reactivity of the Uranyl Peroxide [UO 22 -O 2 )(H 2 O) 2 ]·2H 2 O: Implications for Storage of Spent Nuclear Fuels
journal, July 2012

  • Mallon, Colm; Walshe, Aurora; Forster, Robert J.
  • Inorganic Chemistry, Vol. 51, Issue 15
  • DOI: 10.1021/ic3010823

Raman Spectroscopic and ESI-MS Characterization of Uranyl Peroxide Cage Clusters
journal, January 2014

  • McGrail, Brendan T.; Sigmon, Ginger E.; Jouffret, Laurent J.
  • Inorganic Chemistry, Vol. 53, Issue 3
  • DOI: 10.1021/ic402570b

Effect of co-solutes on the products and solubility of uranium(VI) precipitated with phosphate
journal, January 2014


Transport of U(VI) through sediments amended with phosphate to induce in situ uranium immobilization
journal, February 2015


Unravelling the complexities of inorganic and supramolecular self-assembly in solution with electrospray and cryospray mass spectrometry
journal, January 2009

  • Miras, Haralampos N.; Wilson, Elizabeth F.; Cronin, Leroy
  • Chemical Communications, Issue 11
  • DOI: 10.1039/b819534j

Dynamic interplay between uranyl phosphate precipitation, sorption, and phase evolution
journal, July 2015


Mobility of uranium during weathering
journal, October 1997

  • Murakami, Takashi; Ohnuki, Toshihiko; Isobe, Hiroshi
  • American Mineralogist, Vol. 82, Issue 9-10
  • DOI: 10.2138/am-1997-9-1006

Self-Assembly of Alkali-Uranyl-Peroxide Clusters
journal, September 2010

  • Nyman, May; Rodriguez, Mark A.; Campana, Charles F.
  • Inorganic Chemistry, Vol. 49, Issue 17
  • DOI: 10.1021/ic1005192

Structure and Reactivity of X-ray Amorphous Uranyl Peroxide, U 2 O 7
journal, March 2016


Uranium speciation in acid waste-weathered sediments: The role of aging and phosphate amendments
journal, February 2018


Uranyl Peroxide Cage Cluster Solubility in Water and the Role of the Electrical Double Layer
journal, January 2017


Clusters of Actinides with Oxide, Peroxide, or Hydroxide Bridges
journal, October 2012

  • Qiu, Jie; Burns, Peter C.
  • Chemical Reviews, Vol. 113, Issue 2
  • DOI: 10.1021/cr300159x

Time-Resolved Self-Assembly of a Fullerene-Topology Core–Shell Cluster Containing 68 Uranyl Polyhedra
journal, January 2012

  • Qiu, Jie; Ling, Jie; Sui, Audrey
  • Journal of the American Chemical Society, Vol. 134, Issue 3
  • DOI: 10.1021/ja210163b

Water-soluble multi-cage super tetrahedral uranyl peroxide phosphate clusters
journal, January 2014

  • Qiu, Jie; Ling, Jie; Jouffret, Laurent
  • Chem. Sci., Vol. 5, Issue 1
  • DOI: 10.1039/C3SC52357H

Sulfate-Centered Sodium-Icosahedron-Templated Uranyl Peroxide Phosphate Cages with Uranyl Bridged by μ–η 12 Peroxide
journal, January 2017


Theoretical stability assessment of uranyl phosphates and apatites: Selection of amendments for in situ remediation of uranium
journal, February 2006


Uranium-bearing phases in Hanford nuclear waste
journal, February 2018

  • Reynolds, Jacob G.; Cooke, Gary A.; Page, Jason S.
  • Journal of Radioanalytical and Nuclear Chemistry, Vol. 316, Issue 1
  • DOI: 10.1007/s10967-018-5724-5

Uranyl Peroxide Nanocluster (U 60 ) Persistence and Sorption in the Presence of Hematite
journal, February 2018

  • Sadergaski, Luke R.; Stoxen, Wynn; Hixon, Amy E.
  • Environmental Science & Technology, Vol. 52, Issue 5
  • DOI: 10.1021/acs.est.7b06510

Alpha-radiolysis effects on UO2 alteration in water
journal, January 2001


Intracellular pH Determination by a 31P-NMR Technique. The Second Dissociation Constant of Phosphoric Acid in a Biological System
journal, July 1983


Uranium Speciation As a Function of Depth in Contaminated Hanford Sediments - A Micro-XRF, Micro-XRD, and Micro- And Bulk-XAFS Study
journal, February 2009

  • Singer, David M.; Zachara, John M.; Brown Jr, Gordon E.
  • Environmental Science & Technology, Vol. 43, Issue 3
  • DOI: 10.1021/es8021045

Uranyl peroxide closed clusters containing topological squares
journal, January 2010

  • Unruh, Daniel K.; Burtner, Alicia; Pressprich, Laura
  • Dalton Transactions, Vol. 39, Issue 25
  • DOI: 10.1039/c0dt00074d

Solubility and spectrochemical characteristics of synthetic chernikovite and meta-ankoleite
journal, October 1996


Soluble Hetero-Polyoxovanadates and Their Solution Chemistry Analyzed by Electrospray Ionization Mass Spectrometry
journal, November 2018

  • Warzok, Ulrike; Mahnke, Lisa K.; Bensch, Wolfgang
  • Chemistry - A European Journal, Vol. 25, Issue 6
  • DOI: 10.1002/chem.201803291

Effects of pH, temperature, and aqueous organic material on the dissolution kinetics of meta-autunite minerals, (Na, Ca) 2−1 [(UO 2 )(PO 4 )] 2 · 3H 2 O
journal, January 2006

  • Wellman, Dawn M.; Icenhower, Jonathan P.; Gamerdinger, Amy P.
  • American Mineralogist, Vol. 91, Issue 1
  • DOI: 10.2138/am.2006.1807

Comparative Analysis of Soluble Phosphate Amendments for the Remediation of Heavy Metal Contaminants: Effect on Sediment Hydraulic Conductivity
journal, January 2006

  • Wellman, Dawn M.; Icenhower, Jonathan P.; Owen, Antoinette T.
  • Environmental Chemistry, Vol. 3, Issue 3
  • DOI: 10.1071/EN05023

Efficacy of soluble sodium tripolyphosphate amendments for the in-situ immobilisation of uranium
journal, January 2007

  • Wellman, Dawn M.; Pierce, Eric M.; Valenta, Michelle M.
  • Environmental Chemistry, Vol. 4, Issue 5
  • DOI: 10.1071/EN07030

Dissolution kinetics of synthetic and natural meta-autunite minerals, X 3− n ( n ) + [(UO 2 )(PO 4 )] 2 · xH 2 O, under acidic conditions : META-AUTUNITE MINERALS
journal, November 2007

  • Wellman, D. M.; Gunderson, K. M.; Icenhower, J. P.
  • Geochemistry, Geophysics, Geosystems, Vol. 8, Issue 11
  • DOI: 10.1029/2007GC001695

Sequestration and retention of uranium(VI) in the presence of hydroxylapatite under dynamic geochemical conditions
journal, January 2008

  • Wellman, Dawn M.; Glovack, Julia N.; Parker, Kent
  • Environmental Chemistry, Vol. 5, Issue 1
  • DOI: 10.1071/EN07060