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Title: Americium incorporation into studtite: a theoretical and experimental study

Abstract

Studtite, [UO22-O2)(H2O)2]·2H2O, and metastudtite, [UO22-O2)(H2O)2], are important phase alterations of UO2 in a spent nuclear fuel repository and have previously been shown to react with Np(V). In this work we extend the study to Am(V) on a tracer scale and show spectroscopic evidence that the Am is incorporated into the structure of studtite as Am(III). A computational study on the possible mechanisms for the incorporation of Np and Am shows that protonation of the -yl oxygen is the favoured route and the calculated incorporation energies are large and positive. The results suggest that Am is less favoured compared to Np but energetically more favoured to incorporate both actinide ions into metastudtite rather than studtite. Finally, we have shown that once incorporated, Am readily leaches into water but spectroscopic measurements suggest subtle changes in the structure of studtite.

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [2];  [3];  [4];  [1]; ORCiD logo [3]; ORCiD logo [1]
  1. Univ. of Dublin Trinity College (Ireland)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. Forschungszentrum Juelich (Germany). Inst. for Energy and Climate Research (IEK)
  4. Univ. College Dublin (Ireland)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1700514
Report Number(s):
PNNL-SA-143797
Journal ID: ISSN 1477-9226
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 48; Journal Issue: 34; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Biswas, Saptarshi, Edwards, Samuel J., Wang, Zheming, Si, Hang, Vintró, Luis León, Twamley, Brendan, Kowalski, Piotr M., and Baker, Robert J.. Americium incorporation into studtite: a theoretical and experimental study. United States: N. p., 2019. Web. https://doi.org/10.1039/c9dt02848j.
Biswas, Saptarshi, Edwards, Samuel J., Wang, Zheming, Si, Hang, Vintró, Luis León, Twamley, Brendan, Kowalski, Piotr M., & Baker, Robert J.. Americium incorporation into studtite: a theoretical and experimental study. United States. https://doi.org/10.1039/c9dt02848j
Biswas, Saptarshi, Edwards, Samuel J., Wang, Zheming, Si, Hang, Vintró, Luis León, Twamley, Brendan, Kowalski, Piotr M., and Baker, Robert J.. Thu . "Americium incorporation into studtite: a theoretical and experimental study". United States. https://doi.org/10.1039/c9dt02848j. https://www.osti.gov/servlets/purl/1700514.
@article{osti_1700514,
title = {Americium incorporation into studtite: a theoretical and experimental study},
author = {Biswas, Saptarshi and Edwards, Samuel J. and Wang, Zheming and Si, Hang and Vintró, Luis León and Twamley, Brendan and Kowalski, Piotr M. and Baker, Robert J.},
abstractNote = {Studtite, [UO2(η2-O2)(H2O)2]·2H2O, and metastudtite, [UO2(η2-O2)(H2O)2], are important phase alterations of UO2 in a spent nuclear fuel repository and have previously been shown to react with Np(V). In this work we extend the study to Am(V) on a tracer scale and show spectroscopic evidence that the Am is incorporated into the structure of studtite as Am(III). A computational study on the possible mechanisms for the incorporation of Np and Am shows that protonation of the -yl oxygen is the favoured route and the calculated incorporation energies are large and positive. The results suggest that Am is less favoured compared to Np but energetically more favoured to incorporate both actinide ions into metastudtite rather than studtite. Finally, we have shown that once incorporated, Am readily leaches into water but spectroscopic measurements suggest subtle changes in the structure of studtite.},
doi = {10.1039/c9dt02848j},
journal = {Dalton Transactions},
number = 34,
volume = 48,
place = {United States},
year = {2019},
month = {8}
}

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Works referenced in this record:

Raspite and studtite: Raman spectra of two unique minerals
journal, July 2004

  • Bastians, Simon; Crump, Gregory; Griffith, William P.
  • Journal of Raman Spectroscopy, Vol. 35, Issue 89
  • DOI: 10.1002/jrs.1176

Effects of the different conditions of uranyl and hydrogen peroxide solutions on the behavior of the uranium peroxide precipitation
journal, October 2011


Neptunium(V) Partitioning to Uranium(VI) Oxide and Peroxide Solids
journal, June 2005

  • Douglas, Matthew; Clark, Sue B.; Friese, Judah I.
  • Environmental Science & Technology, Vol. 39, Issue 11
  • DOI: 10.1021/es0405169

A Comparative Relativistic DFT and Ab Initio Study on the Structure and Thermodynamics of the Oxofluorides of Uranium(IV), (V) and (VI)
journal, June 2007

  • Shamov, Grigory A.; Schreckenbach, Georg; Vo, Thach N.
  • Chemistry - A European Journal, Vol. 13, Issue 17
  • DOI: 10.1002/chem.200601244

Raman microspectrometric identification of corrosion products formed on UO2 nuclear fuel during leaching experiments
journal, December 2002


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

Neptunium incorporation in sodium-substituted metaschoepite
journal, April 2007

  • Klingensmith, A. L.; Deely, K. M.; Kinman, W. S.
  • American Mineralogist, Vol. 92, Issue 4
  • DOI: 10.2138/am.2007.2350

Quantum-mechanical evaluation of Np-incorporation into studtite
journal, August 2010

  • Shuller, L. C.; Ewing, R. C.; Becker, U.
  • American Mineralogist, Vol. 95, Issue 8-9
  • DOI: 10.2138/am.2010.3493

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976


Separation of Americium from Curium by Oxidation and Ion Exchange
journal, July 2012

  • Burns, Jonathan D.; Shehee, Thomas C.; Clearfield, Abraham
  • Analytical Chemistry, Vol. 84, Issue 16
  • DOI: 10.1021/ac3018394

Uranyl Sensitization of Samarium(III) Luminescence in a Two-Dimensional Coordination Polymer
journal, December 2011

  • Knope, Karah E.; de Lill, Daniel T.; Rowland, Clare E.
  • Inorganic Chemistry, Vol. 51, Issue 1
  • DOI: 10.1021/ic201450e

Speciation of Uranium in Fernald Soils by Molecular Spectroscopic Methods:  Characterization of Untreated Soils
journal, January 1996

  • Morris, David E.; Allen, Patrick G.; Berg, John M.
  • Environmental Science & Technology, Vol. 30, Issue 7
  • DOI: 10.1021/es950745i

DFT +  U as a reliable method for efficient ab initio calculations of nuclear materials
journal, September 2016


Effect of Secondary Phases Formation in the Leaching of UO 2 Under Simulated Radiolytic Products
journal, January 1994

  • Díaz-Arocas, P.; Quinoñes, J.; Maffiotte, C.
  • MRS Proceedings, Vol. 353
  • DOI: 10.1557/PROC-353-641

Photophysical studies of uranyl complexes. 4. X-ray photoelectron and luminescence studies of hydrolyzed uranyl salts
journal, April 1984

  • Perry, Dale L.; Tsao, Leon; Brittain, Harry G.
  • Inorganic Chemistry, Vol. 23, Issue 9
  • DOI: 10.1021/ic00177a013

Incorporation mechanisms of actinide elements into the structures of U6+ phases formed during the oxidation of spent nuclear fuel
journal, May 1997


X-ray diffraction data on hydrated uranium peroxide
journal, June 1963


Products of in Situ Corrosion of Depleted Uranium Ammunition in Bosnia and Herzegovina Soils
journal, October 2016

  • Wang, Yuheng; von Gunten, Konstantin; Bartova, Barbora
  • Environmental Science & Technology, Vol. 50, Issue 22
  • DOI: 10.1021/acs.est.6b03732

Uranium minerals and their relevance to long term storage of nuclear fuels
journal, May 2014


Formation of Studtite during the Oxidative Dissolution of UO 2 by Hydrogen Peroxide:  A SFM Study
journal, December 2004

  • Clarens, F.; de Pablo, J.; Díez-Pérez, I.
  • Environmental Science & Technology, Vol. 38, Issue 24
  • DOI: 10.1021/es0492891

Synthetic Influences on Neptunium Incorporation in Naturally Occurring Copper Uranyl Phosphates
journal, December 2012

  • Meredith, Nathan A.; Polinski, Matthew J.; Cross, Justin N.
  • Crystal Growth & Design, Vol. 13, Issue 1
  • DOI: 10.1021/cg3015755

Sorption of Am(III) on clays and clay minerals: A review
journal, November 2018

  • Fröhlich, Daniel R.; Kaplan, Ugras
  • Journal of Radioanalytical and Nuclear Chemistry, Vol. 318, Issue 3
  • DOI: 10.1007/s10967-018-6310-6

Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008


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

Microscale characterization of uranium(VI) silicate solids and associated neptunium(V)
journal, January 2005


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


Sorption of strontium on uranyl peroxide: Implications for a high-level nuclear waste repository
journal, September 2010


Fluorescence properties of uranyl nitrates
journal, March 1999


Spectroscopic characterization of trivalent f-element (Eu, Am) solid carbonates
journal, May 2000


Coffinite, USiO 4 , Is Abundant in Nature: So Why Is It So Difficult To Synthesize?
journal, July 2015

  • Mesbah, Adel; Szenknect, Stephanie; Clavier, Nicolas
  • Inorganic Chemistry, Vol. 54, Issue 14
  • DOI: 10.1021/ic502808n

Neptunium substitution in synthetic uranophane and soddyite
journal, November 2007

  • Klingensmith, A. L.; Burns, P. C.
  • American Mineralogist, Vol. 92, Issue 11-12
  • DOI: 10.2138/am.2007.2542

Soft self-consistent pseudopotentials in a generalized eigenvalue formalism
journal, April 1990


Cesium sorption on studtite (UO2O2·4H2O)
journal, January 2010

  • Giménez, Javier; Martínez-Lladó, Xavier; Rovira, Miquel
  • Radiochimica Acta, Vol. 98, Issue 8
  • DOI: 10.1524/ract.2010.1742

Fluorescence spectroscopy of U(VI)-silicates and U(VI)-contaminated Hanford sediment
journal, March 2005

  • Wang, Zheming; Zachara, John M.; Gassman, Paul L.
  • Geochimica et Cosmochimica Acta, Vol. 69, Issue 6
  • DOI: 10.1016/j.gca.2004.08.028

High-precision sampling for Brillouin-zone integration in metals
journal, August 1989


Mineral–Water Interface Reactions of Actinides
journal, October 2012

  • Geckeis, Horst; Lützenkirchen, Johannes; Polly, Robert
  • Chemical Reviews, Vol. 113, Issue 2
  • DOI: 10.1021/cr300370h

The Aqueous Geochemistry of Neptunium:  Dynamic Control of Soluble Concentrations with Applications to Nuclear Waste Disposal
journal, December 1999

  • Kaszuba, John P.; Runde, Wolfgang H.
  • Environmental Science & Technology, Vol. 33, Issue 24
  • DOI: 10.1021/es990470x

Neptunium incorporation into uranyl compounds that form as alteration products of spent nuclear fuel: Implications for geologic repository performance
journal, January 2004

  • Burns, Peter C.; Deely, Kathryn M.; Skanthakumar, Suntharalingam
  • Radiochimica Acta, Vol. 92, Issue 3
  • DOI: 10.1524/ract.92.3.151.30491

An investigation of the interactions of Eu 3+ and Am 3+ with uranyl minerals: implications for the storage of spent nuclear fuel
journal, January 2016

  • Biswas, Saptarshi; Steudtner, Robin; Schmidt, Moritz
  • Dalton Transactions, Vol. 45, Issue 15
  • DOI: 10.1039/C6DT00199H

Stability of Peroxide-Containing Uranyl Minerals
journal, November 2003


Mineralogic controls on aqueous neptunium(V) concentrations in silicate systems
journal, February 2013

  • Alessi, Daniel S.; Szymanowski, Jennifer E. S.; Forbes, Tori Z.
  • Journal of Nuclear Materials, Vol. 433, Issue 1-3
  • DOI: 10.1016/j.jnucmat.2012.09.013

Higher Oxidation States of Americium: Preparation, Characterization and Use for Separations
journal, September 2011

  • Runde, Wolfgang H.; Mincher, Bruce J.
  • Chemical Reviews, Vol. 111, Issue 9
  • DOI: 10.1021/cr100181f

Solubility study and point of zero charge of studtite (UO2O2·4H2O)
journal, October 2014


Np-incorporation into uranyl phases: A quantum–mechanical evaluation
journal, March 2013


Benchmarking the DFT+ U Method for Thermochemical Calculations of Uranium Molecular Compounds and Solids
journal, December 2014

  • Beridze, George; Kowalski, Piotr M.
  • The Journal of Physical Chemistry A, Vol. 118, Issue 50
  • DOI: 10.1021/jp5101126

Quantum-Mechanical Methods for Quantifying Incorporation of Contaminants in Proximal Minerals
journal, July 2014

  • Shuller-Nickles, Lindsay; Bender, Will; Walker, Sarah
  • Minerals, Vol. 4, Issue 3
  • DOI: 10.3390/min4030690