Chemical and elemental mapping of spent nuclear fuel sections by soft X-ray spectromicroscopy

Ditter, Alexander Scott; Smiles, Danil E.; Lussier, Daniel; Altman, Alison B.; Bachhav, Mukesh; He, Lingfeng; Mara, Michael W.; Degueldre, Claude; Minasian, Stefan G.; Shuh, David K.

doi:10.1107/S1600577521012315

Title: Chemical and elemental mapping of spent nuclear fuel sections by soft X-ray spectromicroscopy

Journal Article · 31 December 2021 · Journal of Synchrotron Radiation (Online)

DOI: https://doi.org/10.1107/S1600577521012315 · OSTI ID:1837324

;

; Bachhav, Mukesh;

; Mara, Michael W.;

;

Soft X-ray spectromicroscopy at the O K -edge, U N _4,5 -edges and Ce M _4,5 -edges has been performed on focused ion beam sections of spent nuclear fuel for the first time, yielding chemical information on the sub-micrometer scale. To analyze these data, a modification to non-negative matrix factorization (NMF) was developed, in which the data are no longer required to be non-negative, but the non-negativity of the spectral components and fit coefficients is largely preserved. The modified NMF method was utilized at the O K -edge to distinguish between two components, one present in the bulk of the sample similar to UO ₂ and one present at the interface of the sample which is a hyperstoichiometric UO _{2+ x} species. The species maps are consistent with a model of a thin layer of UO _{2+ x} over the entire sample, which is likely explained by oxidation after focused ion beam (FIB) sectioning. In addition to the uranium oxide bulk of the sample, Ce measurements were also performed to investigate the oxidation state of that fission product, which is the subject of considerable interest. Analysis of the Ce spectra shows that Ce is in a predominantly trivalent state, with a possible contribution from tetravalent Ce. Atom probe analysis was performed to provide confirmation of the presence and localization of Ce in the spent fuel.

View Journal Article

Cite

Export

Save

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE)

Grant/Contract Number:: AC02-05CH11231; AC07-05ID14517

OSTI ID:: 1837324

Journal Information:: Journal of Synchrotron Radiation (Online), Journal Name: Journal of Synchrotron Radiation (Online) Journal Issue: 1 Vol. 29; ISSN 1600-5775; ISSN JSYRES

Publisher:: International Union of Crystallography (IUCr)Copyright Statement

Country of Publication:: Denmark

Language:: English

References (73)

Algorithms for nonnegative matrix and tensor factorizations: a unified view based on block coordinate descent framework Kim, Jingu; He, Yunlong; Park, Haesun Journal of Global Optimization, Vol. 58, Issue 2 https://doi.org/10.1007/s10898-013-0035-4	journal	March 2013
Electron transfer reactions in non-stoichiometric ceria and urania Griffiths, Trevor R.; Hubbard, Hugh V. St. A.; Davies, Mervyn J. Inorganica Chimica Acta, Vol. 225, Issue 1-2 https://doi.org/10.1016/0020-1693(94)04062-1	journal	October 1994
The low temperature oxidation of UO2 and U4O9 Hoekstra, H. R.; Santoro, A.; Siegel, S. Journal of Inorganic and Nuclear Chemistry, Vol. 18 https://doi.org/10.1016/0022-1902(61)80384-9	journal	March 1961
The uranium-cerium-oxygen ternary phase diagram Markin, T. L.; Street, R. S.; Crouch, E. C. Journal of Inorganic and Nuclear Chemistry, Vol. 32, Issue 1 https://doi.org/10.1016/0022-1902(70)80449-3	journal	January 1970
The chemical effects of composition changes in irradiated oxide fuel materials Davies, J. H.; Ewart, F. T. Journal of Nuclear Materials, Vol. 41, Issue 2, p. 143-155 https://doi.org/10.1016/0022-3115(71)90074-2	journal	November 1971
Solubility and migration of fission product barium in oxide fuel Sari, C.; Walker, C. T.; Schumacher, G. Journal of Nuclear Materials, Vol. 79, Issue 1 https://doi.org/10.1016/0022-3115(79)90455-0	journal	January 1979
The chemical state of the fission products in oxide fuels Kleykamp, H. Journal of Nuclear Materials, Vol. 131, Issue 2-3, p. 221-246 https://doi.org/10.1016/0022-3115(85)90460-X	journal	April 1985
Fission gas release from power-ramped UO2 fuel Hastings, I. J.; Smith, A. D.; Fehrenbach, P. J. Journal of Nuclear Materials, Vol. 139, Issue 2 https://doi.org/10.1016/0022-3115(86)90028-0	journal	June 1986
Oxidation of spent fuel in air at 175 to 195°C Einziger, R. E.; Thomas, L. E.; Buchanan, H. C. Journal of Nuclear Materials, Vol. 190 https://doi.org/10.1016/0022-3115(92)90075-V	journal	August 1992
Effect of fission products on air-oxidation of LWR spent fuel Thomas, L. E.; Einziger, R. E.; Buchanan, H. C. Journal of Nuclear Materials, Vol. 201 https://doi.org/10.1016/0022-3115(93)90187-4	journal	May 1993
Thermal conductivity of hyperstoichiometric SIMFUEL Lucuta, P. G.; Matzke, Hj.; Verrall, R. A. Journal of Nuclear Materials, Vol. 223, Issue 1 https://doi.org/10.1016/0022-3115(94)00703-9	journal	May 1995
Diffraction-limited imaging in a scanning transmission x-ray microscope Jacobsen, C.; Williams, S.; Anderson, E. Optics Communications, Vol. 86, Issue 3-4 https://doi.org/10.1016/0030-4018(91)90016-7	journal	November 1991
Uraninite and UO2 in spent nuclear fuel: a comparison Janeczek, Janusz; Ewing, Rodney C.; Oversby, Virginia M. Journal of Nuclear Materials, Vol. 238, Issue 1 https://doi.org/10.1016/S0022-3115(96)00345-5	journal	October 1996
A review of the oxidation of uranium dioxide at temperatures below 400°C McEachern, R. J.; Taylor, P. Journal of Nuclear Materials, Vol. 254, Issue 2-3 https://doi.org/10.1016/S0022-3115(97)00343-7	journal	April 1998
Uranium oxides investigated by X-ray absorption and emission spectroscopies Magnuson, M.; Butorin, S. M.; Werme, L. Applied Surface Science, Vol. 252, Issue 15 https://doi.org/10.1016/j.apsusc.2005.12.131	journal	May 2006
X-ray photoelectron spectroscopy study of the reduction and oxidation of uranium and cerium single oxide compared to (U-Ce) mixed oxide films Eloirdi, R.; Cakir, P.; Huber, F. Applied Surface Science, Vol. 457 https://doi.org/10.1016/j.apsusc.2018.06.148	journal	November 2018
Soft X-ray microscopy and spectroscopy at the molecular environmental science beamline at the Advanced Light Source Bluhm, H.; Andersson, K.; Araki, T. Journal of Electron Spectroscopy and Related Phenomena, Vol. 150, Issue 2-3 https://doi.org/10.1016/j.elspec.2005.07.005	journal	February 2006
The apparent absence of chemical sensitivity in the 4d and 5d X-ray absorption spectroscopy of uranium compounds Tobin, J. G. Journal of Electron Spectroscopy and Related Phenomena, Vol. 194 https://doi.org/10.1016/j.elspec.2014.01.020	journal	June 2014
Soft X-ray spectromicroscopy and ptychography Hitchcock, Adam P. Journal of Electron Spectroscopy and Related Phenomena, Vol. 200 https://doi.org/10.1016/j.elspec.2015.05.013	journal	April 2015
Alteration of submarine basaltic glass from the Ontong Java Plateau: A STXM and TEM study Benzerara, K.; Menguy, N.; Banerjee, N. R. Earth and Planetary Science Letters, Vol. 260, Issue 1-2 https://doi.org/10.1016/j.epsl.2007.05.029	journal	August 2007
Exceptional preservation of fossil plant spores in high-pressure metamorphic rocks Bernard, S.; Benzerara, K.; Beyssac, O. Earth and Planetary Science Letters, Vol. 262, Issue 1-2 https://doi.org/10.1016/j.epsl.2007.07.041	journal	October 2007
Oxidation behaviour of uranium in the internally gelated urania–ceria solid solutions – XRD and XPS studies Suresh Kumar, K.; Mathews, T.; Nawada, H. P. Journal of Nuclear Materials, Vol. 324, Issue 2-3 https://doi.org/10.1016/j.jnucmat.2003.09.014	journal	January 2004
On the oxidation state of UO2 nuclear fuel at a burn-up of around 100MWd/kgHM Walker, C. T.; Rondinella, V. V.; Papaioannou, D. Journal of Nuclear Materials, Vol. 345, Issue 2-3 https://doi.org/10.1016/j.jnucmat.2005.05.010	journal	October 2005
XPS analysis of UxCe1−xO2±δ and determination of oxygen to metal ratio Bera, Santanu; Mittal, V. K.; Venkata Krishnan, R. Journal of Nuclear Materials, Vol. 393, Issue 1 https://doi.org/10.1016/j.jnucmat.2009.05.015	journal	August 2009
Unit mechanisms of fission gas release: Current understanding and future needs Tonks, Michael; Andersson, David; Devanathan, Ram Journal of Nuclear Materials, Vol. 504 https://doi.org/10.1016/j.jnucmat.2018.03.016	journal	June 2018
A novel approach to determine the local burnup in irradiated fuels using Atom Probe Tomography (APT) Bachhav, Mukesh; Gan, Jian; Keiser, Dennis Journal of Nuclear Materials, Vol. 528 https://doi.org/10.1016/j.jnucmat.2019.151853	journal	January 2020
Direct observations of Pd–Te compound formation within noble metal inclusions in spent nuclear fuel Kessler, Sean H.; Lach, Timothy G.; Garrett, Kerry E. Journal of Nuclear Materials, Vol. 538 https://doi.org/10.1016/j.jnucmat.2020.152249	journal	September 2020
Structure of the pellet-cladding interaction layer of a high-burnup Zr-Nb-O nuclear fuel cladding Liu, Xiang; Cinbiz, Mahmut Nedim; Kombaiah, Boopathy Journal of Nuclear Materials, Vol. 556 https://doi.org/10.1016/j.jnucmat.2021.153196	journal	December 2021
Utilization of dual-column focused ion beam and scanning electron microscope for three dimensional characterization of high burn-up mixed oxide fuel Teague, Melissa; Gorman, Brian Progress in Nuclear Energy, Vol. 72 https://doi.org/10.1016/j.pnucene.2013.08.006	journal	April 2014
Electron energy loss spectroscopy investigations through nano-ablated actinide dioxide samples Degueldre, Claude; Veleva, Lyubomira Progress in Nuclear Energy, Vol. 72 https://doi.org/10.1016/j.pnucene.2013.11.016	journal	April 2014
Post irradiation examination of nuclear fuel: Toward a complete analysis Degueldre, Claude; Bertsch, Johannes; Martin, Matthias Progress in Nuclear Energy, Vol. 92 https://doi.org/10.1016/j.pnucene.2016.03.025	journal	September 2016
Ultrastructural and chemical study of modern and fossil sporoderms by Scanning Transmission X-ray Microscopy (STXM) Bernard, S.; Benzerara, K.; Beyssac, O. Review of Palaeobotany and Palynology, Vol. 156, Issue 1-2 https://doi.org/10.1016/j.revpalbo.2008.09.002	journal	July 2009
Identifying anthropogenic uranium compounds using soft X-ray near-edge absorption spectroscopy Ward, Jesse D.; Bowden, Mark; Tom Resch, C. Spectrochimica Acta Part B: Atomic Spectroscopy, Vol. 127 https://doi.org/10.1016/j.sab.2016.11.008	journal	January 2017
The surface chemistry of cerium oxide Mullins, David R. Surface Science Reports, Vol. 70, Issue 1 https://doi.org/10.1016/j.surfrep.2014.12.001	journal	March 2015
In situ site-specific specimen preparation for atom probe tomography Thompson, K.; Lawrence, D.; Larson, D. J. Ultramicroscopy, Vol. 107, Issue 2-3 https://doi.org/10.1016/j.ultramic.2006.06.008	journal	February 2007
Training artificial neural networks for precision orientation and strain mapping using 4D electron diffraction datasets Yuan, Renliang; Zhang, Jiong; He, Lingfeng Ultramicroscopy https://doi.org/10.1016/j.ultramic.2021.113256	journal	March 2021
Atom Probe Mass Spectrometry of Uranium Isotopic Reference Materials Meisenkothen, Frederick; McLean, Mark; Kalish, Irina Analytical Chemistry, Vol. 92, Issue 16 https://doi.org/10.1021/acs.analchem.0c02273	journal	July 2020
Oxygen K-edge X-ray Absorption Spectra Frati, Federica; Hunault, Myrtille O. J. Y.; de Groot, Frank M. F. Chemical Reviews, Vol. 120, Issue 9 https://doi.org/10.1021/acs.chemrev.9b00439	journal	April 2020
Comparison of the Cation Valence and Coordination in Ce ₂ UO ₆ and Ce ₂ MoO ₆ Antonio, Mark R.; Staub, U.; Xue, J. S. Chemistry of Materials, Vol. 8, Issue 11 https://doi.org/10.1021/cm960208c	journal	January 1996
Beer's law and the Isosbestic Points in the Absorption Spectra of Conductive Polymers Vinokurov, Igor A.; Kankare, Jouko The Journal of Physical Chemistry B, Vol. 102, Issue 7 https://doi.org/10.1021/jp972702p	journal	January 1998
Learning the parts of objects by non-negative matrix factorization Lee, Daniel D.; Seung, H. Sebastian Nature, Vol. 401, Issue 6755 https://doi.org/10.1038/44565	journal	October 1999
Redox response of actinide materials to highly ionizing radiation Tracy, Cameron L.; Lang, Maik; Pray, John M. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7133	journal	January 2015
Long-term storage of spent nuclear fuel Ewing, Rodney C. Nature Materials, Vol. 14, Issue 3 https://doi.org/10.1038/nmat4226	journal	February 2015
Nanoscale X-ray imaging Sakdinawat, Anne; Attwood, David Nature Photonics, Vol. 4, Issue 12, p. 840-848 https://doi.org/10.1038/nphoton.2010.267	journal	December 2010
Distribution of metallic fission-product particles in the cladding liner of spent nuclear fuel Clark, Richard A.; Conroy, Michele A.; Lach, Timothy G. npj Materials Degradation, Vol. 4, Issue 1 https://doi.org/10.1038/s41529-019-0107-0	journal	January 2020
Cerium oxide nanoparticles with antioxidant capabilities and gadolinium integration for MRI contrast enhancement Eriksson, Peter; Tal, Alexey A.; Skallberg, Andreas Scientific Reports, Vol. 8, Issue 1 https://doi.org/10.1038/s41598-018-25390-z	journal	May 2018
Investigation at the nanometre scale on the corrosion mechanisms of archaeological ferrous artefacts by STXM Michelin, A.; Drouet, E.; Foy, E. J. Anal. At. Spectrom., Vol. 28, Issue 1 https://doi.org/10.1039/C2JA30250K	journal	January 2013
Non-negative matrix analysis for effective feature extraction in X-ray spectromicroscopy Mak, Rachel; Lerotic, Mirna; Fleckenstein, Holger Faraday Discuss., Vol. 171 https://doi.org/10.1039/C4FD00023D	journal	January 2014
Development of small particle speciation for nuclear forensics by soft X-ray scanning transmission spectromicroscopy Pacold, J. I.; Altman, A. B.; Knight, K. B. The Analyst, Vol. 143, Issue 6 https://doi.org/10.1039/C7AN01838J	journal	January 2018
The duality of electron localization and covalency in lanthanide and actinide metallocenes Smiles, Danil E.; Batista, Enrique R.; Booth, Corwin H. Chemical Science, Vol. 11, Issue 10 https://doi.org/10.1039/C9SC06114B	journal	January 2020
Soft X-ray spectroscopy from image sequences with sub-100 nm spatial resolution Journal of Microscopy, Vol. 197, Issue 2 https://doi.org/10.1046/j.1365-2818.2000.00640.x	journal	February 2000
Covalency in the uranyl ion: A polarized x-ray spectroscopic study Denning, R. G.; Green, J. C.; Hutchings, T. E. The Journal of Chemical Physics, Vol. 117, Issue 17 https://doi.org/10.1063/1.1510445	journal	November 2002
M ‐edge x‐ray absorption spectroscopy of 4 f instabilities in rare‐earth systems (invited) Kaindl, G.; Kalkowski, G.; Brewer, W. D. Journal of Applied Physics, Vol. 55, Issue 6 https://doi.org/10.1063/1.333517	journal	March 1984
Nanoscale oxygen defect gradients in UO _{2+ x} surfaces Spurgeon, Steven R.; Sassi, Michel; Ophus, Colin Proceedings of the National Academy of Sciences, Vol. 116, Issue 35 https://doi.org/10.1073/pnas.1905056116	journal	August 2019
Electrolytic Reduction of Spent Light Water Reactor Fuel Bench-Scale Experiment Results Herrmann, Steven; Li, Shelly; Simpson, Michael Journal of Nuclear Science and Technology, Vol. 44, Issue 3 https://doi.org/10.1080/18811248.2007.9711295	journal	March 2007
Vibrational structure of core to Rydberg state excitations of carbon dioxide and dinitrogen oxide Prince, K. C.; Avaldi, L.; Coreno, M. Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 32, Issue 11 https://doi.org/10.1088/0953-4075/32/11/307	journal	January 1999
X-ray absorption at the oxygen K edge in cubic f oxides examined using a full multiple-scattering approach Wu, Z. Y.; Jollet, F.; Gota, S. Journal of Physics: Condensed Matter, Vol. 11, Issue 37 https://doi.org/10.1088/0953-8984/11/37/314	journal	September 1999
The electronic structure of uranium dioxide: an oxygen K-edge x-ray absorption study Jollet, F.; Petit, T.; Gota, S. Journal of Physics: Condensed Matter, Vol. 9, Issue 43 https://doi.org/10.1088/0953-8984/9/43/022	journal	October 1997
3d x-ray-absorption lines and the 3 d 9 4 f n + 1 multiplets of the lanthanides Thole, B. T.; van der Laan, G.; Fuggle, J. C. Physical Review B, Vol. 32, Issue 8 https://doi.org/10.1103/PhysRevB.32.5107	journal	October 1985
Bulk sensitive x-ray absorption spectroscopy free of self-absorption effects Achkar, A. J.; Regier, T. Z.; Wadati, H. Physical Review B, Vol. 83, Issue 8 https://doi.org/10.1103/PhysRevB.83.081106	journal	February 2011
f - f origin of the insulating state in uranium dioxide: X-ray absorption experiments and first-principles calculations Yu, S. -W.; Tobin, J. G.; Crowhurst, J. C. Physical Review B, Vol. 83, Issue 16 https://doi.org/10.1103/PhysRevB.83.165102	journal	April 2011
Computational study of the energetics of charge and cation mixing in U 1 − x Ce x O 2 Hanken, B. E.; Stanek, C. R.; Grønbech-Jensen, N. Physical Review B, Vol. 84, Issue 8 https://doi.org/10.1103/PhysRevB.84.085131	journal	August 2011
Possible Bose-condensate behavior in a quantum phase originating in a collective excitation in the chemically and optically doped Mott-Hubbard system UO 2 + x Conradson, Steven D.; Durakiewicz, Tomasz; Espinosa-Faller, Francisco J. Physical Review B, Vol. 88, Issue 11 https://doi.org/10.1103/PhysRevB.88.115135	journal	September 2013
Oxidation and crystal field effects in uranium Tobin, J. G.; Yu, S. -W.; Booth, C. H. Physical Review B, Vol. 92, Issue 3 https://doi.org/10.1103/PhysRevB.92.035111	journal	July 2015
Identification of Uranyl Minerals Using Oxygen K-Edge X-Ray Absorption Spectroscopy Ward, Jesse D.; Bowden, Mark; Resch, C. Tom Geostandards and Geoanalytical Research, Vol. 40, Issue 1 https://doi.org/10.1111/j.1751-908X.2015.00337.x	journal	March 2015
Surface degradation of uranium tetrafluoride Tobin, J. G.; Duffin, A. M.; Yu, S. -W. Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 35, Issue 3 https://doi.org/10.1116/1.4979540	journal	May 2017
Sequential analysis of carbonaceous materials in Hayabusa-returned samples for the determination of their origin Uesugi, Masayuki; Naraoka, Hiroshi; Ito, Motoo Earth, Planets and Space, Vol. 66, Issue 1 https://doi.org/10.1186/1880-5981-66-102	journal	August 2014
X-ray absorption near edge structure spectroscopic study of Hayabusa category 3 carbonaceous particles Yabuta, Hikaru; Uesugi, Masayuki; Naraoka, Hiroshi Earth, Planets and Space, Vol. 66, Issue 1 https://doi.org/10.1186/s40623-014-0156-0	journal	December 2014
The universal sample holders of microanalytical instruments of FIB, TEM, NanoSIMS, and STXM-NEXAFS for the coordinated analysis of extraterrestrial materials Ito, Motoo; Tomioka, Naotaka; Uesugi, Kentaro Earth, Planets and Space, Vol. 72, Issue 1 https://doi.org/10.1186/s40623-020-01267-2	journal	September 2020
Non-negative Matrix Factorization and Its Extensions for Spectral Image Data Analysis Shiga, Motoki; Muto, Shunsuke e-Journal of Surface Science and Nanotechnology, Vol. 17, Issue 0 https://doi.org/10.1380/ejssnt.2019.148	journal	January 2019
Annealing-induced lattice recovery in room-temperature xenon irradiated CeO ₂ : X-ray diffraction and electron energy loss spectroscopy experiments Pakarinen, Janne; He, Lingfeng; Hassan, Abdel-Rahman Journal of Materials Research, Vol. 30, Issue 9 https://doi.org/10.1557/jmr.2015.13	journal	February 2015
Spent Nuclear Fuel Bruno, J.; Ewing, R. C. Elements, Vol. 2, Issue 6 https://doi.org/10.2113/gselements.2.6.343	journal	December 2006
Microstructural Changes and Chemical Analysis of Fission Products in Irradiated Uranium-7 wt.% Molybdenum Metallic Fuel Using Atom Probe Tomography Bachhav, Mukesh; Miller, Brandon; Gan, Jian Applied Sciences, Vol. 11, Issue 15 https://doi.org/10.3390/app11156905	journal	July 2021

Similar Records

Speciation mapping of the oxidation layer on aged uranium dioxide using scanning transmission x-ray spectromicroscopy

Journal Article · 2025 · Journal of Nuclear Materials · OSTI ID:2572672

Cicchetti, Nic; Ditter, Alexander; Pacold, Joseph I.; +6 more

Submicrometer spectromicroscopy of UO₂ aged under high humidity conditions

Journal Article · 2022 · Journal of Vacuum Science and Technology A · OSTI ID:1871781

Ditter, Alex S.; Pacold, Joseph I.; Dai, Zurong; +5 more

Induced Ferromagnetism in Epitaxial Uranium Dioxide Thin Films

Journal Article · 2022 · Advanced Science · OSTI ID:1891546

Sharma, Yogesh; Paudel, Binod; Huon, Amanda; +13 more

Title: Chemical and elemental mapping of spent nuclear fuel sections by soft X-ray spectromicroscopy

Citation Formats

References (73)

Similar Records

Related Subjects