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Title: Oxidation and Hydration of U3O8 Materials Following Controlled Exposure to Temperature and Humidity

Abstract

Chemical signatures correlated with uranium oxide processing are of interest to forensic science for inferring sample provenance. Identification of temporal changes in chemical structures of process uranium materials as a function of controlled temperatures and relative humidities may provide additional information regarding sample history. In this study, a high-purity α-U3O8 sample and three other uranium oxide samples synthesized from reaction routes used in nuclear conversion processes were stored under controlled conditions over 2–3.5 years, and powder X-ray diffraction analysis and X-ray absorption spectroscopy were employed to characterize chemical speciation. Signatures measured from the α-U3O8 sample indicated that the material oxidized and hydrated after storage under high humidity conditions over time. Impurities, such as uranyl fluoride or schoepites, were initially detectable in the other uranium oxide samples. After storage under controlled conditions, the analyses of the samples revealed oxidation over time, although the signature of the uranyl fluoride impurity diminished. The presence of schoepite phases in older uranium oxide material is likely indicative of storage under high humidity and should be taken into account for assessing sample history. The absence of a signature from a chemical impurity, such as uranyl fluoride hydrate, in an older material may not preclude its presencemore » at the initial time of production. LA-UR-15-21495.« less

Authors:
 [1];  [2];  [3];  [2];  [2];  [2];  [2];  [4];  [2];  [2];  [2];  [5];  [2]
+ Show Author Affiliations
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of Missouri, Columbia, MO (United States). Dept. of Chemistry
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Univ. of Nevada, Las Vegas, NV (United States). Dept. of Chemistry and Biochemistry
  4. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  5. Univ. of Missouri, Columbia, MO (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Nuclear Science and Security Consortium
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1329579
Alternate Identifier(s):
OSTI ID: 1454611
Report Number(s):
LA-UR-15-21495
Journal ID: ISSN 0003-2700
Grant/Contract Number:  
AC52-06NA25396; AC02-76SF00515; HSGQDC-13-X-00269; HDHQDC-08-X-00805; 2012-DN-130-NF0001-02; NA0000979
Resource Type:
Accepted Manuscript
Journal Name:
Analytical Chemistry
Additional Journal Information:
Journal Volume: 87; Journal Issue: 8; Journal ID: ISSN 0003-2700
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Tamasi, Alison L., Boland, Kevin S., Czerwinski, Kenneth, Ellis, Jason K., Kozimor, Stosh A., Martin, Richard L., Pugmire, Alison L., Reilly, Dallas, Scott, Brian L., Sutton, Andrew D., Wagner, Gregory L., Walensky, Justin R., and Wilkerson, Marianne P. Oxidation and Hydration of U3O8 Materials Following Controlled Exposure to Temperature and Humidity. United States: N. p., 2015. Web. doi:10.1021/ac504105t.
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Tamasi, Alison L., Boland, Kevin S., Czerwinski, Kenneth, Ellis, Jason K., Kozimor, Stosh A., Martin, Richard L., Pugmire, Alison L., Reilly, Dallas, Scott, Brian L., Sutton, Andrew D., Wagner, Gregory L., Walensky, Justin R., & Wilkerson, Marianne P. Oxidation and Hydration of U3O8 Materials Following Controlled Exposure to Temperature and Humidity. United States. https://doi.org/10.1021/ac504105t
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Tamasi, Alison L., Boland, Kevin S., Czerwinski, Kenneth, Ellis, Jason K., Kozimor, Stosh A., Martin, Richard L., Pugmire, Alison L., Reilly, Dallas, Scott, Brian L., Sutton, Andrew D., Wagner, Gregory L., Walensky, Justin R., and Wilkerson, Marianne P. Wed . "Oxidation and Hydration of U3O8 Materials Following Controlled Exposure to Temperature and Humidity". United States. https://doi.org/10.1021/ac504105t. https://www.osti.gov/servlets/purl/1329579.
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@article{osti_1329579,
title = {Oxidation and Hydration of U3O8 Materials Following Controlled Exposure to Temperature and Humidity},
author = {Tamasi, Alison L. and Boland, Kevin S. and Czerwinski, Kenneth and Ellis, Jason K. and Kozimor, Stosh A. and Martin, Richard L. and Pugmire, Alison L. and Reilly, Dallas and Scott, Brian L. and Sutton, Andrew D. and Wagner, Gregory L. and Walensky, Justin R. and Wilkerson, Marianne P.},
abstractNote = {Chemical signatures correlated with uranium oxide processing are of interest to forensic science for inferring sample provenance. Identification of temporal changes in chemical structures of process uranium materials as a function of controlled temperatures and relative humidities may provide additional information regarding sample history. In this study, a high-purity α-U3O8 sample and three other uranium oxide samples synthesized from reaction routes used in nuclear conversion processes were stored under controlled conditions over 2–3.5 years, and powder X-ray diffraction analysis and X-ray absorption spectroscopy were employed to characterize chemical speciation. Signatures measured from the α-U3O8 sample indicated that the material oxidized and hydrated after storage under high humidity conditions over time. Impurities, such as uranyl fluoride or schoepites, were initially detectable in the other uranium oxide samples. After storage under controlled conditions, the analyses of the samples revealed oxidation over time, although the signature of the uranyl fluoride impurity diminished. The presence of schoepite phases in older uranium oxide material is likely indicative of storage under high humidity and should be taken into account for assessing sample history. The absence of a signature from a chemical impurity, such as uranyl fluoride hydrate, in an older material may not preclude its presence at the initial time of production. LA-UR-15-21495.},
doi = {10.1021/ac504105t},
journal = {Analytical Chemistry},
number = 8,
volume = 87,
place = {United States},
year = {Wed Mar 18 00:00:00 EDT 2015},
month = {Wed Mar 18 00:00:00 EDT 2015}
}
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https://doi.org/10.1021/ac504105t
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    Works referencing / citing this record:

    Comparison of morphologies of a uranyl peroxide precursor and calcination products
    journal, January 2016

    • Tamasi, Alison L.; Cash, Leigh J.; Tyler Mullen, W.
    • Journal of Radioanalytical and Nuclear Chemistry
    • DOI: 10.1007/s10967-016-4692-x

    Energetics of hydration on uranium oxide and peroxide surfaces
    journal, June 2019

    • Guo, Xiaofeng; Wu, Di; Ushakov, Sergey V.
    • Journal of Materials Research, Vol. 34, Issue 19
    • DOI: 10.1557/jmr.2019.192
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