Challenges in correlating oxygen stable isotope ratios of hydrates on uranium ore concentrates to process waters

Journal Article · Mon May 29 00:00:00 EDT 2023 · Radiochimica Acta

DOI:https://doi.org/10.1515/ract-2023-0154· OSTI ID:2202914

Chalifoux, Aaron M. ^[1]; Singleton, Michael J. ^[2]; Cisneros, Miguel ^[2]; Oerter, Erik J. ^[2]; Hanson, Alexa B. ^[3]; McDonald, Luther W. ^[1]

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1. University of Utah, Salt Lake City, UT (United States)
2. Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
3. Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Exchange of oxygen stable isotopes (δ¹⁸O values) between precipitation waters and uranium oxides is governed by thermodynamics or kinetics. It has been assumed that meteoric waters can be related to precipitation waters in uranium ore concentrates and their calcination and reduced uranium oxide products. With this assumption, the δ¹⁸O values of uranium materials could provide forensic signatures that identify the production history and geolocation of nuclear materials. To further exploit the potential of δ¹⁸O values in nuclear material analysis, this study examines the oxygen stable isotope exchange in two UOCs, magnesium diuranate (MDU) and sodium diuranate (SDU). MDU and SDU were synthesized from solutions of uranyl nitrate hexahydrate using precipitation waters with unique oxygen isotope compositions. The structures of the MDU and SDU were analyzed using powder X-ray diffraction (p-XRD) and thermal mass loss curves, while the δ¹⁸O values of waters generated during thermal decomposition were analyzed using a thermogravimetric analyzer coupled to an isotope ratio infrared spectrometer (TGA-IRIS). By p-XRD, the MDU was uniform and amorphous across all syntheses with residual crystalline material incorporated as a minor component. Combined with the TGA results, all of the MDU is likely amorphous MgU₂O₇·3H₂O with MgO impurities present throughout. In contrast, the SDU synthesis resulted in multiple phases with many samples exhibiting crystalline phases including a combination of Na(UO₂)₄O₂(OH)₅·5H₂O and Na₂(UO2)₆O₄(OH)₆·8H₂O with a Na₂U₂O₇ minor phase. A small fraction of the SDU samples were amorphous with no crystalline XRD peaks observed. Mass loss curves of the SDU samples revealed that the amorphous samples contained inclusions of similar crystalline phases compared to the crystalline materials. The uniformity of the MDU samples enabled highly reproducible measurements of δ¹⁸O values of the water vapor yielded for two dehydration events at 170 °C and 500 °C. In contrast, the multiphase composition of the SDU samples resulted in poor reproducibility in δ¹⁸O values. In conclusion, neither system revealed any correlation between the δ¹⁸O values of precipitation water, and the waters released during dehydration of the UOCs.

• Research Organization: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
• Sponsoring Organization: USDOE National Nuclear Security Administration (NNSA), Office of Defense Nuclear Nonproliferation
• Grant/Contract Number: AC52-07NA27344
• OSTI ID: 2202914
• Report Number(s): LLNL-JRNL-846797; 1070425
• Journal Information: Radiochimica Acta, Vol. 111, Issue 8; ISSN 0033-8230
• Publisher: de Gruyter
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
nuclear forensics
uranium ore concentrates
oxygen isotope ratios
magnesium diuranate
sodium diuranate