Trace Impurities Identified as Forensic Signatures in CMX‑5 Fuel Pellets Using X‑ray Spectroscopic Techniques

• Published in: Analytical chemistry (Washington) Vol. 94; no. 19; pp. 7084 - 7091
• Main Authors: van Veelen, Arjen, Hickam, Sarah M., Edwards, Nicholas P., Webb, Samuel M., Clark, David L., Wilkerson, Marianne P., Pugmire, Alison L., Bargar, John R.
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 17.05.2022; American Chemical Society (ACS)
• Subjects: analytical chemistry; Chemical composition; Chemistry; exercise; Fabrication; feedstocks; fluorescence; Forensic science; forensic sciences; Fuels; Impurities; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Iron; Lattice vibration; materials; Microstructure; Morphology; Nickel; Nuclear fuels; Pellets; Physical characteristics; Raw materials; Signature analysis; Signatures; Spatial distribution; Stoichiometry; Synchrotrons; Trace impurities; uranium; Uranium dioxide; X ray absorption; X ray imagery; X-radiation; x-ray absorption near edge spectroscopy; X-ray absorption spectroscopy; X-ray fluorescence; Zirconium
• ISSN: 0003-2700; 1520-6882; 1520-6882
• DOI: 10.1021/acs.analchem.2c00629

Small-particle analysis is a highly promising emerging forensic tool for analysis of interdicted special nuclear materials. Integration of microstructural, morphological, compositional, and molecular impurity signatures could provide significant advancements in forensic capabilities. We have applied rapid, high-sensitivity, hard X-ray synchrotron chemical imaging to analyze impurity signatures in two differently fabricated fuel pellets from the 5th Collaborative Materials Exercise (CMX5) of the IAEA Nuclear Forensics International Working Group. The spatial distributions, chemical compositions, and morphological and molecular characteristics of impurities were evaluated using X-ray absorption near-edge structure (XANES) and X-ray fluorescence chemical imaging to discover principal impurities, their granularity, particle sizes, modes of occurrence (distinct grains vs incorporation in the UO2 lattice), and sources and mechanisms of incorporation. Differences in UO2+x stoichiometry were detected at the microscale in nominally identical UO2 ceramics (CMX5-A and CMX5-B), implying the presence of multiple UO2 host phases with characteristic microstructures and feedstock compositions. Al, Fe, Ni, W, and Zr impurities and integrated impurity signature analysis identified distinctly different pellet synthesis and processing methods. For example, two different Al, W, and Zr populations in the CMX5-B sample indicated a more complex processing history than the CMX5-A sample. K-edge XANES measurements reveal both metallic and oxide forms of Fe and Ni but with different proportions between each sample. Altogether, these observations suggest multiple sources of impurities, including fabrication (e.g., force-sieving) and feedstock (mineral oxides). This study demonstrates the potential of synchrotron techniques to integrate different signatures across length scales (angstrom to micrometer) to detect and differentiate between contrasting UO2 fuel fabrication techniques.