Uranium Single Particle Analysis for Simultaneous Fluorine and Uranium Isotopic Determinations via Laser-Induced Breakdown Spectroscopy/Laser Ablation–Multicollector–Inductively Coupled Plasma–Mass Sp

Uranyl fluoride (UO₂F₂) particles (<20 μm) were subjected to first-of-its-kind analysis via simultaneous laser-induced breakdown spectroscopy (LIBS) and laser ablation multi-collector inductively coupled plasma–mass spectrometry (LA–MC–ICP–MS). Briefly, a nanosecond pulsed high-energy laser was focused onto the sample (particle) surface. In a single laser pulse, the UO₂F₂ particle was excited/ionized within the microplasma volume, and the emission of light was collected via fiber optics such that emission spectroscopy could be employed for the detection of uranium (U) and fluorine (F). The ablated particle was simultaneously transported into the MC–ICP–MS for high precision isotopic (i.e., ²³⁴U, ²³⁵U, and ²³⁸U) analysis. This method, LIBS/LA–MC–ICP–MS was optimized and employed to rapidly measure 80+ UO₂F₂ particles, which were subjected to different calcination processes, which results in varying degrees of F loss from the individual particles. In measuring the particles, the average F/U ratios for the populations treated at 100 and 500 °C were 2.78 ± 1.28 and 1.01 ± 0.50, respectively, confirming loss of F through the calcination process. The average ²³⁵U/²³⁸U on the particle populations for the 100 and 500 °C were 0.007262 (22) and 0.007231 (23), which was determined to be <0.2% from the expected value. The ²³⁴U/²³⁸U ratios on the same particles were 0.000053 (11) and 0.000050 (10) for the 100 and 500 °C, respectively, <10% from the expected value. Notably, each population was analyzed in under 5 min, demonstrating the truly rapid analysis technique presented here in this paper.. Authors: Manard, Benjamin T. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000207400627); Quarles, C. Derrick [Elemental Scientific Inc., Omaha, NE (United States)]; Bradley, Veronica C. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:0000000246333009); Spano, Tyler L. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000165729722); Zirakparvar, N. Alex [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000337797730). DOE Contract: AC05-00OR22725. Subjects: 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; Anions; Cations; Fluorine; Materials; Uranium