Isotopic analysis of uranium at the picogram level with single-shot laser induced breakdown spectroscopy

Abstract

Uranium was measured by laser induced breakdown spectroscopy (LIBS) with a limit of detection of 1.3 picograms with spectral-peak height as the analytical parameter, which shows an improvement of several orders of magnitude compared to other reports in the literature. The improvement is a result of optimizing the choice of the U analytical line, the system hardware, and the light collection and detection efficiency. The research established properties of U line emission (intensity, signal-to-background ratio, isotopic splitting, and spectral interferences) to select an optimum wavelength for analysis. The samples were mock particles from dried, monodispersed U solution droplets (∼65 pL in volume) deposited on Si wafers. LIBS emission spectra from several 235U-enriched samples were measured to demonstrate the performance for isotopic analysis. For isotopic measurements, two masses for total U, 100 pg and 325 pg, were studied. The 235U: 238U isotopic ratio was obtained by peak fitting the LIBS spectra without requiring calibration with the use of enriched standards. Depending on the total U mass and the 235U enrichment, typical relative standard deviations of the isotopic analysis ranged from several percent down to about 1%. Further, the developed method and the reported analytical performance were all based on single-shot LIBS. Overall, the study highlights the potential of LIBS as a robust and sensitive technique for isotopic analysis of U-containing particles.