Analytical comparisons of handheld LIBS and XRF devices for rapid quantification of gallium in a plutonium surrogate matrix

• Published in: Journal of analytical atomic spectrometry 2022-05, Vol.37 (5), p.19-198
• Main Authors: Rao, Ashwin P, Jenkins, Phillip R, Auxier, John D, Shattan, Michael B, Patnaik, Anil K
• Format: Article
• Language: English
• Subjects: Absorption; Calibration; Cerium; Gallium; Laser induced breakdown spectroscopy; Plutonium; Portable equipment; Spectrum analysis; X ray fluorescence analysis
• ISSN: 0267-9477; 1364-5544
• DOI: 10.1039/d1ja00404b

This work compares a portable laser-induced breakdown spectroscopy (LIBS) analyzer to a portable X-ray fluorescence (XRF) device for quantification of gallium (Ga) in a plutonium surrogate matrix of cerium (Ce) for the first time. Calibration methods are developed with spectra of Ce-Ga samples from both devices. Metrics such as limit of detection (LoD) and mean average percent error (MAPE) are examined to evaluate calibration performance. While the portable LIBS device can yield a nearly instantaneous analytical measurement, its accuracy is hampered by self-absorption. By employing a self-absorption correction and increasing gating delay, LIBS calibrations with errors in the low single percents and LoDs of 0.1% Ga were constructed. The XRF device produces calibrations with superlative sensitivity, yielding LoDs for gallium in the low tens of parts-per-million (ppm), two orders of magnitude lower than the corrected LIBS models. However, a clear trade-off of measurement fidelity is established between the instantaneous analysis of the LIBS device and the minutes-long XRF measurement yielding superior detection limits. Comparing two handheld elemental analyzers for potential use in plutonium manufacturing quality control.