Simultaneous quantification of uranium(VI), samarium, nitric acid, and temperature with combined ensemble learning, laser fluorescence, and Raman scattering for real-time monitoring.

Abstract

Laser-induced fluorescence spectroscopy (LIFS), Raman spectroscopy, and a stacked regression ensemble was developed for near real-time quantification of uranium(VI) (1-100 μg mL-1), samarium (0-200 μg mL-1) and nitric acid (0.1-4 M) with varying temperature (20 °C-45 °C). LIFS applications range from fundamental lab-scale studies to real-time process monitoring at industrial levels, such as nuclear reprocessing applications, provided the phenomena affecting the fluorescence spectrum are accounted for (e.g., absorption, quenching, complexation). Multiple chemometric models were examined and compared to a more traditional multivariate regression approach called partial least squares (PLS). Results obtained on synthetic samples selected using D-optimal experimental design indicated that a stacked regression method, which included ridge regression, random forest, PLS, and an eXtreme gradient boost algorithm, successfully measured uranium(VI) concentrations directly in nitric acid without measuring luminescence lifetimes or standard addition. The top model resulted in percent root-mean-square error of prediction values of 5.2, 1.9, 3.0, and 2.3% for U(VI), Sm3+, HNO3, and temperature, respectively. The approach may be useful for quantifying fluorescent fission products (e.g., Sm3+) to provide information on burnup of irradiated nuclear fuel. This novel framework reinforces the applicability of LIFS for real-time applications in nuclear fuel cycle applications.