The quantification of plutonium in technological streams during spent nuclear fuel (SNF) reprocessing is an important practical task that has to be solved to ensure the safety of the process. Currently applied methods are tedious, time-consuming and can hardly be implemented in on-line mode. A fast and simple quantitative plutonium (IV) analysis using a potentiometric sensor array based on extracting agents is suggested in this study. The response of the set of specially designed PVC-plasticized membrane sensors can be related to plutonium content in solutions simulating real SNF-reprocessing media through multivariate regression modeling, providing 30% higher precision of plutonium quantification than optical spectroscopy.

Potentiometric multisensor systems were shown to be very promising tools for the quantification of numerous analytes in complex radioactive samples deriving from spent nuclear fuel reprocessing. Traditional multivariate calibration for these multisensor systems is performed with partial least squares regression—an intrinsically linear regression method that can provide suboptimal results when handling potentiometric signals from very complex multi-component samples. In this work, a thorough investigation was performed on the performance of a multisensor system in combination with non-linear multivariate regression models for the quantification of analytes in the PUREX (Plutonium–URanium EXtraction) process. The multisensor system was composed of 17 cross-sensitive potentiometric sensors with plasticized polymeric membranes containing different lipophilic ligands capable of heavy metals, lanthanides, and actinides binding. Regression algorithms such as support vector machines (SVM), random forest (RF), and kernel-regularized least squares (KRLS) were tested and compared to the traditional partial least squares (PLS) method in the simultaneous quantification of the following elements in aqueous phase samples of the PUREX process: U, La, Ce, Sm, Zr, Mo, Zn, Ru, Fe, Ca, Am, and Cm. It was shown that non-linear methods outperformed PLS for most of the analytes.

There is not much known on the stability of plasticized polymeric sensor membranes against ionizing radiation. While recent studies have indicated the applicability of potentiometric sensors with such membranes for quantification of actinides and lanthanides in spent nuclear fuel reprocessing solutions, the real industrial application of such sensors will require their stability in ionizing radiation fields. The present study explores this problem and evaluates the stability of potentiometric sensitivity towards lanthanides and actinides for a variety of plasticized polymeric membranes based on different neutral ligands. We demonstrate that most of the studied sensor compositions retain their sensitivity up to 50–100 kGy of the absorbed gamma radiation dose. The higher doses lead to the gradual loss of sensitivity due to the radiolysis of ligands and a polymer membrane matrix as confirmed by electrochemical impedance and nuclear magnetic resonance studies.

A multisensor system for quantitative determination of minor actinides and other transuranic elements jointly with rare earth elements in multicomponent solutions formed in the course of spent nuclear fuel reprocessing and radioactive waste management was developed and tested. A cell providing the process control in real time was fabricated and tested.