In the pyrochemical separation of used nuclear fuel (UNF), fission product, rare earth, and actinide chlorides accumulate in the molten salt electrolyte over time. Measuring this salt composition in near real-time is advantageous for operational efficiency, material accountability, and nuclear safeguards. Laser-induced breakdown spectroscopy (LIBS) has been proposed and demonstrated as a potential analytical approach for molten LiCl-KCl salts. However, all the studies conducted to date have used a static surface approach which can lead to issues with splashing, low repeatability, and poor sample homogeneity. In this initial study, a novel molten salt aerosol approach has been developed and explored to measure the composition of the salt via LIBS. The functionality of the system has been demonstrated as well as a basic optimization of the laser energy and nebulizer gas pressure used. Initial results have shown that this molten salt aerosol-LIBS system has a great potential as an analytical technique for measuring the molten salt electrolyte used in this UNF reprocessing technology.

In this current study, the molten salt aerosol-laser-induced breakdown spectroscopy (LIBS) system was used to measure the uranium (U) content in a ternary UCl-LiCl-KCl salt to investigate and assess a near real-time analytical approach for material safeguards and accountability. Experiments were conducted using five different U concentrations to determine the analytical figures of merit for the system with respect to U. In the analysis, three U lines were used to develop univariate calibration curves at the 367.01 nm, 385.96 nm, and 387.10 nm lines. The 367.01 nm line had the lowest limit of detection (LOD) of 0.065 wt% U. The 385.96 nm line had the best root mean square error of cross-validation (RMSECV) of 0.20 wt% U. In addition to the univariate calibration approach, a multivariate partial least squares (PLS) model was developed to further analyze the data. Using partial least squares (PLS) modeling, an RMSECV of 0.085 wt% U was determined. The RMSECV from the multivariate approach was significantly better than the univariate case and the PLS model is recommended for future LIBS analysis. Overall, the aerosol-LIBS system performed well in monitoring the U concentration and it is expected that the system could be used to quantitatively determine the U compositions within the normal operational concentrations of U in pyroprocessing molten salts.

Pyroprocessing of used nuclear fuel (UNF) has many advantages-including that it is proliferation resistant. However, as part of the process, special nuclear materials accumulate in the electrolyte salt and present material accountability and safeguards concerns. The main motivation of this work was to explore a laser-induced breakdown spectroscopy (LIBS) approach as an online monitoring technique to enhance the material accountability of special nuclear materials in pyroprocessing. In this work, a vacuum extraction method was used to draw the molten salt (CeCl-GdCl-LiCl-KCl) up into 4 mm diameter Pyrex tubes where it froze. The salt was then removed and the solid salt was measured using LIBS and inductively coupled plasma mass spectroscopy (ICP-MS). A total of 36 samples were made that varied the CeCl and GdCl (surrogates for uranium and plutonium, respectively) concentrations from 0.5 wt% to 5 wt%. From these samples, univariate calibration curves for Ce and Gd were generated using peak area and peak intensity methods. For Ce, the Ce 551.1 nm line using the peak area provided the best calibration curve with a limit of detection (LOD) of 0.099 wt% and a root mean squared error of cross-validation (RMSECV) of 0.197 wt%. For Gd, the best curve was generated using the peak intensities of the Gd 564.2 nm line resulting in a LOD of 0.027 wt% and a RMSECV of 0.295 wt%. The RMSECV for the univariate cases were determined using leave-one-out cross-validation. In addition to the univariate calibration curves, partial least squares (PLS) regression was done to develop a calibration model. The PLS models yielded similar results with RMSECV (determined using Venetian blind cross-validation with 17% left out per split) values of 0.30 wt% and 0.29 wt% for Ce and Gd, respectively. This work has shown that solid pyroprocessing salt can be qualitatively and quantitatively monitored using LIBS. This work has the potential of significantly enhancing the material monitoring and safeguards of special nuclear materials in pyroprocessing.

Laser-induced breakdown spectroscopy (LIBS) was used to detect and measure the concentrations of Ce and Gd in aqueous aerosol solutions. A total of 36 standards, with concentrations of Ce and Gd ranging from 100 parts per million (ppm) to 10 000 ppm, were made to explore the relationship between them. In this study, a Collison nebulizer with an argon carrier gas was used to generate the aerosol droplets. For each liquid sample, ten repetitions of 200 laser shots each were recorded. The percent relative standard deviations (%RSD) were on an average of 7.5% between the ten different sample repetitions. Due to the close proximity of the Ce and Gd lines, it was challenging to identify peaks with low interferences. However, several lines were identified, calibration curves were constructed, and the best curves were generated using the 457.228 nm line for Ce and the 409.861 nm line for Gd. The LODs for these curves were calculated to be 209.7 ppm and 216.4 ppm for the Ce line and Gd line, respectively.

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