No abstract

To enable the deployment of molten salt reactor technology, the development of off-gas treatment systems and advanced monitoring tools capable of operating with high temperatures and radiation fields while delivering near real-time information is necessary. This study aims to fulfill this requirement and proposes laser-induced breakdown spectroscopy (LIBS) for monitoring molten salt aerosol streams. A sheath gas measuring method was developed to protect optical elements from aerosol particles and to ensure a relatively constant aerosol stream for measurement. An aqueous system was studied to demonstrate the utility of LIBS for monitoring possible fission products in an aerosol stream: Gd, Nd, and Sm up to 2000 parts per million (ppm). A calibration model was built using partial least squares (PLS) regression with five, six, and nine latent variables for Gd, Nd, and Sm, respectively. This calibration model successfully estimated the concentrations of three test samples, which were validated with inductively charged plasma optical emission spectroscopy measurements at a 99.9% confidence interval. To enhance these models, a genetic algorithm was used to filter the spectra before entering the PLS model, thereby limiting the spectral features being regressed to those with greater correlations to concentration. This allowed for the number of latent variables used in the PLS models to be reduced to four, three, and three for Gd, Nd, and Sm, respectively. Lastly, the genetic algorithm-filtered PLS models were used to predict the concentrations of the aerosol stream on a real-time dataset and resulted in a 73%, 18%, and 25% improvement in root mean squared error of prediction compared to the original PLS models developed.

This study with surrogate materials shows that laser-induced breakdown spectroscopy (LIBS) is a robust tool with promising capability toward monitoring gaseous (Xe and Kr) and aerosol (Cs and Rb) species in an off-gas stream from a molten salt reactor (MSR). MSRs will continually evolve fission products into the cover gas flowing across the reactor headspace. The cover gas entrains Xe and Kr gases, along with aerosol particles, before passing into an off-gas treatment system. Univariate models of Xe and Kr peaks showed a strong correlation to concentration indicated by their coefficients of determination of 0.983 and 0.997, respectively. Multivariate models were built for all four analytes using partial least squares regression coupled with preprocessing steps including normalization, trimming, and/or genetic algorithm derived filters. The models were evaluated by predicting the concentrations of the analytes in four validation samples, in which all calibration models were successfully validated at a confidence interval of 99.9%. Lastly, pressure controllers were used to regulate the mass flow rate of Kr flowing into the measurement cell in sinusoidal and stepwise waveforms to test the real-time monitoring capabilities of the regression models. Both univariate and partial least squares Kr models were able to successfully quantify the gas concentration in the real-time evaluation. The root mean squared error of prediction (RMSEP) values for these real-time tests were calculated to be 0.051, 0.060, and 0.121 mol% demonstrating the measurement systems’ capability to perform online monitoring with acceptable accuracy.

Selecting optimal combinations of preprocessing methods is a major holdup for chemometric analysis. The analyst decides which method(s) to apply to the data, frequently by highly subjective or inefficient means, such as user experience or trial and error. Here, we present a user-friendly method using optimal experimental designs for selecting preprocessing transformations. We applied this strategy to optimize partial least square regression (PLSR) analysis of Stokes Raman spectra to quantify hydroxylammonium (0–0.5 M), nitric acid (0–1 M), and total nitrate (0–1.5 M) concentrations. The best PLSR model chosen by a determinant (D)-optimal design comprising 26 samples (i.e., combinations of preprocessing methods) was compared with PLSR models built with no preprocessing, a user-selected preprocessing method (i.e., trial and error), and a user-defined design strategy (576 samples). The D-optimal selection strategy improved PLSR prediction performance by more than 50% compared with the raw data and reduced the number of combinations by more than 95.5%.

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)...