Insights into Tetravalent Np Speciation in HNO3 through Spectroelectrochemistry and Multivariate Analysis.

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In situ optical spectroscopy, spectropotentiometry, and multivariate analysis were applied to the Np(IV) nitrate system to better understand speciation and quantify HNO3 concentration. Thin-layer spectropotentiometry, or spectroelectrochemistry, was leveraged to isolate and stabilize Np(IV) without compromising the solution conditions and generate representative Vis-NIR absorption spectra from 0.5 to 10 M HNO3 and benchmark the corresponding Np(IV) molar absorptivity coefficients. Spectra were described with principal component analysis (PCA) to identify the purest Np(IV) absorbance spectra among other oxidation states [e.g., Np(V/VI)] at each acid concentration and then to identify the primary sources of variance within each Np(IV) spectrum with respect to Np(IV) nitrate complexes. Then, partial least-squares regression (PLSR) and support vector regression (SVR) models were built to predict HNO3 concentration from the Np(IV) spectral data. The nonlinear SVR model outperformed the linear PLSR model for the HNO3 concentration predictions. Finally, the inclusion of spectra collected in edge and center point HNO3 concentrations in the calibration set was determined to be crucial for producing models with strong predictive capabilities. The multivariate approach used in this study makes it possible to quantify HNO3 concentration solely based on Np(IV) absorption spectra, which is essential to quantifying processing streams in various online monitoring applications.