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Pu(IV) quantification via visible-near-infrared absorption spectroscopy: tackling interferences using D-optimal design and partial least squares.

Created on 15 Jul 2026

Authors

Luke R Sadergaski, Jeffrey D Einkauf, Sara E Gilson, Laetitia H Delmau, Jonathan D Burns

Published in

Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy. Volume 363. Issue Pt 2. Pages 128411. Jul 09, 2026. Epub Jul 09, 2026.

Abstract

This study presents a novel analytical approach for quantifying Pu(IV) in glove box environments using fiber-optic-based visible-near-infrared absorption spectroscopy in combination with partial least squares regression (PLSR) and design of experiments. The method addresses significant challenges posed by overlapping spectral features arising from Nd(III), which is a common fission product impurity, and the speciation variability of Pu(IV) nitrato complexes in HNO3 concentrations ranging from 2.5 to 11 M. A curated training set consisting of data from 20 samples was developed via D-optimal design to enable robust PLSR model calibration for Pu(IV) using the near-infrared band near 1050 nm. The training set was acquired from samples in cuvettes with a 1-cm path length and was used to build the PLSR model. The robustness of the model was validated with data collected using a dip probe with a 1-cm path length and varying Pu(IV) concentrations. The strong performance of the model indicates good model transfer from cuvette to dip probe and highlights the potential for in situ measurements and online monitoring of reactions in a crystallization reactor vessel. The results demonstrate that this combined spectroscopic and chemometric approach can accurately and simultaneously quantify Pu(IV) and HNO3, thereby offering a promising tool for real-time monitoring in process environments.

PMID:
42447529
Bibliographic data and abstract were imported from PubMed on 15 Jul 2026.

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