Abstract
Optical sensors and chemometric models were leveraged for the quantification of uranium(VI) (0-100 μg mL-1), europium (0-150 μg mL-1), samarium (0-250 μg mL-1), praseodymium (0-350 μg mL-1), neodymium (0-1000 μg mL-1), and HNO3 (2-4 M) with varying corrosion product (iron, nickel, and chromium) levels using laser fluorescence, Raman scattering, and ultraviolet-visible-near-infrared absorption spectra. In this paper, an efficient approach to developing and evaluating tens of thousands of partial least-squares regression (PLSR) models, built from fused optical spectra or multimodal acquisitions, is discussed. Each PLSR model was optimized with unique preprocessing combinations, and features were selected using genetic algorithm filters. The 7-factor D-optimal design training set contained just 55 samples to minimize the number of samples. The performance of PLSR models was evaluated by using an automated latent variable selection script. PLS1 regression models tailored to each species outperformed a global PLS2 model. PLS1 models built using fused spectra data and a multimodal (i.e., analyzed separately) approach yielded similar information, resulting in percent root-mean-square error of prediction values of 0.9-5.7% for the seven factors. The optical techniques and data processing strategies established in this study allow for the direct analysis of numerous species without measuring luminescence lifetimes or relying on a standard addition approach, making it optimal for near-real-time, in situ measurements. Nuclear reactor modeling helped bound training set conditions and identified elemental ratios of lanthanide fission products to characterize the burnup of irradiated nuclear fuel. Leveraging fluorescence, spectrophotometry, experimental design, and chemometrics can enable the remote quantification and characterization of complex systems with numerous species, monitor system performance, help identify the source of materials, and enable rapid high-throughput experiments in a variety of industrial processes and fundamental studies.
| Original language | English |
|---|---|
| Pages (from-to) | 1759-1766 |
| Number of pages | 8 |
| Journal | Analytical Chemistry |
| Volume | 96 |
| Issue number | 4 |
| DOIs | |
| State | Published - Jan 30 2024 |
Funding
This work was supported by the National Nuclear Security Administration Office of Defense Nuclear Nonproliferation (DNN) Research & Development Forensics program and performed at Oak Ridge National Laboratory. This manuscript has been authored by UT-Battelle LLC under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ). This work was supported by the National Nuclear Security Administration Office of Defense Nuclear Nonproliferation (DNN) Research & Development Forensics program and performed at Oak Ridge National Laboratory. This manuscript has been authored by UT-Battelle LLC under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan).