UV–Vis spectroscopy with chemometric data treatment: an option for on-line control in nuclear industry

Kirsanov, Dmitry; Rudnitskaya, Alisa; Legin, Andrey; Бабаин, В. А.

doi:10.1007/s10967-017-5252-8

Cited by 33 publications

(25 citation statements)

References 61 publications

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“…Applying optical spectroscopy for process control in nuclear technology has received much attention in recent decades, but much work is still required. 1,4 Research focused specifically on addressing the difficulty in transferring data collected in a glove box to the hot cell would be valuable. Future studies will examine the performance of models built from an optimized training set that is analyzed directly in a hot cell to one that is derived by means of a calibration transfer function.…”

Section: Future Studies and Applicationsmentioning

confidence: 99%

“…In situ spectroscopic techniques improve processing speed and efficiency, minimize waste, enhance worker safety, and offer the ability to track material inventory in real-time. [1][2][3][4] Spectroscopic approaches are useful for monitoring nitric acid (HNO 3 ) and nitrate salt concentrations in a variety of applications when system performance highly depends on HNO 3 concentration (e.g., plutonium and uranium solvent extraction-the PUREX process). 5,6 Near-infrared spectroscopy (NIR) is used to scan the 750-2500 nm region of the electromagnetic spectrum.…”

Section: Introductionmentioning

confidence: 99%

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Chemometrics and Experimental Design for the Quantification of Nitrate Salts in Nitric Acid: Near-Infrared Spectroscopy Absorption Analysis

et al. 2021

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Implementing remote, real-time spectroscopic monitoring of radiochemical processing streams in hot cell environments requires efficiency and simplicity. The success of optical spectroscopy for the quantification of species in chemical systems highly depends on representative training sets and suitable validation sets. Selecting a training set (i.e., calibration standards) to build multivariate regression models is both time- and resource-consuming using standard one-factor-at-a-time approaches. This study describes the use of experimental design to generate spectral training sets and a validation set for the quantification of sodium nitrate (0–1 M) and nitric acid (0.1–10 M) using the near-infrared water band centered at 1440 nm. Partial least squares regression models were built from training sets generated by both D- and I-optimal experimental designs and a one-factor-at-a-time approach. The prediction performance of each model was evaluated by comparing the bias and standard error of prediction for statistical significance. D- and I-optimal designs reduced the number of samples required to build regression models compared with one-factor-at-a-time while also improving performance. Models must be confirmed against a validation sample set when minimizing the number of samples in the training set. The D-optimal design performed the best when considering both performance and efficiency by improving predictive capability and reducing number of samples in the training set by 64% compared with the one-factor-at-a-time approach. The experimental design approach objectively selects calibration and validation spectral data sets based on statistical criterion to optimize performance and minimize resources.

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Section: Future Studies and Applicationsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Chemometrics and Experimental Design for the Quantification of Nitrate Salts in Nitric Acid: Near-Infrared Spectroscopy Absorption Analysis

et al. 2021

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“…In complex systems with multiple chemical species, the measured optical signals will be proportionally complex. The resulting spectral overlap, matrix effects, ionic strength effects, or signal interferences can inhibit accurate or timely response. , …”

Section: Introductionmentioning

confidence: 99%

Online, Real-Time Analysis of Highly Complex Processing Streams: Quantification of Analytes in Hanford Tank Sample

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Felmy

et al. 2019

Ind. Eng. Chem. Res.

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Processing of hazardous materials is a crucial example where online monitoring can significantly reduce operation risk, cost, and time. This is particularly true in the case of the Hanford site, where nuclear materials from the Cold War era are being processed for environmental cleanup efforts. In exceedingly complex streams such as those at Hanford, online and real-time monitoring can be challenging due to the complexity of instrument signals. Further obstacles are imposed by the caustic nature of processing streams, as well as the radiation damage inflicted on instruments and probes. Online monitoring based on Raman spectroscopy enables the detection of many Hanford tank species of interest. Nine chemical species that comprise the majority of tank waste by volume, including Al(OH)4 –, C2O4 2–, CO3 2–, CrO4 2–, NO3 –, NO3 –, OH–, PO4 3–, and SO4 2–, were detected and quantified. Real-time analysis of Raman signal allows for immediate quantification of target analytes and was successfully accomplished through the use of chemometric models. Furthermore, irradiation tests revealed that Raman monitoring systems can effectively continue to operate even after receiving 1 × 107 rad of γ dose. The online, real-time monitoring system developed here was successfully used to simultaneously quantify nine target analytes in a real sample collected from Hanford tank AP-105.

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“…In this regard, drastic reduction of the samples volumes (for a few milliliters to a few microliters or nanoliters) and the miniaturization of analytical devices that goes on is a real challenge for the nuclear industry renewal and is currently the aim of numerous researchers. 1−3 Raman spectroscopy 4 and UV−vis absorbance 5,6 are the most relevant analytical techniques to measure actinides concentrations in aqueous solutions. Several implementations for in-line monitoring of separation processes at the lab-scale have been recently reported.…”

Section: Introductionmentioning

confidence: 99%

“…Raman spectroscopy and UV–vis absorbance , are the most relevant analytical techniques to measure actinides concentrations in aqueous solutions. Several implementations for in-line monitoring of separation processes at the lab-scale have been recently reported. − In each case, the fluid is pumped to commercial small-volume flow-cells where the analysis is performed.…”

mentioning

confidence: 99%

Uranium(VI) On-Chip Microliter Concentration Measurements in a Highly Extended UV–Visible Absorbance Linearity Range

2018

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The reduction of effluents deriving from analytical control is a serious concern in the nuclear industry, for both production and R&D units. In this work we report an alternative methodology for the standard UV-vis absorbance analyses for actinides concentration monitoring along the plutonium uranium refining extraction (PUREX) process. This methodology, based on photonic lab-on-a-chip (PhLoC) technology, enables drastic sampling reduction down to a few microliters and simultaneously allows to track concentrations over several orders of magnitude while maintaining a detection linearity range. A PhLoC microfluidic platform was specifically designed to allow online sample injection with zero dead volume connectivity and the on-chip spectrophotometric approach, based on a multiple optical path configuration, was tested for the determination of uranium(VI) concentrations from 0.1 to 200 g L, showing that linearity is maintained within high levels of confidence. These results provide the proof of concept for the transposition of current analytical methods for actinides, including plutonium, to microfluidic systems.

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UV–Vis spectroscopy with chemometric data treatment: an option for on-line control in nuclear industry

Cited by 33 publications

References 61 publications

Chemometrics and Experimental Design for the Quantification of Nitrate Salts in Nitric Acid: Near-Infrared Spectroscopy Absorption Analysis

Chemometrics and Experimental Design for the Quantification of Nitrate Salts in Nitric Acid: Near-Infrared Spectroscopy Absorption Analysis

Online, Real-Time Analysis of Highly Complex Processing Streams: Quantification of Analytes in Hanford Tank Sample

Uranium(VI) On-Chip Microliter Concentration Measurements in a Highly Extended UV–Visible Absorbance Linearity Range

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