Development and testing of a novel micro-Raman probe and application of calibration transfer method for the quantitative analysis of microfluidic nitric acid streams

Nelson, Gilbert L.; Lines, Amanda M.; Casella, Amanda J.; Bello, Job M.; Bryan, Samuel A.

doi:10.1039/c7an01761h

Development and testing of a novel micro-Raman probe and application of calibration transfer method for the quantitative analysis of microfluidic nitric acid streams

Journal Article · Wed Mar 07 04:00:00 EST 2018 · Analyst

DOI:https://doi.org/10.1039/c7an01761h· OSTI ID:1526242

Nelson, Gilbert L. ^[1]; Lines, Amanda M. ^[2]; Casella, Amanda J. ^[2]; Bello, Job M. ^[3]; ^[2]

UNIVERSITY PROGRAMS
BATTELLE (PACIFIC NW LAB)
Spectra Solutions Inc.

To simplify and improve the safety of reprocessing used nuclear fuel, an initial assessment was made of Raman microscopy applied to microfluidic volumes with a view toward the on-line spectroscopic measurement of highly radioactive solutions. This study compares a microscopic Raman probe (excitation focal point diameter 70 µm) to a larger, well studied probe (excitation focal point diameter 125 µm) used in prior investigations. This was done by chemometrically modeling and predicting concentrations of HNO3 solutions (0 M to 8 M) as they flowed through microfluidic cells based upon spectra from each probe. Spectra recorded for each probe using the same static HNO3 solution set contained in 2 dram glass vials were used as training sets to produce models for the respective probes. Modeling required baseline, normalization and smoothing preprocessing to compensate for a reduced path length between the static glass vial training set (4 cm) and the reduced path length flow cell (1 cm), wide ranging solution concentrations, and the associated non-linear spectral changes, and abrupt and uneven concentration changes of flowing solutions. The micro-Raman probe is able to produce spectra that may be analyzed chemometrically to accurately predict the concentration of flowing HNO3 solutions down to microliter volumes. Based upon RMSECV and RMSEP modeling statistics concentration predictions of the micro-Raman probe are comparable to those obtained for a macro-Raman on identical samples.

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1526242

Report Number(s):: PNNL-SA-120604

Journal Information:: Analyst, Journal Name: Analyst Journal Issue: 5 Vol. 143

Country of Publication:: United States

Language:: English

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