Processing nuclear waste from sites
such as Hanford is a significant
environmental cleanup need while being a significant logistical challenge.
Integration of process monitoring tools, which can provide in situ and real-time feedback about the process, can significantly
alleviate needs to collect grab samples for process control and product
characterization. Raman spectroscopy paired with chemometric analysis
is one process monitoring tool that can provide chemical composition
information on a large number of chemical targets in nuclear waste
streams. However, methods to improve limits of detection as well as
drop uncertainty in quantification are needed. Optimizing instrument
specifications can achieve this; here, this is demonstrated by comparing
limits of detection for key analytes when using Raman systems with
671, 532, and 405 nm excitation wavelengths. Generally, limits of
detection decrease (allowing the measurement of lower salt concentrations)
with decreasing wavelength. Similarly, data collection times and averaging
were optimized. Finally, multiple chemometric modeling approaches
were leveraged, including multiblock methods that combined data from
all three Raman systems to simultaneously quantify targets with improved
sensitivity.