On the use of spectra from portable Raman and ATR-IR instruments in synthesis route attribution of a chemical warfare agent by multivariate modeling

Abstract

Collecting data under field conditions for forensic investigations of chemical warfare agents calls for the use of portable instruments. In this study, a set of aged, crude preparations of sulfur mustard were characterized spectroscopically without any sample preparation using handheld Raman and portable IR instruments. The spectral data was used to construct Random Forest multivariate models for the attribution of test set samples to the synthetic method used for their production. Colored and fluorescent samples were included in the study, which made Raman spectroscopy challenging although fluorescence was diminished by using an excitation wavelength of 1064 nm. The predictive power of models constructed with IR or Raman data alone, as well as with combined data was investigated. Both techniques gave useful data for attribution. Model performance was enhanced when Raman and IR spectra were combined, allowing correct classification of 19/23 (83%) of test set spectra. The results demonstrate that data obtained with spectroscopy instruments amenable for field deployment can be useful in forensic studies of chemical warfare agents.