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Title: Organic Chemical Attribution Signatures for the Sourcing of a Mustard Agent and Its Starting Materials

Chemical attribution signatures (CAS) are being investigated for the sourcing of chemical warfare (CW) agents and their starting materials that may be implicated in chemical attacks or CW proliferation. The work reported here demonstrates for the first time trace impurities produced during the synthesis of tris(2-chloroethyl)amine (HN3) that point to specific reagent stocks used in the synthesis of this CW agent. Thirty batches of HN3 were synthesized using different combinations of commercial stocks of triethanolamine (TEA), thionyl chloride, chloroform, and acetone. The HN3 batches and reagent stocks were then analyzed for impurities by gas chromatography/mass spectrometry. Reaction-produced impurities indicative of specific TEA and chloroform stocks were exclusively discovered in HN3 batches made with those reagent stocks. In addition, some reagent impurities were found in the HN3 batches that were presumably not altered during synthesis and believed to be indicative of reagent type regardless of stock. Supervised classification using partial least squares discriminant analysis (PLSDA) on the impurity profiles of chloroform samples from seven stocks resulted in an average classification error by cross-validation of 2.4%. A classification error of zero was obtained using the seven-stock PLSDA model on a validation set of samples from an arbitrarily selected chloroform stock. In amore » separate analysis, all samples from two of seven chloroform stocks that were purposely not modeled had their samples matched to a chloroform stock rather than assigned a “no class” classification.« less
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Publication Date:
OSTI Identifier:
Report Number(s):
Journal ID: ISSN 0003-2700; 400904120
DOE Contract Number:
Resource Type:
Journal Article
Resource Relation:
Journal Name: Analytical Chemistry; Journal Volume: 88; Journal Issue: 10
American Chemical Society (ACS)
Research Org:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org:
Country of Publication:
United States
chemical forensics