Part 1: Tracing Russian VX to its synthetic routes by multivariate statistics of chemical attribution signatures

Karin Höjer Holmgren; Carlos A Valdez; Roger Magnusson; Alexander K Vu; Sandra Lindberg; Audrey M Williams; Armando Alcaraz; Crister Åstot; Saphon Hok; Rikard Norlin

doi:10.1016/j.talanta.2018.02.104

Part 1: Tracing Russian VX to its synthetic routes by multivariate statistics of chemical attribution signatures

Talanta. 2018 Aug 15:186:586-596. doi: 10.1016/j.talanta.2018.02.104. Epub 2018 Mar 8.

Affiliations

¹ The Swedish Defence Research Agency, FOI CBRN Defence and Security, SE-901 82 Umeå, Sweden.
² Forensic Science Center, Lawrence Livermore National Laboratory, 7000 East Avenue L-091, Livermore, California 94550, United States.
³ Forensic Science Center, Lawrence Livermore National Laboratory, 7000 East Avenue L-091, Livermore, California 94550, United States. Electronic address: hok2@llnl.gov.
⁴ The Swedish Defence Research Agency, FOI CBRN Defence and Security, SE-901 82 Umeå, Sweden. Electronic address: rikard.norlin@foi.se.

PMID: 29784407
DOI: 10.1016/j.talanta.2018.02.104

Abstract

Chemical attribution signatures (CAS) associated with different synthetic routes used for the production of Russian VX (VR) were identified. The goal of the study was to retrospectively determine the production method employed for an unknown VR sample. Six different production methods were evaluated, carefully chosen to include established synthetic routes used in the past for large scale production of the agent, routes involving general phosphorus-sulfur chemistry pathways leading to the agent, and routes whose main characteristic is their innate simplicity in execution. Two laboratories worked in parallel and synthesized a total of 37 batches of VR via the six synthetic routes following predefined synthesis protocols. The chemical composition of impurities and byproducts in each route was analyzed by GC/MS-EI and 49 potential CAS were recognized as important markers in distinguishing these routes using Principal Component Analysis (PCA). The 49 potential CAS included expected species based on knowledge of reaction conditions and pathways but also several novel compounds that were fully identified and characterized by a combined analysis that included MS-CI, MS-EI and HR-MS. The CAS profiles of the calibration set were then analyzed using partial least squares discriminant analysis (PLS-DA) and a cross validated model was constructed. The model allowed the correct classification of an external test set without any misclassifications, demonstrating the utility of this methodology for attributing VR samples to a particular production method. This work is part one of a three-part series in this Forensic VSI issue of a Sweden-United States collaborative effort towards the understanding of the CAS of VR in diverse batches and matrices. This part focuses on the CAS in synthesized batches of crude VR and in the following two parts of the series the influence of food matrices on the CAS profiles are investigated.

Keywords: Chemical Warfare Agents; Chemical attribution signatures; Forensics; Impurity profiling; PLS-DA; Russian VX.