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

Abstract

Chemical attribution signatures (CAS) associated with different synthetic routes used for the production of Russian VX (VR) were identified here. 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 modelmore » 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.« less

Authors:
 [1];  [2];  [1];  [2];  [1];  [2];  [2];  [1];  [2];  [1]
  1. Swedish Defence Research Agency, Umeå (Sweden)
  2. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Forensic Science Center
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Swedish Defence Research Agency, Umeå (Sweden)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); Dept. of Homeland Security (DHS) (United States); Swedish Civil Contingencies Agency
OSTI Identifier:
1512616
Report Number(s):
LLNL-JRNL-738098
Journal ID: ISSN 0039-9140; 887647
Grant/Contract Number:  
AC52-07NA27344; HSHQPM-10-X-00014; HSHQPM-11-X-00247; 2014–5170
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Talanta
Additional Journal Information:
Journal Volume: 186; Journal ID: ISSN 0039-9140
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
chemical attribution signatures; Russian VX; chemical warfare agents; impurity profiling; forensics; PLS-DA

Citation Formats

Holmgren, Karin Höjer, Valdez, Carlos A., Magnusson, Roger, Vu, Alexander K., Lindberg, Sandra, Williams, Audrey M., Alcaraz, Armando, Åstot, Crister, Hok, Saphon, and Norlin, Rikard. Part 1: Tracing Russian VX to its synthetic routes by multivariate statistics of chemical attribution signatures. United States: N. p., 2018. Web. doi:10.1016/j.talanta.2018.02.104.
Holmgren, Karin Höjer, Valdez, Carlos A., Magnusson, Roger, Vu, Alexander K., Lindberg, Sandra, Williams, Audrey M., Alcaraz, Armando, Åstot, Crister, Hok, Saphon, & Norlin, Rikard. Part 1: Tracing Russian VX to its synthetic routes by multivariate statistics of chemical attribution signatures. United States. doi:10.1016/j.talanta.2018.02.104.
Holmgren, Karin Höjer, Valdez, Carlos A., Magnusson, Roger, Vu, Alexander K., Lindberg, Sandra, Williams, Audrey M., Alcaraz, Armando, Åstot, Crister, Hok, Saphon, and Norlin, Rikard. Thu . "Part 1: Tracing Russian VX to its synthetic routes by multivariate statistics of chemical attribution signatures". United States. doi:10.1016/j.talanta.2018.02.104. https://www.osti.gov/servlets/purl/1512616.
@article{osti_1512616,
title = {Part 1: Tracing Russian VX to its synthetic routes by multivariate statistics of chemical attribution signatures},
author = {Holmgren, Karin Höjer and Valdez, Carlos A. and Magnusson, Roger and Vu, Alexander K. and Lindberg, Sandra and Williams, Audrey M. and Alcaraz, Armando and Åstot, Crister and Hok, Saphon and Norlin, Rikard},
abstractNote = {Chemical attribution signatures (CAS) associated with different synthetic routes used for the production of Russian VX (VR) were identified here. 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.},
doi = {10.1016/j.talanta.2018.02.104},
journal = {Talanta},
issn = {0039-9140},
number = ,
volume = 186,
place = {United States},
year = {2018},
month = {3}
}

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