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Chemical forensic profiling and attribution signature determination of sarin nerve agent using GC–MS, LC–MS and NMR

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Abstract

Sarin is a highly toxic nerve agent classified by the Chemical Weapon Convention as a Schedule 1 chemical with no use other than to kill or injure. Moreover, in recent times, chemical warfare agents have been deployed against both military and civilian populations. Chemical warfare agents always contain minor impurities that can provide important chemical attribution signatures (CAS) that can aid in forensic investigations. In order to understand the trace molecular composition of sarin, various analytical approaches including GC–MS, LC–MS and NMR were used to determine the chemical markers of a set of sarin samples. Precursor materials were studied and the full characterisation of a synthetic process was undertaken in order to provide new insights into potential chemical attribution signatures for this agent. Several compounds that were identified in the precursor were also found in the sarin samples linking it to its method of preparation. The identification of these CAS contributes critical information about a synthetic route to sarin, and has potential for translation to related nerve agents.

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Data Availability

The datasets generated during and/or analysed during the current study are not publicly available due to obligations pertaining to non-proliferation of chemical warfare agents.

Abbreviations

AMDIS:

Automated mass spectral deconvolution and identification system

BSTFA:

N,O-Bis(trimethylsilyl)trifluoroacetamide

CAS:

Chemical attribution signature

CAS#:

Chemical abstracts service number

CI:

Chemical ionisation (mass spectrometry)

CWA:

Chemical warfare agent

CWC:

Chemical weapons convention

DC:

Methylphosphonic dichloride

DCM:

Dichloromethane

DF:

Methylphosphonic difluoride

DVB:

Divinylbenzene

EI:

Electron ionisation (mass spectrometry)

FPD:

Flame photometric detector

GB:

Sarin (isopropyl methylphosphonofluoridate)

IPA:

Isopropanol

OCAD:

OPCW central analytical database

OPCW:

Organisation for the Prohibition of Chemical Weapons

PDMS:

Polydimethylsiloxane

SPME:

Solid-phase microextraction

TMCS:

Trimethylchlorosilane

TSP:

Trimethylsilylpropanoic acid

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Acknowledgements

The authors would like to acknowledge Craig Brinkworth, Claudio Ceccato and Hung Tran for their contributions to this work.

Funding

This research was fully funded by the government of Australia.

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Authors and Affiliations

  1. Defence Science and Technology Group, 506 Lorimer St, Fishermans Bend, VIC, 3207, Australia

    Renée L. Webster, Simon P. B. Ovenden, Lyndal J. McDowall, Genevieve H. Dennison, Melissa J. Laws, Nathan W. McGill, Jilliarne Williams & Shannon D. Zanatta

Authors
  1. Renée L. Webster
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  2. Simon P. B. Ovenden
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  3. Lyndal J. McDowall
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  4. Genevieve H. Dennison
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  5. Melissa J. Laws
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  6. Nathan W. McGill
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  7. Jilliarne Williams
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  8. Shannon D. Zanatta
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Contributions

R. Webster and S. Ovenden contributed to the study conception and design. Material preparation, data collection and analysis were performed by all authors. The first draft of the manuscript was written by R. Webster and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

Corresponding author

Correspondence to Renée L. Webster.

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This research did not involve work on humans or animals and no biological material was used.

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The authors declare no competing interests.

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Webster, R.L., Ovenden, S.P.B., McDowall, L.J. et al. Chemical forensic profiling and attribution signature determination of sarin nerve agent using GC–MS, LC–MS and NMR. Anal Bioanal Chem 414, 3863–3873 (2022). https://doi.org/10.1007/s00216-022-04027-1

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  • DOI: https://doi.org/10.1007/s00216-022-04027-1

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