Stable-Carbon Isotope Ratios for Sourcing the Nerve-Agent Precursor Methylphosphonic Dichloride and Its Products

Moran, James J.; Fraga, Carlos G.; Nims, Megan K.

doi:10.1016/J.TALANTA.2018.04.021

Title: Stable-Carbon Isotope Ratios for Sourcing the Nerve-Agent Precursor Methylphosphonic Dichloride and Its Products

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Abstract

The ability to connect a chemical threat agent to a specific batch of a synthetic precursor can provide a fingerprint to contribute to effective forensic investigations. Stable isotope analysis can leverage intrinsic, natural isotopic variability within the molecules of a threat agent to unlock embedded chemical fingerprints in the material. Methylphosphonic dichloride (DC) is a chemical precursor to the nerve agent sarin. DC is converted to methylphosphonic difluoride (DF) as part of the sarin synthesis process. We used a suite of commercially available DC stocks to both evaluate the potential for δ¹³C analysis to be used as a fingerprinting tool in sarin-related investigations and to develop sample preparation techniques (using chemical hydrolysis) that can simplify isotopic analysis of DC and its synthetic products. We demonstrate that natural isotopic variability in DC results in at least three distinct, isotope-resolved clusters within the thirteen stocks we analyzed. Isotopic variability in the carbon feedstock (i.e., methanol) used for DC synthesis is likely inherited by the DC samples we measured. Here, we demonstrate that the hydrolysis of DC and DF to methylphosphonic acid (MPA) can be used as a preparative step for isotopic analysis because the reaction does not impart a significant isotopic fractionation.more »« less

Authors:

Moran, James J. ^[1]; Fraga, Carlos G. ^[1]; Nims, Megan K. ^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Publication Date:: Tue Apr 10 00:00:00 EDT 2018

Research Org.:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1433506

Report Number(s):: PNNL-SA-130651
Journal ID: ISSN 0039-9140; PII: S0039914018303667

Grant/Contract Number:: AC05-76RL01830; HSHQPM-15-X-00055

Resource Type:: 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:: 07 ISOTOPE AND RADIATION SOURCES; chemical attribution signature; chemical forensics; sarin; isotope ratio mass spectrometry; methylphosphonyl difluoride

Citation Formats


                    Moran, James J., Fraga, Carlos G., and Nims, Megan K. Stable-Carbon Isotope Ratios for Sourcing the Nerve-Agent Precursor Methylphosphonic Dichloride and Its Products.  United States: N. p., 2018. 
Web.  doi:10.1016/J.TALANTA.2018.04.021.

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                    Moran, James J., Fraga, Carlos G., & Nims, Megan K. Stable-Carbon Isotope Ratios for Sourcing the Nerve-Agent Precursor Methylphosphonic Dichloride and Its Products.  United States.  https://doi.org/10.1016/J.TALANTA.2018.04.021

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                    Moran, James J., Fraga, Carlos G., and Nims, Megan K. Tue .  
"Stable-Carbon Isotope Ratios for Sourcing the Nerve-Agent Precursor Methylphosphonic Dichloride and Its Products".  United States.  https://doi.org/10.1016/J.TALANTA.2018.04.021.  https://www.osti.gov/servlets/purl/1433506.

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@article{osti_1433506,

  title        = {Stable-Carbon Isotope Ratios for Sourcing the Nerve-Agent Precursor Methylphosphonic Dichloride and Its Products},

  author       = {Moran, James J. and Fraga, Carlos G. and Nims, Megan K.},

  abstractNote = {The ability to connect a chemical threat agent to a specific batch of a synthetic precursor can provide a fingerprint to contribute to effective forensic investigations. Stable isotope analysis can leverage intrinsic, natural isotopic variability within the molecules of a threat agent to unlock embedded chemical fingerprints in the material. Methylphosphonic dichloride (DC) is a chemical precursor to the nerve agent sarin. DC is converted to methylphosphonic difluoride (DF) as part of the sarin synthesis process. We used a suite of commercially available DC stocks to both evaluate the potential for δ13C analysis to be used as a fingerprinting tool in sarin-related investigations and to develop sample preparation techniques (using chemical hydrolysis) that can simplify isotopic analysis of DC and its synthetic products. We demonstrate that natural isotopic variability in DC results in at least three distinct, isotope-resolved clusters within the thirteen stocks we analyzed. Isotopic variability in the carbon feedstock (i.e., methanol) used for DC synthesis is likely inherited by the DC samples we measured. Here, we demonstrate that the hydrolysis of DC and DF to methylphosphonic acid (MPA) can be used as a preparative step for isotopic analysis because the reaction does not impart a significant isotopic fractionation. MPA is more chemically stable, less toxic, and easier to handle than DC or DF. Further, the hydrolysis method we demonstrated can be applied to a suite of other precursors or to sarin itself, thereby providing a potentially valuable forensic tool.},

  doi          = {10.1016/J.TALANTA.2018.04.021},

  journal      = {Talanta},

  number       = ,

  volume       = 186,

  place        = {United States},

  year         = {Tue Apr 10 00:00:00 EDT 2018},

  month        = {Tue Apr 10 00:00:00 EDT 2018}

}

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Stable-carbon isotope ratios for sourcing the nerve-agent precursor methylphosphonic dichloride and its products

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The ability to connect a chemical threat agent to a specific batch of a synthetic precursor can provide a fingerprint to contribute to effective forensic investigations. Stable isotope analysis can leverage intrinsic, natural isotopic variability within the molecules of a threat agent to unlock embedded chemical fingerprints in the material. Methylphosphonic dichloride (DC) is a chemical precursor to the nerve agent sarin. It is converted to methylphosphonic difluoride (DF) as part of the sarin synthesis process. We used a suite of commercially available DC stocks to both evaluate the potential for δ13C analysis to be used as a fingerprinting toolmore »« less
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