Assessment of two benzylation strategies for the analysis of nerve-agent derived ethyl- and pinacolyl methyl phosphonic acids in sandy loam soil by GC–MS

Gokool, Vidia A.; Vu, Alexander K.; Hok, Saphon; Valdez, Carlos A.

doi:10.1016/j.forc.2024.100616

Title: Assessment of two benzylation strategies for the analysis of nerve-agent derived ethyl- and pinacolyl methyl phosphonic acids in sandy loam soil by GC–MS

Journal Article · 05 November 2024 · Forensic Chemistry

DOI: https://doi.org/10.1016/j.forc.2024.100616 · OSTI ID:2481657

Gokool, Vidia A. ^[1]; Vu, Alexander K. ^[1]; Hok, Saphon ^[1]; Valdez, Carlos A. ^[1]

Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Despite their prohibition by the Chemical Weapons Convention, nerve agents (NAs) remain in use against military and civilian targets. Due to their high reactivity, NAs readily degrade to phosphonic acids, making them important markers in the inspection of areas of presumed NA use. In this work, we assess the use of benzylation to modify ethyl- and pinacolyl methylphosphonic acids, degradation products of VX and Soman respectively, for their efficient detection in a soil matrix at ~10 and ~1 μg/g using GC–MS. The soil matrix, Sandy Loam (SL), was chosen for its ubiquitous nature, complex composition with silica particles embedded in clay, and low organic content. In this study, we demonstrate that benzylation via benzyl bromide yields a LOD = 25.6 ng/mL for benzylated-EMPA and LOD = 30.1 ng/mL for benzylated-PMPA. This is superior to the use of p-methoxybenzyl trichloroacetimidate in providing stable phosphonic acid ester derivatives for analysis. A base-modified procedure for p-methoxybenzylation was explored in this study yielding a LOD = 29.1 ng/mL for p-methoxybenzylated-EMPA and LOD = 39.8 ng/mL for p-methoxybenzylated-PMPA. Both benzylation pathways (benzyl bromide and p-methoxybenzyl trichloroacetimidate) can be used to yield phosphonic acid derivatives that provide further confirmation of these Soman and VX degradation products in soil samples in investigative scenarios. The work herein represents the first application of benzylation methods for the analysis of these NA markers in the acidic, silicon-based SL soil.

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Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 2481657

Report Number(s):: LLNL-JRNL--869786; 1105254

Journal Information:: Forensic Chemistry, Journal Name: Forensic Chemistry Journal Issue: N/A Vol. 41; ISSN 2468-1709

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
GC-MS
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VX
nerve agent
phosphonic acids

Title: Assessment of two benzylation strategies for the analysis of nerve-agent derived ethyl- and pinacolyl methyl phosphonic acids in sandy loam soil by GC–MS

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