Derivatization of organophosphorus nerve agent degradation products for gas chromatography with ICPMS and TOF-MS detection

Anal Bioanal Chem. 2007 Jun;388(4):809-23. doi: 10.1007/s00216-007-1164-8. Epub 2007 Mar 14.

Abstract

Separation and detection of seven V-type (venomous) and G-type (German) organophosphorus nerve agent degradation products by gas chromatography with inductively coupled plasma mass spectrometry (GC-ICPMS) is described. The nonvolatile alkyl phosphonic acid degradation products of interest included ethyl methylphosphonic acid (EMPA, VX acid), isopropyl methylphosphonic acid (IMPA, GB acid), ethyl hydrogen dimethylamidophosphate sodium salt (EDPA, GA acid), isobutyl hydrogen methylphosphonate (IBMPA, RVX acid), as well as pinacolyl methylphosphonic acid (PMPA), methylphosphonic acid (MPA), and cyclohexyl methylphosphonic acid (CMPA, GF acid). N-(tert-Butyldimethylsilyl)-N-methyltrifluroacetamide with 1% TBDMSCl was utilized to form the volatile TBDMS derivatives of the nerve agent degradation products for separation by GC. Exact mass confirmation of the formation of six of the TBDMS derivatives was obtained by GC-time of flight mass spectrometry (TOF-MS). The method developed here allowed for the separation and detection of all seven TBDMS derivatives as well as phosphate in less than ten minutes. Detection limits for the developed method were less than 5 pg with retention times and peak area precisions of less than 0.01 and 6%, respectively. This method was successfully applied to river water and soil matrices. To date this is the first work describing the analysis of chemical warfare agent (CWA) degradation products by GC-ICPMS.

Publication types

  • Research Support, N.I.H., Extramural

MeSH terms

  • Chemical Warfare Agents / chemistry
  • Chemical Warfare Agents / metabolism*
  • Gas Chromatography-Mass Spectrometry / methods*
  • Organophosphonates / analysis
  • Organophosphonates / chemistry
  • Organophosphorus Compounds / analysis
  • Organophosphorus Compounds / chemistry
  • Organosilicon Compounds / analysis
  • Organosilicon Compounds / chemistry
  • Organothiophosphorus Compounds / chemistry
  • Organothiophosphorus Compounds / metabolism*
  • Rivers / chemistry
  • Sensitivity and Specificity
  • Soil / chemistry
  • Soman / analogs & derivatives
  • Soman / analysis
  • Soman / chemistry
  • Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization / methods*
  • Temperature
  • Time Factors
  • Volatilization
  • Water Pollutants, Chemical / analysis

Substances

  • Chemical Warfare Agents
  • Organophosphonates
  • Organophosphorus Compounds
  • Organosilicon Compounds
  • Organothiophosphorus Compounds
  • Soil
  • Water Pollutants, Chemical
  • t-butyldimethylsilyl compounds
  • ethyl methylphosphonic acid
  • isopropyl methylphosphonic acid
  • cyclohexyl methylphosphonic acid
  • methylphosphonic acid
  • tert-butyldimethylsilyl chloride
  • pinacolyl methylphosphonic acid
  • Soman