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

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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.

Illustrated here are six parent organophosphorus nerve agents corresponding to the degradation products analyzed by gas chromatography with ICPMS and ToF-MS detection. The authors would like to thank Daisy-Malloy Hamburg and Kevin M. Kubachka for creating this figure

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References

  1. OPCW (1993) Convention on the prohibition of the development, production, stockpiling and use of chemical weapons and on their destruction. Organization for the Prohibition of Chemical Weapons (OPCW), The Hague, The Netherlands

  2. OPCW (2006) Weapons. Accessed September 27, 2006. http://www.opcw.org/docs/cwc_eng.pdf

  3. Ember LR (2006) ACS Chem Eng News 84:87–89

    Google Scholar 

  4. Tornes JA, Opstad AM, Johnsen BA (2006) Sci Total Environ 356:235–246

    Article  PubMed  CAS  Google Scholar 

  5. Barr JR, Driskell WJ, Aston LS, Martinez RA (2004) J Anal Toxicol 28:372–378

    PubMed  CAS  Google Scholar 

  6. Smith JR, Schlager JJ (1996) J High Res Chromatogr 19:151–154

    Article  CAS  Google Scholar 

  7. Vasilevskii SV, Kireev AF, Rybal’chenko IV, Suvorkin VN (2002) J Anal Chem USSR 57:491–497

    Article  CAS  Google Scholar 

  8. Saradhi UVRV, Prabhakar S, Reddy TJ, Vairamani M (2006) J Chromatogr A 1129:9–13

    Article  PubMed  CAS  Google Scholar 

  9. Gupta AK, Pardasani D, Kanaujia PK, Tak V, Dubey DK (2006) Rapid Commun Mass Spectrom 20:2115–2119

    Article  PubMed  CAS  Google Scholar 

  10. Lee HSN, Basheer C, Lee HK (2006) J Chromatogr A 1124:91–96

    Article  PubMed  CAS  Google Scholar 

  11. Logan TP, Allen ED, Way MR, Swift AT, Soni S-D, Koplovitz I (2006) Toxicol Mech Methods 16:359–363

    Article  CAS  Google Scholar 

  12. Steiner WE, Clowers BH, Matz LM, Siems WF, Hill HH Jr (2002) Anal Chem 74:4343–4352

    Article  PubMed  CAS  Google Scholar 

  13. Steiner WE, Harden CS, Hong F, Klopsch SJ, Hill HH, McHughVM (2006) J Am Soc Mass Spectrom 17:241–245

    Article  PubMed  CAS  Google Scholar 

  14. Hooijschuur EWJ, Kientz CE, Brinkman UAT (2001) J Chromatogr A 928:187–199

    Article  PubMed  CAS  Google Scholar 

  15. Pumera M (2006) J Chromatogr A 1113:5–13

    Article  PubMed  CAS  Google Scholar 

  16. Meier UC (2004) Anal Chem 76:392–398

    Article  PubMed  CAS  Google Scholar 

  17. Koskela H, Grigoriu N, Vanninen P (2006) Anal Chem 78:3715–3722

    Article  PubMed  CAS  Google Scholar 

  18. Wada T, Nagasawa E, Hanaoka S (2006) Appl Organomet Chem 20:573–579

    Article  CAS  Google Scholar 

  19. Richardson DD, Sadi BBM, Caruso JA (2006) J Anal Atom Spectrom 21:396–403

    Article  CAS  Google Scholar 

  20. Shah M, Meija J, Cabovska B, Caruso JA (2006) J Chromatogr A 1103:329–336

    Article  PubMed  CAS  Google Scholar 

  21. Vonderheide AP, Meija J, Montes-Bayon M, Caruso JA (2003) J Anal Atom Spectrom 18:1097–1102

    Article  CAS  Google Scholar 

  22. Proefrock D, Leonhard P, Wilbur S, Prange A (2004) J Anal Atom Spectrom 19:623–631

    Article  CAS  Google Scholar 

  23. Shah M, Caruso JA (2005) J Sep Sci 28:1969–1984

    Article  PubMed  CAS  Google Scholar 

  24. Purdon JG, Pagotto JG, Miller RK (1989) J Chromatogr 475:261–272

    Article  CAS  Google Scholar 

  25. Black RM, Clarke RJ, Read RW, Reid MTJ (1994) J Chromatogr A 662:301–321

    Article  PubMed  CAS  Google Scholar 

  26. Creasy WR, Rodriguez AA, Stuff JR, Warren RW (1995) J Chromatogr A 709:333–344

    Article  CAS  Google Scholar 

  27. Sng MT, Ng WF (1999) J Chromatogr A 832:173–182

    Article  PubMed  CAS  Google Scholar 

  28. Black RM, Muir B (2003) J Chromatogr A 1000:253–281

    Article  PubMed  CAS  Google Scholar 

  29. Crenshaw MD, Cummings DB (2004) Phosphorus Sulfur 179:1009–1018

    Article  CAS  Google Scholar 

  30. Wang Q, Xie J, Gu M, Feng J, Ruan J (2005) Chromatographia 62:167–173

    Article  CAS  Google Scholar 

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Acknowledgements

The authors would like to thank Agilent technologies for their continued support of our research, as well as NIEHS Grant ES04908 (supplement 3P42-E5004908-15S4).

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Authors and Affiliations

  1. Department of Chemistry, McMicken College of Arts and Sciences, University of Cincinnati, Cincinnati, OH, 45221-0172, USA

    Douglas D. Richardson & Joseph A. Caruso

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  1. Douglas D. Richardson
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  2. Joseph A. Caruso
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Correspondence to Joseph A. Caruso.

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Richardson, D.D., Caruso, J.A. Derivatization of organophosphorus nerve agent degradation products for gas chromatography with ICPMS and TOF-MS detection. Anal Bioanal Chem 388, 809–823 (2007). https://doi.org/10.1007/s00216-007-1164-8

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  • DOI: https://doi.org/10.1007/s00216-007-1164-8

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