Abstract
The use of negative ion monitoring mode with an atmospheric pressure ion mobility orthogonal reflector time-of-flight mass spectrometer [IM(tof)MS] to detect chemical warfare agent (CWA) degradation products from aqueous phase samples has been determined. Aqueous phase sampling used a traditional electrospray ionization (ESI) source for sample introduction and ionization. Certified reference materials (CRM) of CWA degradation products for the detection of Schedule 1, 2, or 3 toxic chemicals or their precursors as defined by the chemical warfare convention (CWC) treaty verification were used in this study. A mixture of six G-series nerve related CWA degradation products (EMPA, IMPA, EHEP, IHEP, CHMPA, and PMPA) and their related collision induced dissociation (CID) fragment ions (MPA and EPA) were found in each case to be clearly resolved and detected using the IM(tof)MS instrument in negative ion monitoring mode. Corresponding ions, masses, drift times, K o values, and signal intensities for each of the CWA degradation products are reported.
Article PDF
Avoid common mistakes on your manuscript.
References
Burgen, A. S. V.; Hobbiger, F. The Inhibition of Cholinesterases by Alkyl Phosphates and Alkylphenol Phosphate. Br. J. Pharmacol. Chemother. 1951, 6, 593–605.
Grob, D.; Harvey, A. M. The Effects and Treatment of Nerve Gas Poisoning. Am. J. Med. 1953, 14, 52–63.
Grob, D. The Manifestations and Treatment of Poisoning Due to Nerve Gas and Other Organic Phosphate Anticholinesterase Compounds. Arch. Int. Med. 1956, 98, 221–239.
Grob, D.; Harvey, J. C. Effects in Man of the Anticholinesterase Compound Sarin. J. Clin. Invest. 1958, 37, 350–368
Koelle, G. B.; Compton, J. A. F. Military Chemical and Biological Agents: Chemical and Toxicological Properties; Telford Press: Caldwell, NJ, 1987;
Ballantyne, B.; Marrs, T. C. Pharmacology and Toxicology of Organophosphates; Butterworth-Heinemann: Oxford, 1992; pp 35–39.
Fox, M.; Scott, D. The Genetic Toxicology of Nitrogen and Sulfur Mustard. Mutat. Res. 1980, 75, 131–168;
Somani, S. M.; Babu, S. R. Toxicodynamics of Sulfur Mustard. Int. J. Clin. Pharm. Therap. Toxicol. 1989, 9, 419–435;
Papinmeister, B.; Feister, A. J.; Robinson, S. I.; Ford, R. D. Medical Defense Against Mustard Gas: Toxic Mechanisms and Pharmacological Implications; CRC Press, Boca Raton, FL, 1991.
Gosselin, R. E.; Smith, R. P.; Hodge, H. C. Clinical Toxicology of Commercial Products, 5th ed.; Williams and Wilkins: Baltimore, 1984;
Hathaway, G. J.; Proctor, N. H.; Hughes, J. P.; Fischman, M. L. Proctor and Hughes’ Chemical Hazards of the Workplace, 3rd ed.; Van Nostrand Reinhold: NewYork, 1991.
Berghoff, R. S. The More Common Gases: Their Effect on the Respiratory Tract. Observation on Two Thousand Cases. Arch. Int. Med. 1919, 24, 678–684;
Gilchrist, H. L.; Matz, P. B. The Use of Mustard Gas with Report Cases. Med. Bull. Veterans Admin. 1933, 9, 339–390;
Cucinell, S. A. Review of the Toxicity of Long-Term Phosgene Exposure. Arch. Environ. Health 1974, 28, 272–275.
Kingery, A. F.; Allen, H. E. The Environmental Fate of Organophosphate Nerve Agents: A Review. Toxicol. Environ. Chem. 1995, 47, 155–184.
Vasil’ev, I. A.; Shvyryaev, B. V.; Liberman, B. M.; Sheluchenko, B. V.; Petrunin, V. A.; Gorskii, V. G. Kinetics and Mechanism of Sarin Reaction with Monoethanolamine and Mathematical Modeling of a Reactor Unit for Detoxification. Mendeleev Chem. J. 1995, 39(4), 5–10;
Yang, Y. C.; Bake, J. A.; Ward, J. R. Decontamination of Chemical Warfare Agents. Chem. Rev. 1992, 92, 1729–1743;
Yang, Y. C. Chemical Detoxification of Nerve Agent VX. Acc. Chem. Res. 1999, 32, 109–115;
Wagner, G. W.; Yang, Y. C. Rapid Nucleophilic/Oxidative Decontamination of Chemical Warfare Agents. Ind. Eng. Chem. Res. 2002, 41(8), 1925–1928.
Cheicante, R. L.; Stuff, J. R.; Durst, H. D. Separation of Sulfur Containing Chemical Warfare Related Compounds in Aqueous Samples by Micellar Electrokinetic Chromatography. J. Cap. Elec. 1995, 4, 157–163.
Larsson, L. The Alkaline Hydrolysis of Two Sarin Analogs and of Tabun. Acta Chim. Scand. 1958, 12, 783–785;
Gustafson, R. L.; Martell, A. E. A Kinetic Study of the Copper (II) Chelate-Catalyzed Hydrolysis of Isopropyl Mehtylphosphonofluoridate. J. Am. Chem. Soc. 1962, 84, 2309–2316;
Epstein, J. Rate of Decomposition of GB (Isopropyl Methylphosphonafluoridate) in Seawater. Science 1970, 170, 1936–1938;
Ellin, R. I.; Groff, W. A.; Kaminskis, A. The Stability of Sarin and Soman in Dilute Aqueous Solutions and the Catalytic Effect of Acetate Ion. J. Environ. Sci. Health B 1981, B16(6), 713–717;
Desire, B.; Saint-Andre, S. Interaction of Soman with β-Cyclodextrin. Fundam. Appl. Toxicol. 1986, 7(4), 646–657;
Hammond, P. S.; Forster, J. S. A Polymeric Amine-Copper (II) Complex as Catalyst for the Hydrolysis of 1,2,2-Trimethylpropyl Methylphosphonofluoridate (Soman) and bis(1 -Methylethyl)Phosphonofluoridate (DFP). J. Appl. Polym. Sci. 1991, 43(10), 1925–1931.
Ketelaar, J. A. A.; Gersmann, H. R.; Beck, M. M. Metal-Catalyzed Hydrolysis of Thiophosphoric Esters. Nature 1956, 177, 392–393.
Epstein, J.; Callahan, J. J.; Bauer, V. E. Kinetics and Mechanisms of Hydrolysis of Phosphonothiolates in Dilute Aqueous Solution. Phosphorus Relat. Group V Elem 1974, 4, 157–163,
Yang, Y. C.; Szafraniec, L. L.; Beaudry, W. T.; Bunton, C. A. Perhydrolysis of Nerve Agent VX. J. Org. Chem 1993, 58, 6964–6965.
Bartlett, P. D.; Swain, C. G. Kinetics of Hydrolysis and Displacement Reactions of β,β′-Dichlorodiethyl Sulfide (Mustard Gas) and of β-Chloro-β-Hydroxydiethyl Sulfide (Mustard Chlorohydrin). J. Am. Chem. Soc. 1949, 71, 1406–1415.
Waters, W. A.; Williams, J. H. Hydrolyses and Derivatives of Some Vesicant Arsenicals. J. Chem. Soc. 1950, Abstr. 18–22;
Yang, Y. C.; Szfraniec, L. L.; Beaudry, W. T.; Ward, R. J. Kinetics and Mechanism of Hydrolysis of 2-Chloroethyl Sulfides. J. Org. Chem. 1988, 53(14), 3293–3297;
Meylan, W. M.; Howard, P. H. Atom/Fragment Contribution Method for Estimating Octanol-Water Partition Coefficients. J. Pharm. Sci. 1995, 84(1), 83–92.
Douglas, D. E.; Winkler, C. A. Preparation, Purification, Physical Properties, and Hydrolysis of Cyanogen Chloride. Can. J. Res. 1947, 25B, 186–381.
Francke, S. Manual of Military Chemistry, Vol. I. Chemistry of Chemical Warfare Agents; Deutscher Militirverlag: Berlin, 1967; Translated from German by U.S. Department of Commerce, National Bureau of Standards, Institute for Applied Technology, NTIS no. AD-849-866
Khorkin, A. A.; Temkin, O. N.; Flid, R. M. Kinetics of Acidic Hydrolysis of Prussic Acid. Zhurnal. Fizicheskoi. Khimii. 1967, 41(2), 299–302.
Leitner, C. Chemical Warfare and the Red Cross Disintoxication of Water Contaminated with Gases. Chim. Et. Indust. 1930, 23, 381–386;
Dardan, D.; Popa, S. Influence of Alkalinity on the Adsorbing Poser of Activated Carbon for Warfare Gases: Phosgene, Chlorine, Chloropicrin, and Hydrocyanic Acid. Chim. Et. Indust. 1940, 44, 206;
Potter, H. H. The Effects of War Gases on Water Supplies: Decontamination. J. New Eng. W. W. Assc. 1943, 57, 137–162.
Roach, M. C.; Unger, L. W.; Zare, R. N.; Reimer, L. M.; Pumpliano, J. W.; Frost, J. W. Fluorescence Detection of Alkylphosphonic Acids Using p-(9-Anthroyloxy)Phenacyl Bromide. Anal. Chem. 1987, 59, 1056–1059;
Purdon, J. G.; Pagotto, J. G.; Miller, R. K. Preparation, Stability, and Quantitative Analysis by Gas Chromatography and Gas Chromatography-Electron Impact Mass Spectrometry of Tert-Butyldimethylsilyl Derivatives of Some Alkylphophonic and Alkyl Methylphosphonic Acids. J. Chromatogr. 1989, 475, 261.
Toernes, J. A.; Johnson, B. A. Gas Chromatographic Determination of Methylphosphonic Acids with Trimethylphenylammonium Hydroxide. J. Chromatogr. 1989, 467, 129–138;
Kientz, C. E. Chromatography and Mass Spectrometry of Chemical Warfare Agents, Toxins, and Related Compounds: State of the Art and Future Prospects. J. Chromatogr. 1998, 814(1), 1–23.
Kingery, A. F.; Allen, H. E. Ion Chromatographic Separation of Closely Related Nerve Agent Degradation Products Using and Organic Modifier to Provide Selectivity. Anal. Chem. 1994, 66(1), 155–159;
Bossle, P. C.; Reutter, D. J.; Sarver, E. W. Analysis for Alkyl Methylphosphonic Acids in Aqueous Matrixes by Ion-Pair Reversed-Phase Ion Chromatography. J. Chromatogr. 1987, 407, 399–404.
Berkout, V. D.; Cotter, R. J.; Segers, D. P. Miniaturized, E.I./Q/oa TOF Mass Spectrometer. Am. Soc. Mass Spectrom. 2001, 12, 641–647.
Asbury, R. G.; Wu, C.; Siems, W. F.; Hill, H. H. Separation and Identification of Some Chemical Warfare Degradation Products Using Electro-Spray High Resolution Ion Mobility Spectrometry with Mass Selected Detection. Anal. Chem. 2000, 404, 273–283
Tabrizchi, M.; Khayamian, T.; Taj, N. Design and Optimization of a Corona Discharge Ionization Source for Ion Mobility Spectrometry. Rev. Sci. Instrum. 2000, 71, 2321–2328.
Wils, E. R. J.; Hulst, A. G. Determination of Organophosphorus Acids by Thermospray Liquid Chromatography-Mass Spectrometry. J. Chromatogr. 1988, 454, 261–272;
Kostianen, R.; Bruins, A. P.; Hakkinen, V. M. A. Identification of Degradation Products of Some Chemical Warfare Agents by Capillary Electrophoresis-Ionspray Mass Spectrometry. J. Chromatogr. 1993, 634, 113–118;
Borrett, V. T.; Mathews, R. J.; Colton, R.; Traeger, J. C. Verification of the United Nations Chemical Weapons Convention: The Application of Electrospray Mass Spectrometry. Rapid Comm. Mass Spectrom. 1996, 114;
Black, R. M.; Read, R. W. Application of Liquid Chromatography-Atmospheric Pressure Chemical Ionization Mass Spectrometry and Tandem Mass Spectrometry to the Analysis and Identification of Degradation Products of Chemical Warfare Agents. J. Chromatogr. 1997, 759, 79–92;
D’Agostino, P. A.; Chenier, C. L.; Hancock, J. R. Packed Capillary Liquid Chromatography-Electrospray Mass Spectrometry of Snow Contaminated with Sarin. J. Chromatogr. A 2002, 950, 149–156;
D’Agostino, P. A.; Hancock, J. R.; Provost, L. R. Determination of Sarin, Soman, and Their Hydrolysis Products in Soil by Packed Capillary Liquid Chromatography-Electrospray Mass Spectrometry. J. Chromatogr. A. 2001, 291–299;
Read, R. W.; Black, R. M. Rapid Screening Procedures for the Hydrolysis Products of Chemical Warfare Agents Using Positive and Negative Ion Liquid Chromatography-Mass Spectrometry with Atmospheric Pressure Chemical Ionization. J. Chromatogr. A 1999, 862, 169–177;
D’Agostino, P. A.; Hancock, J. R.; Provost, L. R. Packed Capillary Liquid Chromatography-Electrospray Mass Spectrometry Analysis of Organophosphorus Chemical Warfare Agents. J. Chromatogr. A 1999, 840, 289–294;
Black, R. M.; Read, R. W. Analysis of Degradation Products of Organophosphorus Chemical Warfare Agents and Related Compounds by Liquid Chromatography-Mass Spectrometry Using Electrospray and Atmospheric Pressure Chemical Ionization. J. Chromatogr. A 1998, 794, 233–244.
Noami, M.; Kataoka, M.; Seto, Y. Improved tert-Butyldimethylsilylation Gas Chromatographic/Mass Spectrometric Detection of Nerve Gas Hydrolysis Products from Soils by Pretreatment of Aqueous Alkaline Extraction and Strong Anion-Exchange Solid-Phase Extraction. Anal. Chem. 2002, 74, 4709–4715;
Driskell, W. J.; Shih, M.; Needham, L. L.; Barr, D. B. Quantitation of Organophosphorus Nerve Agent Metabolites in Human Urine Using Isotope Dilution Gas Chromatography-Tandem Mass Spectrometry. J. Anal. Toxicol. 2006, 26, 6–10;
Schneider, J. F.; Boparai, A. S.; Reed, L. L. Screening for Sarin in Air and Water by Solid-Phase Microextraction-Gas Chromatography-Mass Spectrometry. J. Chromatogr. Sci. 2001, 39, 420–424.
Brickhouse, M. D.; Creasy, W. R.; Williams, B. R.; Morrissey, K. M.; O’Connor, R. J.; Durst, H. D. Multiple-Technique Analytical Characterization of a Mixture Containing Chemical-Weapons Simulant from a Munition. J. Chromatogr. A 2000, 883, 185–198;
Bartram, P. W.; Brickhouse, M. D.; Connell, T. R.; Creasy, W. R.; Henderson, V. D.; Hovanec, J. W.; Morrissey, K. M.; Stuff, J. R.; Wagner, G. W.; Williams, B. R. NMR, LC/MS, GC-IRD/MS, and GC-AED/MS Analysis of the Reactions of GD and VX with Ozone. Proceedings of the ERDEC Conference Aberdeen Proving Grounds, November, 1999, pp 691–697.
Steiner, W. E.; Clowers, B. H.; Matz, L. M.; Siems, W. F.; Hill, H. H. Rapid Screening of Aqueous Chemical Warfare Agent Degradation Products: Ambient Pressure Ion Mobility Mass Spectrometry (IMMS). Anal. Chem. 2002, 74, 4343–4352.
Steiner, W. E.; Haigh, P. B.; Clowers, B. H.; Hill, H. H. Secondary Ionization of Chemical Warfare Agent Simulants Using Atmospheric Pressure Ion Mobility Time-of-Flight Mass Spectrometry [IM(tof)MS]. Anal. Chem. 2003, 75, 6068–6078.
Steiner, W. E.; Klopsch, S. J.; English, W. A.; Hill, H. H., Jr. Detection of a Chemical Warfare Agent Simulant in Various Aerosol Matrices by Ion Mobility Time-of-Flight Mass Spectrometry [IM(tof)MS]. Anal. Chem. 2005, 77(15), 4792–4799.
Wu, C.; Siems, W. F.; Asbury, G. R.; Hill, H. H., Jr. Electrospray Ionization High-Resolution Ion Mobility Spectrometry-Mass Spectrometry. Anal. Chem. 1998, 70, 4929–4938.
Dugourd, P. H.; Hudgins, R. R.; Clemmer, D. E.; Jarrold, M. F. High-Resolution Ion Mobility Measurements. Rev. Sci. Instrum. 1997, 68, 1122–1129.
Eiceman, G. A.; Karpas, Z. Ion Mobility Spectrometry, 2nd ed.; CRC Press: Boca Ration, FL, 2005.
Guevremont, R. High-Field Asymmetric Waveform Ion Mobility Spectrometry: A New Tool for Mass Spectrometry. J. Chromatogr. A 2004, 1058(1/2), 3–19
Chemical Weapons Convention (CWC) bans the development, production, acquisition, stockpiling, and use of chemical weapons and on their destruction. Washington D.C. United States Bureau of Arms Control and Disarmament Agency Entered into force April 29, 1997.
Steiner, W. E.; Clowers, B. H.; Fuhrer, K.; Gonin, M.; Matz, L. M.; Siems, W. F.; Schultz, A. J.; Hill, H. H. Electrospray Ionization With Ambient Pressure Ion Mobility Separation And Mass Analysis By Orthogonal Time-of-Flight Mass Spectrometry. Rapid Commununication in Mass Spectrometry 2001, 15(23), 2221–2226;
Shumate, C. B.; Hill, H. H. Coronaspray Nebulization and Ionization of Liquid Samples for Ion Mobility Spectrometry. Anal. Chem. 1989, 61, 601–606.
St. Louis, R. H.; Hill, H. H., Jr. Ion Mobility Spectrometry in Analytical Chemistry. Crit. Rev. Anal. Chem. 1990, 21, 321–355.
Ionwerks 3-D Software Ionwerks Inc, Houston TX, 2004.
Transform V3.4, Fortner Software LLC, Serling VA, 1998. Research Systems IDL virtual machine 6.0 Software, Research Systems Inc, Boulder CO, 2004.
Author information
Authors and Affiliations
Corresponding author
Additional information
Published online January 18, 2006
Rights and permissions
About this article
Cite this article
Steiner, W.E., Harden, C.S., Hong, F. et al. Detection of aqueous phase chemical warfare agent degradation products by negative mode ion mobility time-of-flight mass spectrometry [IM(tof)MS]. The official journal of The American Society for Mass Spectrometry 17, 241–245 (2006). https://doi.org/10.1016/j.jasms.2005.11.004
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1016/j.jasms.2005.11.004