Secondary electrospray ionization (SESI) of ambient vapors for explosive detection at concentrations below parts per trillion

  • Pablo Martínez-Lozano
  • Juan Rus
  • Gonzalo Fernández de la Mora
  • Marta Hernández
  • Juan Fernández de la Mora


We determine the sensitivity of several commercial atmospheric pressure ionization mass spectrometers towards ambient vapors, ionized by contact with an electrospray of acidified or ammoniated solvent, a technique often referred to as secondary electrospray ionization (SESI). Although a record limit of detection of 0.2 × 10−12 atmospheres (0.2 ppt) is found for explosives such as PETN and 0.4 ppt for TNT (without preconcentration), this still implies the need for some 108–109 vapor molecules/s for positive identification of explosives. This extremely inefficient use of sample is partly due to low charging probability (∼10−4), finite ion transmission, and counting probability in the mass spectrometer (1/10 in quadrupoles), and a variable combination of duty cycle and background noise responsible typically for a 103 factor loss of useful signal.


PETN Sample Flow Rate TATP Desorption Electrospray Ionization Explosive Detection 
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  1. 1.
    Fialkov, A. B.; Steiner, U.; Lehotay, S. J.; Amirav, A. Sensitivity and Noise in GC-MS: Achieving Low Limits of Detection for Difficult Analytes. Int. J. Mass Spectrom. 2007, 260(1), 31–48.CrossRefGoogle Scholar
  2. 2.
    Lindinger, W.; Hansel, A.; Jordan, A. On-Line Monitoring of Volatile Organic Compounds at pptv Levels by Means of Proton-Transfer-Reaction Mass-Spectrometry (PTR-MS): Medical Applications, Food Control, and Environmental Research. Int. J. Mass Spectrom. Ion Processes. 1998, 173(3), 191–241.CrossRefGoogle Scholar
  3. 3.
    Smith, D.; Španěl, P. Selected Ion Flow Tube Mass Spectrometry (SIFT-MS) for On-Line Trace Gas Analysis. Mass Spectrom. Rev. 2005, 24(5), 661–700.CrossRefGoogle Scholar
  4. 4.
    McMurry, P. H.; Fink, M.; Sakurai, H.; Stolzenburg, M. R.; Mauldin, R. L.; Smith, J.; Eisele, F.; Moore, K.; Sjostedt, S.; Tanner, D.; Huey, L. G.; Nowak, J. B.; Edgerton, E.; Voisin, D. A Criterion for New Particle Formation in the Sulfur-Rich Atlanta Atmosphere. J. Geophys. Res. D: Atmospheres. 2005, 110(22)D22S02, 1–10.Google Scholar
  5. 5.
    Asano, K. G.; Goeringer, D. E.; McLuckey, S. A. Parallel Monitoring for Multiple Targeted Compounds by Ion Trap Mass Spectrometry. Anal. Chem. 1995, 67(17), 2739–2742.CrossRefGoogle Scholar
  6. 6.
    McLuckey, S. A.; Goeringer, D. E.; Asano, K. G.; Vaidyanathan, G.; Stephenson, J. L. Jr. High Explosives Vapor Detection by Glow Discharge-Ion Trap Mass Spectrometry. Rapid Commun. Mass Spectrom. 1996, 10(3), 287–298.CrossRefGoogle Scholar
  7. 7.
    Steinfeld, J. A.; Wormhoudt, J. Explosives Detection: A Challenge for Physical Chemistry. Annu. Rev. Phys. Chem. 1998, 49, 203–232.CrossRefGoogle Scholar
  8. 8.
    Lane, D. A.; Thomson, B. A. Monitoring a Chlorine Spill from a Train Derailment. J. Air Pollution Control Assoc. 1981, 31(2), 122–127.CrossRefGoogle Scholar
  9. 9.
    Davidson, W. R.; Thomson, B. A.; Akery, A. K.; Sleeman, R. Proceedings of the First International Symposium on Explosive Detection Technology; Atlantic City, NJ, November 13–15, 1991; pp 653–662.Google Scholar
  10. 10.
    Davidson, W. R.; Stott, W. R.; Akery, A.K.; Sleeman, R. Proceedings of the First International Symposium on Explosive Detection Technology; Atlantic City, NJ, November 13–15, 1991; pp 663–671.Google Scholar
  11. 11.
    Sleeman R.; Bennett, G.; Davidson, W. R.; Fisher, W. Proceedings of the International Symposium on Contraband and Cargo Inspection Technologies; Washington D.C., October 28–30, 1992; pp 57–63.Google Scholar
  12. 12.
    Davidson, W. R.; Stott, W. R.; Sleeman, R.; Akery, A. K. Conference on Substance Detection Systems, 1993, Innsbruck, Austria. Proc. SPIE. 1994, 2092, 108.CrossRefGoogle Scholar
  13. 13.
    Stott, W. R.; Davidson, W. R.; Sleeman, R.. Proc. SPIE. 1994, 2092, 53.CrossRefGoogle Scholar
  14. 14.
    Bennett, G.; Sleeman, R.; Davidson, W. R.; Stott, W. R.. Proc. SPIE. 1994, 2276, 363.CrossRefGoogle Scholar
  15. 15.
    Davidson W. R.; Stott, W. R. Proceedings of the 50th ASMS Conference on Mass Spectrometry and Allied Topics; Orlando FL, June, 2002; TPK 300.Google Scholar
  16. 16.
    Fenn, J. B.; Mann, M.; Meng, C. K.; Wong, S. F.; Whitehouse, C. Electrospray Ionization for Mass Spectrometry of Large Biomolecules. Science 1989, 246, 64–71.CrossRefGoogle Scholar
  17. 17.
    Yinon, J.; McClellan, J. E.; Yost, R. A. Electrospray Ionization Tandem Mass Spectrometry Collision-Induced Dissociation Study of Explosives in an Ion Trap Mass Spectrometer. Rapid Commun. Mass Spectrom. 1997, 11, 1961–1970.CrossRefGoogle Scholar
  18. 18.
    Evans, C. S.; Sleeman, R.; Luke, J.; Keely, B. J. A Rapid and Efficient Mass Spectrometric Method for the Analysis of Explosives. Rapid Commun. Mass Spectrom. 2002, 16, 1883–1891.CrossRefGoogle Scholar
  19. 19.
    Venter, A.; Ifa, D. R.; Cooks, R. G.; Poehlein, S. K.; Chin, A.; Ellison, D. A Desorption Electrospray Ionization Mass Spectrometry Study of Aging Products of Diphenylamine Stabilizer in Double-Base Propellants. Propell. Expl. Pyrotech. 2006, 31(6), 472–476.CrossRefGoogle Scholar
  20. 20.
    Cotte-Rodriguez, I.; Chen, H.; Cooks, R. G. Rapid Trace Detection of Triacetone Triperoxide (TATP) by Complexation Reactions During Desorption Electrospray Ionization. Chem. Commun. 2006, 9, 953–955.CrossRefGoogle Scholar
  21. 21.
    Cody, R. B.; Laramee, J. A.; Durst, H. D. Versatile New Ion Source for the Analysis of Materials in Open Air Under Ambient Conditions. Anal. Chem. 2005, 77(8), 2297–2302.CrossRefGoogle Scholar
  22. 22.
    Whitehouse, C. M.; Levin, F.; Meng, C. K.; Fenn, J. B. Proceedings of the 34th ASMS Conference on Mass Spectrometry and Allied Topics; Cincinnati, OH, June 8–13, 1986; p 507.Google Scholar
  23. 23.
    Fuerstenau, S.; Kiselev, P.; Fenn, J. B. Proceedings of the 47th ASMS Conference on Mass Spectrometry Allied Topics; Dallas, TX, June, 1999; ThOE 3:00.Google Scholar
  24. 24.
    Wu, C.; Siems, W. F.; Hill, H. Jr. Secondary Electrospray Ionization Ion Mobility Spectrometry/Mass Spectrometry of Illicit Drugs. Anal. Chem. 2000, 72, 396–403.CrossRefGoogle Scholar
  25. 25.
    Tam, M.; Hill, H. Jr. Secondary Electrospray Ionization-Ion Mobility Spectrometry for Explosive Vapor Detection. Anal. Chem. 2004, 76(10), 2741–2747.CrossRefGoogle Scholar
  26. 26.
    Takáts, Z.; Wiseman, J. M.; Gologan, B.; Cooks, R. G. Mass Spectrometry Sampling Under Ambient Conditions with Desorption Electrospray Ionization. Science 2004, 306, 471–473.CrossRefGoogle Scholar
  27. 27.
    Chen, H.; Venter, A.; Cooks, R. G. Extractive Electrospray Ionization for Direct Analysis of Undiluted Urine, Milk and Other Complex Mixtures without Sample Preparation. Chem. Commun. 2006, 2042–2044.Google Scholar
  28. 28.
    Chen, H.; Wortmann, A.; Zhang, W.; Zenobi, R. Rapid In Vivo Fingerprinting of Nonvolatile Compounds in Breath. Angew. Chem. Int. Ed. 2007, 46, 580–583.CrossRefGoogle Scholar
  29. 29.
    Martínez-Lozano, P.; Fernández de la Mora, J. Electrospray Ionization of Volatiles in Breath. Int. J. Mass Spectrom. 2007, 265, 68–72.CrossRefGoogle Scholar
  30. 30.
    Chen, H.; Sun, Y.; Wortmann, A.; Gu, H.; Zenobi, R. Differentiation of Maturity and Quality of Fruit Using Noninvasive Extractive Electrospray Ionization Quadrupole Time-of-Flight Mass Spectrometry. Anal. Chem. 2007, 79, 1447–1455.CrossRefGoogle Scholar
  31. 31.
    Chingin, K.; Gamez, G.; Chen, H.; Zhu, L.; Zenobi, R. Rapid Classification of Perfumes by Extractive Electrospray Ionization Mass Spectrometry (EESI-MS). Rapid Commun. Mass Spectrom. 2008, 22, 2009–2014.CrossRefGoogle Scholar
  32. 32.
    Javaheri, H.; Thomson, B.A. Proceedings of the 57th ASMS Conference on Mass Spectrometry and Allied Topics; Indianapolis, IN, June, 2007.Google Scholar
  33. 33.
    Dionne, B. C.; Rounbehler, D. P.; Achter, E. K.; Hobbs, J. R.; Fine, D. H. Vapor Pressure of Explosives. J. Energ. Mat. 1986, 4(1), 447–472.CrossRefGoogle Scholar
  34. 34.
    El-Faramawy, A.; Siu, K. W. M.; Thomson, B. A. Efficiency of Nano-Electrospray Ionization. J. Am. Soc. Mass Spectrom. 2005, 16(10), 1702–1707.CrossRefGoogle Scholar

Copyright information

© American Society for Mass Spectrometry 2009

Authors and Affiliations

  • Pablo Martínez-Lozano
    • 1
    • 2
  • Juan Rus
    • 2
  • Gonzalo Fernández de la Mora
    • 2
  • Marta Hernández
    • 3
  • Juan Fernández de la Mora
    • 1
  1. 1.Mechanical Engineering DepartmentYale UniversityNew HavenUSA
  2. 2.SEADMValladolidSpain
  3. 3.CARTIFValladolidSpain

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