Abstract
Considering current security issues, powerful tools for detection of security-relevant substances such as traces of explosives and drugs/drug precursors related to clandestine laboratories are required. Especially in the field of detection of explosives and improvised explosive devices, several relevant compounds exhibit a very low vapor pressure. Ambient pressure laser desorption is proposed to make these substances available in the gas phase for the detection by adapted mass spectrometers or in the future with ion-mobility spectrometry as well. In contrast to the state-of-the-art thermal desorption approach, by which the sample surface is probed for explosive traces by a wipe pad being transferred to a thermal desorber unit, by the ambient pressure laser desorption approach presented here, the sample is directly shockwave ablated from the surface. The laser-dispersed molecules are sampled by a heated sniffing capillary located in the vicinity of the ablation spot into the mass analyzer. This approach has the advantage that the target molecules are dispersed more gently than in a thermal desorber unit where the analyte molecules may be decomposed by the thermal intake. In the technical realization, the sampling capillary as well as the laser desorption optics are integrated in the tip of an endoscopic probe or a handheld sampling module. Laboratory as well as field test scenarios were performed, partially in cooperation with the Federal Criminal Police Office (Bundeskriminalamt, BKA, Wiesbaden, Germany), in order to demonstrate the applicability for various explosives, drugs, and drug precursors. In this work, we concentrate on the detection of explosives. A wide range of samples and matrices have been investigated successfully.
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References
Kojima K, Sakairi M, Takada Y, Nakamura J (2000) Vapor detection of TNT and RDX using atmospheric pressure chemical ionization mass spectrometry with counter-flow introduction (CFI). J Mass Spectrom Soc Jpn 48(5):3
Pella PA (1977) Measurement of vapor pressures of TNT, 2,4-DNT, 2,6-DNT and EGDN. J Chem Thermodyn 9(4):301–305. doi:10.1016/0021-9614(77)90049-0
Handschuh M, Nettesheim S, Zenobi R (1998) Laser induced desorption of thin molecular films investigated with high time resolution. J Chem Phys 108(16):6548–6549. doi:10.1063/1.476066
Weickhardt C, Kaiser N, Borsdorf H (2012) Ion mobility spectrometry of laser desorbed pesticides from fruit surfaces. International Journal for Ion Mobility Spectrometry 15(2):55–62. doi:10.1007/s12127-012-0091-3
Burgess D, Viswanathan R, Hussla I, Stair PC, Weitz E (1983) Pulsed laser induced thermal desorption of CO from copper surfaces. J Chem Phys 79(10):5200–5202. doi:10.1063/1.445647
O'Neill E, Harrington D, Allison J (2009) Interpretation of laser desorption mass spectra of unexpected inorganic species found in a cosmetic sample of forensic interest: fingernail polish. Anal Bioanal Chem 394(8):2029–2038. doi:10.1007/s00216-009-2760-6
Smith G, Krancevic B, Huestis D, Oser H (2009) Laser desorption studies using laser-induced fluorescence of large aromatic molecules. Appl Phys B-Lasers Opt 94(1):127–132. doi:10.1007/s00340-008-3295-9
Bauer C, Geiser P, Burgmeier J, Holl G, Schade W (2006) Pulsed laser surface fragmentation and mid-infrared laser spectroscopy for remote detection of explosives. Appl Phys B-Lasers Opt 85(2–3):251–256. doi:10.1007/s00340-006-2372-1
Morgan JS, Bryden WA, Miragliotta JA, Aamodt LC (1999) Improved detection of explosive residues by laser thermal desorption. Johns Hopkins APL Tech Dig 20(3):389–395
Cooks RG, Ouyang Z, Takats Z, Wiseman JM (2006) Ambient mass spectrometry. Science 311(5767):1566–1570. doi:10.1126/science.1119426
Alberici R, Simas R, Sanvido G, Romao W, Lalli P, Benassi M, Cunha I, Eberlin M (2010) Ambient mass spectrometry: bringing MS into the “real world”. Anal Bioanal Chem 398(1):265–294. doi:10.1007/s00216-010-3808-3
Talaty N, Mulligan CC, Justes DR, Jackson AU, Noll RJ, Cooks RG (2008) Fabric analysis by ambient mass spectrometry for explosives and drugs. Analyst 133(11):1532–1540
Bennett MJ, Steiner RR (2009) Detection of gamma-hydroxybutyric acid in various drink matrices via AccuTOF-DART. J Forensic Sci 54(2):370–375. doi:10.1111/j.1556-4029.2008.00955.x
Takats Z, Cotte-Rodriguez I, Talaty N, Chen HW, Cooks RG (2005) Direct, trace level detection of explosives on ambient surfaces by desorption electrospray ionization mass spectrometry. Chem Commun 15:1950–1952. doi:10.1039/b418697d
Cotte-Rodriguez I, Takats Z, Talaty N, Chen HW, Cooks RG (2005) Desorption electrospray ionization of explosives on surfaces: sensitivity and selectivity enhancement by reactive desorption electrospray ionization. Anal Chem 77(21):6755–6764. doi:10.1021/ac050995
Cotte-Rodriguez I, Hernandez-Soto H, Chen H, Cooks RG (2008) In situ trace detection of peroxide explosives by desorption electrospray ionization and desorption atmospheric pressure chemical ionization. Anal Chem 80(5):1512–1519. doi:10.1021/ac7020085
Takats Z, Wiseman JM, Gologan B, Cooks RG (2004) Mass spectrometry sampling under ambient conditions with desorption electrospray ionization. Science 306(5695):471–473
Nemes P, Vertes A (2007) Laser ablation electrospray ionization for atmospheric pressure, in vivo, and imaging mass spectrometry. Anal Chem 79(21):8098–8106. doi:10.1021/ac071181r
Hillenkamp F, Karas M (2000) Matrix-assisted laser desorption/ionisation, an experience. Int J Mass Spectrom 200(1–3):71–77
Karas M, Hillenkamp F (1988) Laser desorption ionization of proteins with molecular masses exceeding 10000 daltons. Anal Chem 60(20):2299–2301
Huang MZ, Yuan CH, Cheng SC, Cho YT, Shiea J (2010) Ambient ionization mass spectrometry. In: Annual review of analytical chemistry, vol 3. Annual Review of Analytical Chemistry. Annual Reviews, Palo Alto, pp. 43–65. doi:10.1146/annurev.anchem.111808.073702. Accessed 01/12/11
Eiceman GA, Anderson GK, Danen WC, Ferris MJ, Tiee JJ (1988) Laser desorption and ionization of solid polycyclic aromatic hydrocarbons in air with analysis by ion mobility spectrometry. Anal Lett 21(4):539–552
Perdian DC, Schieffer GM, Houk RS (2009) Atmospheric pressure laser desorption/ionization of plant metabolites and plant tissue using colloidal graphite. Rapid Commun Mass Spectrom 24(4):397–402. doi:10.1002/rcm.4405
Grange AH, Sovocool GW (2011) Detection of illicit drugs on surfaces using direct analysis in real time (DART) time-of-flight mass spectrometry. Rapid Commun Mass Spectrom 25(9):1271–1281. doi:10.1002/rcm.5009
Luosujarvi L, Arvola V, Haapala M, Pol J, Saarela V, Franssila S, Kotiaho T, Kostiainen R, Kauppila TJ (2008) Desorption and ionization mechanisms in desorption atmospheric pressure photoionization. Anal Chem 80(19):7460–7466. doi:10.1021/ac801186x
Stockle R, Setz P, Deckert V, Lippert T, Wokaun A, Zenobi R (2001) Nanoscale atmospheric pressure laser ablation-mass spectrometry. Anal Chem 73(7):1399–1402. doi:10.1021/ac001440b
Shahar T, Dagan S, Amirav A (1998) Laser desorption fast gas chromatography-mass spectrometry in supersonic molecular beams. Journal of the American Society for Mass Spectrometry 9(6):628–637
Weickhardt C (2003) Laser desorption combined with hyperthermal surface ionization time-of-flight mass spectrometry. Anal Chem 75(20):5602–5607. doi:10.1021/ac0302197
Li L, Lubman DM (1988) Pulsed laser desorption method for volatilizing thermally labile molecules for supersonic jet spectroscopy. Rev Sci Instrum 59(4):557–561. doi:10.1063/1.1139832
Butcher DJ (1999) Vacuum ultraviolet radiation for single-photoionization mass spectrometry: a review. Microchem J 62(3):354–362. doi:10.1006/mchj.1999.1745
Schramm E, Kurten A, Holzer J, Mitschke S, Muhlberger F, Sklorz M, Wieser J, Ulrich A, Putz M, Schulte-Ladbeck R, Schultze R, Curtius J, Borrmann S, Zimmermann R (2009) Trace detection of organic compounds in complex sample matrixes by single photon ionization ion trap mass spectrometry: real-time detection of security-relevant compounds and online analysis of the coffee-roasting process. Anal Chem 81(11):4456–4467. doi:10.1021/ac900289r
Lockyer NP, Vickerman JC (1997) Single photon ionisation mass spectrometry using laser-generated vacuum ultraviolet photons. Laser Chem 17(3):139–159. doi:10.1155/1997/53174
Shi YJ, Lipson RH (2005) An overview of organic molecule soft ionization using vacuum ultraviolet laser radiation. Can J Chem-Rev Can Chim 83(11):1891–1902. doi:10.1139/v05-193
Mallard WG, Linstrom PJ (2000). NIST Chemistry WebBook, NIST Standard Reference Database: National Institute of Standards and Technology (NIST)
Isaacman G, Chan AWH, Nah T, Worton DR, Ruehl CR, Wilson KR, Goldstein AH (2012) Heterogeneous OH oxidation of motor oil particles causes selective depletion of branched and less cyclic hydrocarbons. Environ Sci Technol 46(19):10632–10640. doi:10.1021/es302768a
Hankin SM, Tasker AD, Robson L, Ledingham KWD, Fang X, McKenna P, McCanny T, Singhal RP, Kosmidis C, Tzallas P, Jaroszynski DA, Jones R, Issac RC, Jamison S (2002) Femtosecond laser time-of-flight mass spectrometry of labile molecular analytes: laser-desorbed nitro-aromatic molecules. Rapid Commun Mass Spectrom 16(2):111–116
Mullen C, Irwin A, Pond BV, Huestis DL, Coggiola MJ, Oser H (2006) Detection of explosives and explosives-related compounds by single photon laser ionization time-of-flight mass spectrometry. Anal Chem 78(11):3807–3814. doi:10.1021/ac060190h
Mullen C, Huestis D, Coggiola M, Oser H (2006) Laser photoionization of triacetone triperoxide (TATP) by femtosecond and nanosecond laser pulses. Int J Mass Spectrom 252(1):69–72. doi:10.1016/j.ijms.2006.01.018
Pond BV, Mullen C, Suarez I, Kessler J, Briggs K, Young SE, Coggiola MJ, Crosley DR, Oser H (2007) Detection of explosive-related compounds by laser photoionization time-of-flight mass spectrometry. Appl Phys B-Lasers Opt 86(4):735–742. doi:10.1007/s00340-006-2465-x
Yamaguchi S, Uchimura T, Imasaka T (2009) Gas chromatography/time-of-flight mass spectrometry of triacetone triperoxide based on femtosecond laser ionization. Rapid Commun Mass Spectrom 23(19):3101–3106. doi:10.1002/rcm.4225
Schramm E, Muehlberger F, Mitschke S, Reichardt G, Schulte-Ladbeck R, Puetz M, Zimmermann R (2008) Determination of the ionization potentials of security-relevant substances with single photon ionization mass spectrometry using synchrotron radiation. Appl Spectrosc 62(2):238–247
March RE (1997) An introduction to quadrupole ion trap mass spectrometry. J Mass Spectrom 32(4):351–369. doi:10.1002/(sici)1096-9888(199704)32:4<351::aid-jms512>3.0.co;2-y
Smeraglia J, Baldrey SF, Watson D (2002) Matrix effects and selectivity issues in LC-MS-MS. Chromatographia 55:S95–S99. doi:10.1007/bf02493363
Yinon J, McClellan JE, Yost RA (1997) Electrospray ionization tandem mass spectrometry collision-induced dissociation study of explosives in an ion trap mass spectrometer. Rapid Commun Mass Spectrom 11(18):1961–1970. doi:10.1002/(sici)1097-0231(199712)11:18<1961::aid-rcm99>3.0.co;2-k
Schramm E, Holzer J, Putz M, Schulte-Ladbeck R, Schultze R, Sklorz M, Ulrich A, Wieser J, Zimmermann R (2009) Real-time trace detection of security-relevant compounds in complex sample matrices by thermal desorption-single photon ionization-ion trap mass spectrometry (TD-SPI-ITMS). Anal Bioanal Chem 395(6):1795–1807. doi:10.1007/s00216-009-2916-4
Gillis RG, Lacey MJ, Shannon JS (1974) Chemical ionisation mass spectra of explosives. Organic Mass Spectrometry 9(3):359–364. doi:10.1002/oms.1210090317
Pate CT, Mach MH (1978) Analysis of explosives using chemical ionization mass spectroscopy. International Journal of Mass Spectrometry and Ion Physics 26(3):267–277
Gielsdorf W (1981) Identifizierung einiger Sprengstoffe mit Hilfe spezieller GC/MS-Techniken, insbesondere der PPNICI-Methode. Fresenius Zeitschrift Fur Analytische Chemie 308(2):123–128
Wu YH, Lin KL, Chen SC, Chang YZ (2008) Integration of GC/EI-MS and GC/NCI-MS for simultaneous quantitative determination of opiates, amphetamines, MDMA, ketamine, and metabolites in human hair. J Chromatogr B 870(2):192–202. doi:10.1016/j.jchromb.2008.06.017
Collin OL, Zimmermann CM, Jackson GP (2009) Fast gas chromatography negative chemical ionization tandem mass spectrometry of explosive compounds using dynamic collision-induced dissociation. Int J Mass Spectrom 279(2–3):93–99. doi:10.1016/j.ijms.2008.10.009
Boumsellek S, Alajajian SH, Chutjian A (1992) Negative-ion formation in the explosives RDX, PETN, and TNT by using the reversal electron attachment detection technique. Journal of the American Society for Mass Spectrometry 3(3):243–247
Jurschik S, Sulzer P, Petersson F, Mayhew CA, Jordan A, Agarwal B, Haidacher S, Seehauser H, Becker K, Mark TD (2010) Proton transfer reaction mass spectrometry for the sensitive and rapid real-time detection of solid high explosives in air and water. Anal Bioanal Chem 398(7–8):2813–2820. doi:10.1007/s00216-010-4114-9
Zimmermann R, Mühlberger F, Ulrich A, Wieser J (2007) Photoionisierungs-Massenspektrometrie mit neuer Lichtquelle. Nachrichten aus der Chemie 55(4):425–429. doi:10.1002/nadc.200747960
Geissler R, Saraji-Bozorgzad MR, Groger T, Fendt A, Streibel T, Sklorz M, Krooss BM, Fuhrer K, Gonin M, Kaisersberger E, Denner T, Zimmermann R (2009) Single photon ionization orthogonal acceleration time-of-flight mass spectrometry and resonance enhanced multiphoton ionization time-of-flight mass spectrometry for evolved gas analysis in thermogravimetry: comparative analysis of crude oils. Anal Chem 81(15):6038–6048. doi:10.1021/ac900216y
Streibel T, Fendt A, Geissler R, Kaisersberger E, Denner T, Zimmermann R (2009) Thermal analysis/mass spectrometry using soft photo-ionisation for the investigation of biomass and mineral oils. J Therm Anal Calorim 97(2):615–619. doi:10.1007/s10973-008-9769-5
Muhlberger F, Streibel T, Wieser J, Ulrich A, Zimmermann R (2005) Single photon ionization time-of-flight mass spectrometry with a pulsed electron beam pumped excimer VUV lamp for on-line gas analysis: setup and first results on cigarette smoke and human breath. Anal Chem 77(22):7408–7414. doi:10.1021/ac051194+
Muhlberger F, Wieser J, Morozov A, Ulrich A, Zimmermann R (2005) Single-photon ionization quadrupole mass spectrometry with an electron beam plumped excimer light source. Anal Chem 77(7):2218–2226. doi:10.1021/ac048319f
Saraj-Bozorgzad M, Geissler R, Streibel T, Muhlberger F, Sklorz M, Kaisersberger E, Denner T, Zimmermann R (2008) Thermogravimetry coupled to single photon ionization quadrupole mass spectrometry: a tool to investigate the chemical signature of thermal decomposition of polymeric materials. Anal Chem 80(9):3393–3403. doi:10.1021/ac702599y
Muhlberger F, Wieser J, Ulrich A, Zimmermann R (2002) Single photon ionization (SPI) via incoherent VUV-excimer light: robust and compact time-of-flight mass spectrometer for on-line, real-time process gas analysis. Anal Chem 74(15):3790–3801. doi:10.1021/ac0200825
Fendt A, Streibel T, Sklorz M, Richter D, Dahmen N, Zimmermann R (2012) On-line process analysis of biomass flash pyrolysis gases enabled by soft photoionization mass spectrometry. Energy Fuel 26(1):701–711. doi:10.1021/ef2012613
Mitschke S, Adam T, Streibel T, Baker RR, Zimmermann R (2005) Application of time-of-flight mass spectrometry with laser-based photoionization methods for time-resolved on-line analysis of mainstream cigarette smoke. Anal Chem 77(8):2288–2296. doi:10.1021/ac050075r
Rosen JM, Dickinson C (1969) Vapor pressures and heats of sublimation of some high melting organic explosives. J Chem Eng Data 14(1):120. doi:10.1021/je60040a044
Östmark H, Wallin S, Ang HG (2012) Vapor pressure of explosives: a critical review. Propellants, Explosives, Pyrotechnics 37(1):12–23. doi:10.1002/prep.201100083
Meyer R, Köhler J, Homburg A (2002) Explosives, 5th edn. Wiley-VCH, Weinheim, p 177
Acknowledgments
This investigation was performed within the SAFE-inside project funded by the Federal Ministry of Education and Research (BMBF), FKZ 13N9529. We want especially thank the German Federal Criminal Police Office (BKA) for providing the samples and the opportunity of a measurement campaign with real crime samples in Wiesbaden.
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Published in the topical collection Photo Ionisation in Mass Spectrometry with guest editor Ralf Zimmermann.
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Ehlert, S., Hölzer, J., Rittgen, J. et al. Rapid on-site detection of explosives on surfaces by ambient pressure laser desorption and direct inlet single photon ionization or chemical ionization mass spectrometry. Anal Bioanal Chem 405, 6979–6993 (2013). https://doi.org/10.1007/s00216-013-6839-8
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DOI: https://doi.org/10.1007/s00216-013-6839-8