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R. Zimmermann et al. CORESTA SSPT 2015, Jeju, South Korea, October 4th- 8th 2015
On-line puff resolved analysis of e-cigarette vapours and heat-not-burn tobacco products
R.Zimmermann1, S.Ehlert1,2, T.Streibel1, J.M. Wolter1, J. Heide1, A.Walte2
1 University of Rostock, Chair of Analytical Chemistry, Inst. of Chemistry, Germany [email protected]
R. Zimmermann et al. CORESTA SSPT 2015, Jeju, South Korea, October 4th- 8th 2015
Content
1. Photo ionisation mass spectrometry (PIMS) in tobacco or
nicotine product smoke/vapour on-line analysis
2. Photo ionisation mass spectrometry concept for analysis of aldehydes and other toxicants in e-cigarettes
3. Photo ionisation mass spectrometry concept for analysis of toxicants in tobacco heating products
4. Outlook, summary and conclusion
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R. Zimmermann et al. CORESTA SSPT 2015, Jeju, South Korea, October 4th- 8th 2015
PIMS - Soft photo ionisation in vacuum (no fragmentation as in EI-MS and no matrix effects as in CI-MS) direct MS analysis
Two photo ionisation techniques of different selectivity are applied:
IE
Sn
S0
REMPI
b) Resonance-Enhanced Multiphoton Ionisation (REMPI) - ionisation by UV laser pulses (210-270 nm, ~107 W/cm2) - highly efficient soft two-photon ionization of aromatics - ppb/ppt on-line concentration range
IE
S0 SPI
a) Vacuum UV Single Photon Ionisation (SPI) - ionisation with 118 nm laser photons (10.5 eV) or incoherent VUV radiation (excimer lamp, e.g. 9.8 eV) - soft ionization of most organic compounds - ppb on-line concentration range
Introduction: Photo ionization - SPI and REMPI
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R. Zimmermann et al. CORESTA SSPT 2015, Jeju, South Korea, October 4th- 8th 2015
PIMS - Soft photo ionisation in vacuum (no fragmentation as in EI-MS and no matrix effects as in CI-MS) direct MS analysis
Two photo ionisation techniques of different selectivity are applied:
IE
Sn
S0
REMPI
b) Resonance-Enhanced Multiphoton Ionisation (REMPI) - ionisation by UV laser pulses (210-270 nm, ~107 W/cm2) - highly efficient soft two-photon ionization of aromatics - ppb/ppt on-line concentration range
IE
S0 SPI
a) Vacuum UV Single Photon Ionisation (SPI) - ionisation with 118 nm laser photons (10.5 eV) or incoherent VUV radiation (excimer lamp, e.g. 9.8 eV) - soft ionization of most organic compounds - ppb on-line concentration range
Mass analysis by time-of-flight (TOFMS), ion trap (ITMS) etc.
Introduction: Photo ionization - SPI and REMPI
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R. Zimmermann et al. CORESTA SSPT 2015, Jeju, South Korea, October 4th- 8th 2015
Tobacco smoke (2R4F)
Introduction: Photo ionization - SPI and REMPI
N2
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R. Zimmermann et al. CORESTA SSPT 2015, Jeju, South Korea, October 4th- 8th 2015
Tobacco smoke (2R4F)
Introduction: Photo ionization - SPI and REMPI
N2
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R. Zimmermann et al. CORESTA SSPT 2015, Jeju, South Korea, October 4th- 8th 2015
R. Zimmermann et al. CORESTA SSPT 2015, Jeju, South Korea, October 4th- 8th 2015
Photo ionization – mass spectrometry: On-line tobacco smoke analysis
Photo ionization MS smoke profiler for Industrial applications (Borgwaldt KC)
Stand-alone photo ionization MS for flexible applications (Photonion GmbH)
• Easy to use integrated smoke machine- PI-mass spectrometer system
• Compact oa-TOFMS mass analyzer (R~900) • Different VUV-lamps for SPI + EI ion source • Specific software solution
• High flexibility and sensitivity • Direct Reflectron TOF mass analyzer (R~2000) • REMPI, laser-SPI and VUV lamp SPI source • EI ion source and switchable ionization • Multiple coupling options, custom made software
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R. Zimmermann et al. CORESTA SSPT 2015, Jeju, South Korea, October 4th- 8th 2015
Photo ionization – mass spectrometry: On-line tobacco smoke analysis
Photo ionization MS smoke profiler for Industrial applications (Borgwaldt KC)
Stand-alone photo ionization MS for flexible applications (Photonion GmbH)
• Easy to use integrated smoke machine- PI-mass spectrometer system
• Compact oa-TOFMS mass analyzer (R~900) • Different VUV-lamps for SPI + EI ion source • Specific software solution
• High flexibility and sensitivity • Direct Reflectron TOF mass analyzer (R~2000) • REMPI, laser-SPI and VUV lamp SPI source • EI ion source and switchable ionization • Multiple coupling options, custom made software
• Integrated smoke machine – SPI-TOFMS system ( ISO, intense, human, e-cig. profiles) for industrial routine & research
• Quantitative puff-resolved on-line analysis of tobacco smoke toxicants (e.g. isoprene, butadiene, benzene) and of e-cigarette and heat-not-burn product smoke composition
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R. Zimmermann et al. CORESTA SSPT 2015, Jeju, South Korea, October 4th- 8th 2015
Photo ionization – mass spectrometry: On-line tobacco smoke analysis
Photo ionization MS smoke profiler for Industrial applications (Borgwaldt KC)
Stand-alone photo ionization MS for flexible applications (Photonion GmbH)
• Easy to use integrated smoke machine- PI-mass spectrometer system
• Compact oa-TOFMS mass analyzer (R~900) • Different VUV-lamps for SPI + EI ion source • Specific software solution
• High flexibility and sensitivity • Direct Reflectron TOF mass analyzer (R~2000) • REMPI, laser-SPI and VUV lamp SPI source • EI ion source and switchable ionization • Multiple coupling options, custom made software
• Integrated smoke machine – SPI-TOFMS system ( ISO, intense, human, e-cig. profiles) for industrial routine & research
• Quantitative puff-resolved on-line analysis of tobacco smoke toxicants (e.g. isoprene, butadiene, benzene) and of e-cigarette and heat-not-burn product smoke composition
• Flexible, ultra-high performance PI-TOFMS system for research and industrial process analysis
• System can be coupled to: - Thermal analysis, - µ-probe sampling device, - Smoking machine (e-cig./HnB), - Human smoking analyzer (Gas/PM) - Smoke particle matter analyzer - Fast gas chromatography pre- separation (puff-resolved)
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R. Zimmermann et al. CORESTA SSPT 2015, Jeju, South Korea, October 4th- 8th 2015
Photo ionization – mass spectrometry: On-line tobacco smoke analysis
Stand-alone photo ionization MS for flexible applications (Photonion GmbH)
• High flexibility and sensitivity • Direct Reflectron TOF mass analyzer (R~2000) • REMPI, laser-SPI and VUV lamp SPI source • EI ion source and switchable ionization • Multiple coupling options, custom made software
General information on e-cigarette and heat not burn SPI/REMPI-TOF analysis tests Mass spectrometer: Photonion LASER TOF : 118 nm (10.5 eV) SPI or 266 nm REMPI Smoke machine: Borgwaldt LM1 Smoke protocol: human smoking profiles replayed SA7 (~80-112 ml, e-cig) or ISO & modified intense (HnB) Transfer line temp: 200°C TOFMS Acquisition rate: 10 Hz
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R. Zimmermann et al. CORESTA SSPT 2015, Jeju, South Korea, October 4th- 8th 2015
p
Normalized SPI-TOFMS mass spectra of cigarette, e-cigarette & heat-not-burn devices
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R. Zimmermann et al. CORESTA SSPT 2015, Jeju, South Korea, October 4th- 8th 2015
normal cigarette charcoal heated HnB device
e-cigarette Electrical heated pod HnB device
Puff resolved SPI-MS analysis of nicotine release of cigarette, e-cigarette & heat-not-burn devices
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R. Zimmermann et al. CORESTA SSPT 2015, Jeju, South Korea, October 4th- 8th 2015
~ bell shaped
~ constant
linear increasing
linear increasing
normal cigarette charcoal heated HnB device
e-cigarette Electrical heated pod HnB device
Puff resolved SPI-MS analysis of nicotine release of cigarette, e-cigarette & heat-not-burn devices
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R. Zimmermann et al. CORESTA SSPT 2015, Jeju, South Korea, October 4th- 8th 2015
Main components (Laser-SPI) of e-cigarette smoke (Type I, no nicotine) Aerosolizer compounds: Glycerol and propylene glycol
e-cigarette (refillable with flavor containing reservoirs, puffing triggered vaporizer)
76
45
76
45
45
45
76 76
60
60 60
60
SPI-TOFMS e-cigarette analysis (Type I, reusable, automatic activation)
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R. Zimmermann et al. CORESTA SSPT 2015, Jeju, South Korea, October 4th- 8th 2015
e-cigarette I (refillable with flavor containing reservoirs, puffing triggered vaporizer)
m/z
Main components (Laser-SPI) of e-cigarette smoke (Type I, no nicotine) Aerosolizer compounds: Glycerol and propylene glycol + aroma compounds (often single compound or simple flavour compound mixture)
C6H14O
SPI-TOFMS e-cigarette analysis (Type I, reusable, automatic activation)
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R. Zimmermann et al. CORESTA SSPT 2015, Jeju, South Korea, October 4th- 8th 2015
44 60/61/62
74
74
162
162 56
56
156
138 -H2O Glycerol: 44, 56, 61, 74
Main components (Laser-SPI) of e-cigarette smoke (Type II) Aerosolizer compounds: Glycerol, nicotine and menthol
60/61/62 44
SPI-TOFMS e-cigarette analysis (Type II, reusable, automatic activation)
[Menthol-H2O] 138
e-cigarette (refillable with nicotine/flavor containing reservoirs, puffing triggered vaporizer)
R. Zimmermann et al. CORESTA SSPT 2015, Jeju, South Korea, October 4th- 8th 2015
Eclipse Ploom IQOS
SPI-TOFMS for on-line analysis of Heat-not-Burn tobacco product smoke
Tobacco extract pod
Battery
Heat source
Mouth piece
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R. Zimmermann et al. CORESTA SSPT 2015, Jeju, South Korea, October 4th- 8th 2015
General information TOFMS: Photonion Laser TOF Smoking machine: Borgwaldt LM1 Smoke protocol: * ISO 3308:1991 or * modified intense profile (50 ml/30 sec) Transfer line temp: 200°C Ion source: 10.5 eV laser SPI
ISO 3308:1991 35 ml (2s) every 60 s Intense HnB/e-cig-profile (I-profile) 50 ml (3s) every 30 s
SPI-TOFMS for on-line analysis of Heat-not-Burn tobacco product smoke: Puff profiles
59 60 61 62 63 640
5
10
15
20
25
30
35
40
Flow
Time in s
intern lab ISO
0 60 120 180 660 720 780 8400
5
10
15
20
25
30
35
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Flow
Time in s
intern lab ISO intense
intense
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R. Zimmermann et al. CORESTA SSPT 2015, Jeju, South Korea, October 4th- 8th 2015
R. Zimmermann et al. CORESTA SSPT 2015, Jeju, South Korea, October 4th- 8th 2015
Summary
• PI-MS (REMPI, SPI): On-line method for real-time analysis of trace gases, aerosolizer, aroma cpds. & pyrolysis products
• Analysis of e-cig. vapors: Puff-resolved detection of acet-
aldehyde, glycerol, propylene glycol, flavors, nicotine etc. • For aldehyde quantitation on-line GC - PI-MS • Analysis of HnB-smoke: Puff-resolved detection of tobacco
compounds and aerosolizer-compounds • Massive reduction of gaseous toxicants and tar-compounds • Strong influence of puff-profile, device, age of material etc. on-line measurement required
• Spin-off company Photonion GmbH: Custom-build PI-MS
Systems for Research and Cooperation with Borgwaldt KC
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R. Zimmermann et al. CORESTA SSPT 2015, Jeju, South Korea, October 4th- 8th 2015
Zimmermann group @ Joint Mass Spectrometry Centre Acknowledgements Dr. J. Maguhn Dr. T. Streibel Dr. J. Schnelle-Kreis Dr. M. Sklorz Dr. J. Lintelmann Dr. E. Feicht Dr. M. Kirchner Dr. P. Richthammer Dr. J. Passig Dr. G. Jakobi Dr. S. Smita Dr. J. Orasche Dr. G Ferron Dr. S. Haack Dr. S. Ehlert E. Hübner T. Gröger T. Miersch A. Sutherland S. Ly-Verdu S. Wohlfahrt M. Fischer C. Rüger T. Schwemer G. Dragan H. Czech V. Kohlmeier Y. Giessen J. Parra
S. Erdmann B. Wegglert S. Otto S. Krüger P. Sattler G. Abbazade M. Oster E. Karg B. Gruber M. Jennerwein F. Li L. Müller A. Rheda X. Wu S. Scholtes C. Radischat L. Müller K. Lau M. Hahn Y. Huang G. Kocsis J.Varga S. Scholtes C. Kühl R.Reiss M. Oster M. Fuchs
Joint Mass Spectrometry Centre Funding: • Uni Rostock und Helmholtz Zentrum München • Deutsche Forschungsgemeinschaft (DFG) • Bundesministerium für Bildung &Forschung (BMBF) • Bayerische Forschungsstiftung (BFS) • Deutsche Gesetzl. Unfallversich. (DGUV) • Bundeskriminalamt (BKA) • Companies (SASOL Ltd., Netzsch GmbH, Photonion GmbH,
Airsense GmbH, Borgwaldt KC etc.) • Helmholtz-Impulse and Networking- Fonds
(Virtual Helmholtz Institute - HICE)
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R. Zimmermann et al. CORESTA SSPT 2015, Jeju, South Korea, October 4th- 8th 2015
Zimmermann group @ Joint Mass Spectrometry Centre Acknowledgements Dr. J. Maguhn Dr. T. Streibel Dr. J. Schnelle-Kreis Dr. M. Sklorz Dr. J. Lintelmann Dr. E. Feicht Dr. M. Kirchner Dr. P. Richthammer Dr. J. Passig Dr. G. Jakobi Dr. S. Smita Dr. J. Orasche Dr. G Ferron Dr. S. Haack Dr. S. Ehlert E. Hübner T. Gröger T. Miersch A. Sutherland S. Ly-Verdu S. Wohlfahrt M. Fischer C. Rüger T. Schwemer G. Dragan H. Czech V. Kohlmeier Y. Giessen J. Parra
S. Erdmann B. Wegglert S. Otto S. Krüger P. Sattler G. Abbazade M. Oster E. Karg B. Gruber M. Jennerwein F. Li L. Müller A. Rheda X. Wu S. Scholtes C. Radischat L. Müller K. Lau M. Hahn Y. Huang G. Kocsis J.Varga S. Scholtes C. Kühl R.Reiss M. Oster M. Fuchs
Joint Mass Spectrometry Centre Funding: • Uni Rostock und Helmholtz Zentrum München • Deutsche Forschungsgemeinschaft (DFG) • Bundesministerium für Bildung &Forschung (BMBF) • Bayerische Forschungsstiftung (BFS) • Deutsche Gesetzl. Unfallversich. (DGUV) • Bundeskriminalamt (BKA) • Companies (SASOL Ltd., Netzsch GmbH, Photonion GmbH,
Airsense GmbH, Borgwaldt KC etc.) • Helmholtz-Impulse and Networking- Fonds