R. Zimmermann et al. 68th TSRC, Charlottesville, VA, USA, Sept. 28th- Oct. 1st 2014
On-line photo ionization mass spectrometry for characterization
of smoke from e-cigarettes or heat-not-burn devices
R. Zimmermann1, S. Ehlert1,2, J. Heide1, R. Hertz-Schünemann1, A. Walte2,
C. Liu3, K. McAdam3,T. Streibel1
1 Joint Mass Spectrometry Centre University of Rostock, Chair of Analytical Chemistry,
Inst. of Chemistry, Germany and Helmholtz-Zentrum
München, KMS-Cooperation Group Analysis of
Complex Molecular Systems, Germany
2 Photonion GmbH Schwerin, Germany
ρħotonıoη
3 BAT Ltd. Southampton, UK
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R. Zimmermann et al. 68th TSRC, Charlottesville, VA, USA, Sept. 28th- Oct. 1st 2014
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 and 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. 68th TSRC, Charlottesville, VA, USA, Sept. 28th- Oct. 1st 2014
Tobacco smoke (2R4F)
Introduction: Photo ionization - SPI and REMPI
N2
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R. Zimmermann et al. 68th TSRC, Charlottesville, VA, USA, Sept. 28th- Oct. 1st 2014
PI-MS for time- and space-resolved chemical
mapping: Distribution maps (middle of puff)
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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)
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
266 nm REMPI
252 nm REMPI
Smoke machine: Borgwaldt LM1
Smoke protocol: replayed SA7/ human
smoking profiles (~80-112
ml, avrgd.92 ml, e-cig)
or adapted reference
profiles (HnB)
Transfer line temp: 200°C
Acquisition rate: 10 Hz
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Photo ionization – mass spectrometry:
On-line e-cigarette/heat-not-burn device analysis
e-cigarette vapors: Simple composition (aerosolizers,
flavor,nicotine and potential pyrolysis products )
Heat-not-burn devices smoke: More complex composition
(tobacco compounds, pyrolysis products and aerosolizers)
Photoionisation Mass spectrometry: Soft ionization & detection
of most tobacco related smoke compounds
But: E-cigarettes/heat-not-burn devices use high amounts of
(poly-)alcohols such as glycerol or propylene glycol as aerosolizers.
Many (poly)alcohols exhibit unstable radical-cations and tend
to heavily fragment even under photoionisation condition (if not
tunable VUV-light is used)
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R. Zimmermann et al. 68th TSRC, Charlottesville, VA, USA, Sept. 28th- Oct. 1st 2014
-H2O
Bell et al. (2013): Dissociative Photoionization of Glycerol and its Dimer
Occurs Predominantly via a Ternary Hydrogen-Bridged Ion-Molecule
Complex. In: J. Am. Chem. Soc. 135 (38),S. 14229
SPI - Glycerol fragmentation pathways:
Glycerol marker ions
Glycerol indicator masses:
m/z 74, 60, 56, 44
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R. Zimmermann et al. 68th TSRC, Charlottesville, VA, USA, Sept. 28th- Oct. 1st 2014
Propylene glycol indicator masses:
m/z 76, 61 (little 60 and 62), 45
SPI – Propylene glycol fragmentation pathways:
Propylene glycol marker ions
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R. Zimmermann et al. 68th TSRC, Charlottesville, VA, USA, Sept. 28th- Oct. 1st 2014 9
Main components (Laser-SPI) of e-cigarette smoke (Type I, no
nicotine) Aerosolizer compounds: Glycerol and propylene glycol
e-cigarette I (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. 68th TSRC, Charlottesville, VA, USA, Sept. 28th- Oct. 1st 2014
SPI-TOFMS e-cigarette analysis
(Type I, reusable, automatic activation)
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 (simple flavour
compound mixture)
C6H14O
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R. Zimmermann et al. 68th TSRC, Charlottesville, VA, USA, Sept. 28th- Oct. 1st 2014
44 60/61/62
74
74
162
162 56
56
156
138 -H2O
162
84
-pyridine
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 II (refillable with nicotine/flavor containing reservoirs, puffing triggered vaporizer)
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R. Zimmermann et al. 68th TSRC, Charlottesville, VA, USA, Sept. 28th- Oct. 1st 2014
156 138
menthol
162
nicotine
menthol
glycerol
glycerol/acetaldehyde
nicotine
Laser-SPI: Puff profiles (menthol)
e-cigarette II (refillable with nicotine/flavor containing reservoirs, puffing triggered vaporizer)
92 74
glycerol
SPI-TOFMS e-cigarette analysis
(Type II, reusable, automatic activation)
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R. Zimmermann et al. 68th TSRC, Charlottesville, VA, USA, Sept. 28th- Oct. 1st 2014
Power Cigs
Flavour: tobacco
Ingredients:
Propylene glycol
Glycerol
Water
Flavours
Nicotine (18 mg/ml – 1,8%)
www.powercigs-shop.de
e-cigarette III (refillable with nicotine/flavor containing reservoirs, puffing triggered vaporizer)
e-cigarettes:
Temperatures of vapour
producing unit/coil/wire
in many products easily
can reach high temp-
eratures (300°C or more)
significant thermal
decomposition of e-cig.-
components may occur !
0 25 50 75 100 125 150 175 200 225 250 275 300
0,0
0,2
0,4
0,6
0,8
0,0
0,2
0,4
0,6
0,8
Sig
na
l in
ten
sity [V
]
mass [m/z]
REMPI 252 nm
Sig
na
l in
ten
sity [V
] REMPI 266 nm
84/85
126
84/85
126
0 25 50 75 100 125 150 175 200 225 250 275 300
0,0
0,2
0,4
0,6
0,8
0,0
0,2
0,4
0,6
0,8
Sig
na
l in
ten
sity [V
]
mass [m/z]
REMPI 252 nm
Sig
na
l in
ten
sity [V
] REMPI 266 nm
Trace components (Laser-REMPI) of e-cigarette smoke (Type III)
Aromatic trace contaminants or pyrolysis products?
REMPI-TOFMS e-cigarette analysis
(Type III, reusable, automatic activation)
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R. Zimmermann et al. 68th TSRC, Charlottesville, VA, USA, Sept. 28th- Oct. 1st 2014
Polycyclic aromatic hydrocarbons in e-cigarette smoke (Type III,
„tobacco flavor”) by REMPI-TOFMS: Pyrolysis in vaporizer?
• Alkylated phenanthrenes (178, 192, 206, 220, 234)
• Alkylated pyrenes (202, 216)
e-cigarette III (refillable with nicotine/flavor containing reservoirs, puffing triggered vaporizer)
REMPI-TOFMS e-cigarette analysis
(Type III, reusable, automatic activation)
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R. Zimmermann et al. 68th TSRC, Charlottesville, VA, USA, Sept. 28th- Oct. 1st 2014
Puff-resolved analysis of polycyclic aromatic hydrocarbons (PAH)
in e-cigarette smoke (Type III „tobacco flavor) by REMPI-TOFMS:
e-cigarette III (refillable with nicotine/flavor containing reservoirs, puffing triggered vaporizer)
REMPI-TOFMS e-cigarette analysis
(Type III, reusable, automatic activation)
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Puff-resolved analysis of polycyclic aromatic hydrocarbons (alkylated
phenanthrenes) in e-cigarette smoke („tobacco flavor) by REMPI-TOFMS
e-cigarette III (refillable with nicotine/flavor containing reservoirs, puffing triggered vaporizer)
C1- phenanthrene
C2- phenanthrene
C3- phenanthrene
C4- phenanthrene
phenanthrene
REMPI-TOFMS e-cigarette analysis
(Type III, reusable, automatic activation)
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R. Zimmermann et al. 68th TSRC, Charlottesville, VA, USA, Sept. 28th- Oct. 1st 2014
Heat not burn cigarette I (charcoal heated tobacco vaporizer)
SPI-TOFMS heat-not-burn device analysis
(Type I, charcoal heated system, c-HnB)
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R. Zimmermann et al. 68th TSRC, Charlottesville, VA, USA, Sept. 28th- Oct. 1st 2014
60/61/62
Heat not burn cigarette I (charcoal heated tobacco vaporizer)
Aerosolizer: Glycerol
SPI-TOFMS heat-not-burn device analysis
(Type I, charcoal heated system, c-HnB)
+ tobacco compounds
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Guajacol
Nicotine
Dihydroxybenzene
Furfurylalcohol
Furfural
Isoprene
Isoprene
Acetaldehyde/
Glycerol
SPI-TOFMS heat-not-burn device analysis
(Type I, charcoal heated system, c-HnB)
Heat not burn cigarette I (charcoal heated tobacco vaporizer)
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06.10.2014
Puff by puff resolved REMPI-TOFMS measurements of standard and c-HnB
Cigarette: Comparison exemplarily shown for xylene (m/z 106)
100 200 300 400
Standard cigarette charcoal heat not burn
RE
MP
I-S
igna
l @ 2
66nm
fo
r m
/z 1
06
Time [s]
Xylene
Heat not burn cigarette I (charcoal heated tobacco vaporizer)
REMPI-TOFMS heat-not-burn device analysis
(Type I, charcoal heated system, c-HnB)
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Reference cig.
Time [s]
c-HnB
Reference cig.
c-HnB
Heat not burn cigarette I (charcoal heated tobacco vaporizer, c-HnB)
Puff by puff resolved REMPI-TOFMS measurements of standard and c-HnB-
Cigarette: Polycyclic aromatic hydrocarbons (m/z 128/202)
Eclipse (HnB I, Charcoal-HnB):
charcoal heated tobacco vaporizer
REMPI-TOFMS heat-not-burn device analysis
(Type I, charcoal heated system, c-HnB)
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Heat not burn cigarette II (electrical heated tobacco pod vaporizer)
Simulated smoke protocol: puff volume: 75 ml, Puff duration: 2 s, delay: 20 s
SPI-TOFMS heat-not-burn device analysis
(Type II, electrical heated pod system, p-HnB)
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R. Zimmermann et al. 68th TSRC, Charlottesville, VA, USA, Sept. 28th- Oct. 1st 2014 23
dehydrated
Aerosolizer: Propylene glycol
SPI-TOFMS heat-not-burn device analysis
(Type II, electrical heated pod system, p-HnB)
Heat not burn cigarette II (electrical heated tobacco pod vaporizer)
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0
0,5
1
1,5
2
2,5
3
0 500 1000 1500 2000
sig
na
l in
ten
sity [V
]
time [s]
m/z 45
m/z 44
m/z 76
SPI-TOFMS heat-not-burn device analysis
(Type II, electrical heated pod system, p-HnB)
Heat not burn cigarette II (electrical heated tobacco pod vaporizer)
Aerosolizer: Propylene glycol
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Aerosolizer/Acetone
(Propyleneglycol)
Aerosolizer/Acetaldehyde
(Propyleneglycol)
Aerosolizer
(Propyleneglycol)
Dihydoxybenzene
Guajacol Isoprene
Furfural
Nicotine
Aerosolizer
Tobacco pyrolysis
Nicotine
SPI-TOFMS heat-not-burn device analysis
(Type II, electrical heated pod system, p-HnB)
Heat not burn cigarette II (electrical heated tobacco pod vaporizer)
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p
Normalized SPI-TOFMS mass spectra of
cigarette, e-cig. & heat-not-burn devices)
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p
Normalized SPI-TOFMS mass spectra of
cigarette, e-cig. & heat-not-burn devices)
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EBEL SPI can also be used for direct on line monitoring
Dr. M. Bente Dr. M. Saraji
Contact: [email protected]
Instrumental Solutions and
Applications
• Flexible Systems for Research
and Industry: Photo-TOF
(SPI/REMPI/EI)
• On-line Analysis of Cigarette
Smoke (OEM for Borgwaldt KC)
• Evolved Gas Analysis in TA
(OEM for Netzsch GmbH)
Multi-component on-line trace
gas analysers
Photoionisation mass spectrometry
Dr. S.Ehlert
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Summary
• PI-MS (REMPI, SPI): On-line method for real-time analysis
of trace gases, aerosolizer, aroma cpds. & pyrolysis products
• Puff-resolved monitoring of gaseous cigarette smoke
compounds (mapping, on-line anaylsis)
• Analysis of e-cig. vapors: Puff-resoved detection of acet-
aldehyde, glycerol, propylene glycol, flavors, nicotine and
aromatic pyrolysis products
• Analysis of HnB-smoke: Puff-resolved detection of tobacco
compounds and aerosolizers, comparison of c- and p-HnB
• Spin-off company Photonion GmbH: Custom-build PI-MS
Systems for Research and Cooperation with Borgwaldt KC
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Acknowledgements Zimmermann group @
Joint Mass Spectrometry Centre
Dr. J. Maguhn
Dr. T. Streibel
Dr. J. Schnelle-Kreis
Dr. M. Sklorz
Dr. J. Lintelmann
Dr. G. Matuschek
Dr. E. Feicht
Dr. Kirchner
Dr. P. Richthammer
Dr. J. Passig
Dr. G. Jakobi
Dr. M. Arteaga
J. Orasche
E. Hübner
M. Schäffer
T. Gröger
R. Hertz
C. Busch
J. Hölzer
K. Mthembu
C. Schepler
A. Sutherland
S. Ly-Verdu
S. Wohlfahrt
M. Fischer
C. Rüger
T. Schwemer
C.-G. Dragan
H. Czech
S. Erdmann
B. Weggler
B. Werner
J. Kleeblatt
S. Otto
H. Grabow
K. Kiersch
S. Krüger
J. Rittgen
P. Sattler
G. Seibert
R. Qadir
A. Wüst
M. Oster
E. Karg
B. Gruber M. Kürsten
M. Jennerwein
F. Li
L. Müller
A. Rheda
X. Wu
S. Scholtes
C. Radischat
M. Antretter
E. Müller
K. Lau
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)
Dr. T. Streibel Dr. S.Ehlert
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