On-line photo ionization mass spectrometry for

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

[email protected]

2 Photonion GmbH Schwerin, Germany

[email protected]

ρħotonıoη

3 BAT Ltd. Southampton, UK

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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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Tobacco smoke (2R4F)

Introduction: Photo ionization - SPI and REMPI

N2

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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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-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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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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(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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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


(Type II, reusable, automatic activation)

[Menthol-H2O]

138

e-cigarette II (refillable with nicotine/flavor containing reservoirs, puffing triggered vaporizer)

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http://commons.wikimedia.org/wiki/File:Menthol_neutral.svg

http://commons.wikimedia.org/wiki/File:Nikotin_-_Nicotine.svg



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


(Type II, reusable, automatic activation)

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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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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)




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Puff-resolved analysis of polycyclic aromatic hydrocarbons (PAH)

in e-cigarette smoke (Type III „tobacco flavor) by REMPI-TOFMS:




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Puff-resolved analysis of polycyclic aromatic hydrocarbons (alkylated

phenanthrenes) in e-cigarette smoke („tobacco flavor) by REMPI-TOFMS


C1- phenanthrene

C2- phenanthrene

C3- phenanthrene

C4- phenanthrene

phenanthrene



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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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60/61/62


Aerosolizer: Glycerol



+ tobacco compounds

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Guajacol

Nicotine

Dihydroxybenzene

Furfurylalcohol

Furfural

Isoprene

Isoprene

Acetaldehyde/

Glycerol




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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


REMPI-TOFMS heat-not-burn device analysis


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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


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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


(Type II, electrical heated pod system, p-HnB)

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dehydrated

Aerosolizer: Propylene glycol




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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




Aerosolizer: Propylene glycol

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Aerosolizer/Acetone

(Propyleneglycol)

Aerosolizer/Acetaldehyde

(Propyleneglycol)

Aerosolizer

(Propyleneglycol)

Dihydoxybenzene

Guajacol Isoprene

Furfural

Nicotine

Aerosolizer

Tobacco pyrolysis

Nicotine




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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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Documents

On-line photo ionization mass spectrometry for