hyphenation of a cigarette smoking simulator and a micro ...• the system allows a time-resolved...

Hyphenation of a cigarette smoking simulator and a

micro-probe between a time-of-flight mass spectrometer

for the analysis of pyrolysis and combustion products

from a burning cigarette

02.10.2012 CORESTA Congress Sapporo | © 2009 UNIVERSITÄT ROSTOCK | HELMHOLTZZENTRUM münchen 1

Christian Busch, Romy Hertz, Thorsten Streibel, Ralf Zimmermann University of Rostock

Division of Analytical and Technical Chemistry

Chuan Liu, Kevin G. McAdam British American Tobacco

GR&D Centre - Southampton

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02.10.2012 2

Outline

CORESTA Congress Sapporo | © 2009 UNIVERSITÄT ROSTOCK | HELMHOLTZZENTRUM münchen

1) General introduction: On-line cigarette smoke analysis

2) µ-Probe: Direct cigarette smoke analysis

3) Cigarette smoking simulator: Smoking under flexible burning conditions

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1) General introduction


Classification of the analysis technique:

• Analytical off-line methods (Smoke collection, sample preparation, analysis)

e.g. ISO 10315:2000 – Cigarettes – Determination of nicotine in smoke condensates

• Puff resolved methods (One puff is collected and subsequently analysed)

e.g. Multidimensional GC–MS; Y. Takanami et al., J. Chromatogr. Sci., 2003 (41) 317-322

2D-GC-MS , T. Groeger et al., J. Sep. Sci., 2008 (31) 3366 -3374

• On-line methods – few components (Direct and real-time analysis)

e.g. FTIR; S. Li et al., J. Anal. Appl. Pyrolysis, 2002 (65) 137 -145

Quantum cascade laser spectroscopy; M.E. Parrish et al, Spectrochim. Acta A, Mol. Biomol.

Spectrosc., 2007 (67) 4 -15

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02/10/2012 4



Classification of the topic:

• On-line methods – multi components (Direct and real-time analysis)

e.g. REMPI-TOFMS; R. Zimmermann, R. Dorfner; J. Anal. Appl. Pyrolysis, 1999 (49) 257-266

SPI/REMPI-TOFMS; T. Adam, S. Mitschke, R. R. Baker, BTI, 2009 (23) 203-226

Theoretical aspects (Single and resonance enhanced multi photon ionisation)

Compound

(ground state)

Compound

(electronic

excited state)

Condition:

Photon‘s energy

≥

Ionisation potential

Ionised

species

TOFMS

(m/z)

Compound

(excited

intermediate state)

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02.10.2012 5



SPI – Single photon ionisation

• Laser-SPI: 118 nm = 10.49 eV

• Detection of small molecules and aromatics

(e.g. NH3, NO, isoprene, benzene, pyridine, nicotine, ...)

• Detection of bulk gases (e.g. N2, CO2, H2O) is suppressed IP > 10.49 eV

REMPI – Resonance enhanced multi photon ionisation

• Suited wavelengths: 248 nm = 5.0 eV and 266 nm = 4.66 nm

• Sensitive and selective for mono- and polycyclic aromatic hydrocarbons (PAH)

(e.g. xylene and phenanthrene) and phenols (e.g. dihydroxybenzene).

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02.10.2012 6 CORESTA Congress Sapporo | © 2009 UNIVERSITÄT ROSTOCK | HELMHOLTZZENTRUM münchen

Microprobe sampling device

• R.R. Baker studied the local formation of selected combustion gases.

(H2, O2, CO, CO2, methane, ethane, propane) [R.R. Baker; BTI,1981 (11) 1-17]

• Intra-puff resolved analysis of volatile smoke compounds (resolution = 10 Hz).

• No smoke composition changes:

→ due to aging reactions.

→ due to filtration processes (inside the burning coal).

2) µ-Probe - Introduction and Motivation

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2) µ-Probe - Experimental description


Borgwaldt

RM1/G

SPI/

REMPI

TOFMS

puncture

sealed with

glue

2R4F

heated

capillary

Al-based

body

SS-tip

Unfiltered whole smoke:

necessity of heating to

prevent clogging of the

capillary

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Microprobe sampling device

Correlation of ISO puffing time and interval to the distance between paper burn line (PBL) and µ-probe.

2) µ-Probe - Results (continuous monitoring)

[R. Hertz, T. Streibel, C. Liu, K. G. McAdam, R. Zimmermann, Anal. Chim. Acta, 2012 (714) 104-113]

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Averaged mass spectrum (8 puffs) from whole smoke inside of a 2R4F cigarette

(ISO puffing parameters, n = 5).

2) µ-Probe - Results (mass spectrum)


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3D-plots show the comprehensive on-line monitoring of the complete cigarette smoking process

(a) SPI and (b) REMPI (n ≥ 3).

2) µ-Probe - Results (SPI vs. REMPI)


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a)


2) µ-Probe - Results (pyrolysis vs. combustion)


On-line monitoring of the cigarette smoking process of selected masses (a) SPI and (b) REMPI (n ≥ 3).

b)

P

P

P

P C

C

C

C

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2) µ-Probe – Results (statistical analysis)


Principal component analysis (PCA)

(a) Signal intensity and distance plot

for puffs 7–8 and smouldering phase.

(b and c) PCA results of the SPI

measurement with the µ-probe and

2R4F-cigarettes under ISO puffing

conditions (n = 5).

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• The system allows a time-resolved analysis of combustion (e.g. butadiene,

isoprene) and pyrolysis gases (e.g. phenol, nicotine) originating within a

burning cigarette.

• Chemical reactions inside the cigarette’s coal during puffing and

smouldering can be observed.

→ Change from pyrolysis to combustion after the PBL reached the µ-probe.

Mapping of compound formation inside the cigarette/burning coal.

→ Different puffs, inclusion of higher PAH, …

2) µ-Probe – Summary and Outlook

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Simulation of the smoking process by:

o three powerful IR-Lamps (→ burning coal, puffing/smouldering temp.)

o a moving shuttle (→ consumption of the tobacco rod)

Change of the burning atmosphere.

(A cigarette can be “smoked” under inert (N2) conditions!)

Change of the naturally occurring puffing/smouldering temperature.

Separation of compound’s formation mechanisms (e.g. pyrolysis and combustion).

3) Cigarette smoking simulator - Motivation

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1 2

3

4

5

6

3) Cigarette smoking simulator - Experimental description

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Mean signal intensity of 8 selected compounds of ten smoked 3R4F cigarettes under nitrogen (blue)

and air (red) atmosphere (intensity maximum normalised).

[C. Busch, T. Streibel, C. Liu, K. G. McAdam, R. Zimmermann, Anal. Bioanal. Chem., 2012 (403) 419-430]

3) Cigarette smoking simulator - Results (puff by puff)

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Principal component analysis

Burning atmosphere and puff number:

• Separation and grouping of experiments

• Compounds’ formation is influenced

Separation of substance groups

[C. Busch, T. Streibel, C. Liu, K. G. McAdam, R. Zimmermann, Anal. Bioanal. Chem., 2012 (403) 419-430]


Carbohydrate fragments

3) Cigarette smoking simulator - Results (statistics)

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• The system allows the investigation of tobacco’s thermochemical reactions

outside of from natural restrictions.

• Nearly all compounds’ yields decreased after changing the burning

atmosphere from inert to oxidative.

• Only small changes concerning the overall pattern of smoke constituents

can be observed.

• Smoke components derive mainly from the pyrolysis and distillation zone of

the cigarette.

→ Independent from the burning atmosphere.

3) Cigarette smoking simulator - Summary

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02.10.2012 19

Acknowledgement


THANK YOU FOR YOUR ATTENTION!

www.bat-science.com

www.jmsc.de

www.photonion.de

Further information about cigarette smoke analysis:

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hyphenation of a cigarette smoking simulator and a micro ...• the system allows a time-resolved...

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