highly time-resolved two-dimensional mapping of the ...distance between pbl and µ-probe [mm] mass...

R. Zimmermann et al. 68th TSRC, Charlottesville, VA, USA, Sept. 28th- Oct. 1st 2014

Highly time-resolved two-dimensional mapping of the molecular

combustion and pyrolysis product concentrations during a

puff in a burning cigarette

R. Zimmermann1, R. Hertz-Schünemann1, S. Ehlert1,3, A. Walte3, C. Liu2,

K. McAdam2, S.Coburn2, 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

2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed


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

2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed


Why using (vacuum-) photo ionization for fast on-line monitoring?

+ soft ionization (fragmentation-free ionization of many tobacco

smoke chemicals and reduced fragmentation of labile compounds )

+ SPI - universal ionization (incl. alkanes), IE-threshold selectivity

+ REMPI: selective for aromatic compounds

+ two easily switchable laser PI techniques: REMPI & SPI (+EI)

+ sensitive and fast: ppb concent. in sub-second time resolution

+ no matrix effects: “physical ionization”


2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed


Tobacco smoke (2R4F)


2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed


2R4F - Mainstream 2R4F - Sidestream

1st puff

2nd puff

3rd puff

4th puff

5th puff

6th puff

7th puff

8th puff

1st puff

8th puff

Photo ionization – mass spectrometry:

On-line tobacco smoke analysis Adam et al., Mitschke et al., Streibel et al.

2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed


20

30

40

50

0 50 100 150 200 250 300 350 400 450 500

0

1

2

3

Con

cent

ratio

n [p

pm]

N

N

Ion

sign

al [a

rb. u

nits

]

Time[s]

nicotine

1,3-butadiene ”first puff high”

phenomenon

”normal”

behaviour


On-line tobacco smoke analysis

2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed



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 system

(smoke machine)

• Compact oa-TOFMS mass analyzer (R~900)

• Different VUV-lamps for SPI ion source

• EI ion source

• 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.

• Integrated smoke machine – SPI-

TOFMS system (programmable

profiles: ISO, intense, human, e-cig.)

for industrial routine & research

• Quantitative puff-resolved on-line

analysis of tobacco smoke toxicants

(e.g., isoprene, butadiene, benzene,

acetaldehyde)

• Analysis 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,

- Human smoking analyzer (Gas/PM)

- Smoke particle matter analyzer

- Fast gas chromatography pre-

separation (puff- resoved)

2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed


• Research Cigarettes: Well defined model-system for solid state combustion

• Tobacco: Bio mass consisting mainly of Celluloses (“glucose-polymer”)

and Lignin (“phenolic-polymer”) with alkaloid content( nicotine)

• Very reproducible “automated” machine smoking (ISO-testing): One

bell-shaped puff (35 ml/2s) per minute

P = Pyrolysis/

Distillation zone

C = Combustion zone

Application of PI-MS for analysis of pyrolysis &

combustion products within the cigarette

2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed


Heating

element 100 W

Heating

element 50 W

Al

µ-probe

sampling tip

Connector to transfer line



2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed


Heating

element 100 W

Heating

element 50 W

Al

Sampling tip

Connector to transfer line



2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed


Rich pyrolysis/combustion product spectrum: Masses up to 300 m/z detectable

For example: Higher

molecular weight signature

of fatty acids

mass 228 Tetradecanoic acid

mass 242 Pentadecanoic acid

mass 256 Hexadecanoic acid

(Palmitic acid)

mass 270 Heptadecanoic acid

OH

O CH3

OH

OCH3

OH

O CH3

CH3 OH

O

25 50 75 100 125 150 175 200 225 250 275 300

0,000

0,025

0,050

0,075

0,100

0,125

0,150

0,175

0,200

CH3

CH3 CH2

O H

N

CH3

H

CH3

O

S

PI@

11

8n

m /

In

ten

sity [

a.u

.]

m/z

58

44

68

78

849496

110

124122

136

162

17NH

3

CH3 CH3

O

CH3H

O

CH2

CH3

CH2

OCH3

CH3

O

O

OH

OH

O

CH3

O

OCH3

O

CH3

OH

OH

O

OCH3

OH

175 200 225 250 275

0,000

0,001

0,002

0,003

0,004

208

256

270

176

190

188

204

228

N

N

CH3

H

278

214

SPI (

11

8 n

m)

inte

nsi

ty

[R. Hertz et al. Anal. Chim. Acta, 2012 (714) 104-113]



SPI: Universal ionization: 2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed


40 80 120 160 200 240 280 320 360 400

0,00

0,05

0,10

0,15

0,20

0,25

0,30

248

234

220

206

192

178

168

146

132

117

10494

78

REMP

@24

8nm

/ Inten

sity [

a.u.]

m/z

Intensity

59

40 80 120 160 200 240 280 320 360 400

0,00

0,05

0,10

0,15

0,20

0,25

0,30

248

234

220

206

192

178

168

146

132

117

10494

78

RE

MP

@24

8nm

/ In

tens

ity [a

.u.]

m/z

Intensity

59

118

Rich pyrolysis/combustion product spectrum: Aromatics and Polycyclic Aromatic

Hydrocarbons (PAH) with masses up to 500 m/z detectable

REMPI: Selective for Monocyclic and

Polycyclic Aromatic Hydrocarbons (PAH):

Higher molecular

weight signature

e.g. alkylated

“tar”-aromatics



m/z

128

142 156

170

OH

2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed


SPI-TOFMS REMPI-TOFMS

n=5 n=3

µ-probe

position

at PBL

µ-probe

position

at PBL

P C

PI-MS



2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed


70 60 50 40 30 20 10 0 -10

0

20

40

600

5

10

15

0

2

4

0

1

2

3

0,0

0,5

1,0

1,570 60 50 40 30 20 10 0 -10

Distance between PBL and µ-probe [mm]

mass 162 Nicotine,

Anabasine

mass 68 Isoprene, Furan

mass 58 Acetone, Propanal

mass 54 1,3-Butadiene

SP

I@1

26

nm

/ In

ten

sity [a

.u.]

mass 44 Acetaldehyde

70 60 50 40 30 20 10 0 -10

0

2

4

6

0

1

23

4

0

1

2

3

0,000

0,005

0,010

0,015

0,0

0,2

0,4

0,6

0,00

0,03

0,06

0,09

0,12

70 60 50 40 30 20 10 0 -10

SP

I@1

26

nm

/ In

ten

sity [a

.u.]

Distance between PBL and µ-probe [mm]

mass 94 Phenol

mass 92 Toluene

mass 78 Benzene

mass 34 H2S

mass 30 NO

mass 17 NH3

pyrolysis products

Combustion/hot

pyrolysis products



2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed


PI-MS for time- and space-resolved chemical

mapping of the pyrolysis/combustion zone

Pressure and temperature changes

during the measurement

SPI Signals are normalized with

respect to the nitrogen LEI signals

Mapping: Addressing multiple position in cigarette during a puff

2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed


3,53,0

2,0

1,0

0

-1,0

-2,0

-3,0-3,5

x

x

x

x

x

x

x

x

x

x

x

xx x x

x

x

x

x

xx

x

x

x

xx

x

x

x

xx

x

x

x

xx

x

x

x

x

x

x

x

x

x

x

x

x

x

x

x

x x

x

x

x

x

x

x

x

x

x

x

x

x

x

x x

x

x

Cig

are

tte

dia

me

ter

[mm

]

Distance from Paper Burn Line [mm]

1086420-2-4-6-10

x measured pointsx mirrored points

* Relative to benzene,

Substance Relative cross section

Acetone Cross section: 0.31*

Isoprene Cross section: 0.59*

Ammonia -

Phenol -

Nicotine -

Substance Quantification

NO External calibration

Benzene External calibration

Toluene External calibration

Acetaldehyde Cross section: 0.20*

Butadiene Cross section: 0.60*



Puff 3th starts

@ PBL 1.3cm = 0

5 replicates per

sampling point

more than

200 cigarette

measurements

2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed


5 measurements averaged value at puff

maximum for this sampling point:

~ 50 ppm NO and 9 ppm benzene



5 measurements averaged value at puff

end for this sampling point:

~ 110 ppm NO and 1 ppm benzene

2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed



mapping: Distribution maps (middle of puff)

2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed



mapping: Distribution maps (time-resolved)

2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed



mapping: Distribution map “movie”

2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed


Fuel-N

N-Volatiles Char-N

NO

Pyrolysis Pyrolysis

Reburning

Heterogenious

Oxidation

+CxHy

(Re)formation

+DT +DT


mapping: NOx formation and destruction

Normann et al. Prog. Energy Comb. Sci. 35 (5), 385 (2009).

NOx-Formation in bio mass (tobacco) combustion:

Temperature not sufficient for Thermal NOx-formation (Zeldovich-mech.)

Rate of Prompt NOx-formation (Fenimore-mech.) small

Fuel NOx-Formation is dominating: Heterogeneous (from N-containing

char) and Homogeneous (via N-volatiles as HCN etc.) fuel NOx-Formation

2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed



mapping: 3D-Distribution maps (middle of puff)

2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed


PBL Effective homogeneous formation/destruction kinetics

of NO and benzene in a volume increment at puff

peak along center line


mapping: Effective formation/destruction kinetics

2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed


PI-MS for time- and space-resolved

chemical mapping: Other compounds

2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed


Summary

• PI-MS (REMPI, SPI): Soft ionization method for analysis of

trace gases and combustion effluents

• Puff-resolved monitoring of gaseous cigarette smoke

compounds (health risk estimation tobacco research)

• PI-MS with µ-probe sampling: Analyzing the composition

of the pyrolysis and combustion zones: Cigarette as “solid

fuel combustion model”

• “Machine smoking” allows repetitive highly dynamic PI-MS

measurements: Mapping approach NOx-formation

• Spin-off company Photonion GmbH: Custom-build and

standard PI-MS Systems for Industry and Research

2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed


ρħotonıoη

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

trace gas analysers

On-line photoionisation mass spectrometry

Dr. S.Ehlert

2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed


Sampling within coffee-bean during roasting: Setup and mass spectra

Outlook – Further microprobe-PI-MS applications:

Flavor formation in coffee roasting

2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed


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. R. Hertz-

Schünemann S.Ehlert

2014

_TS

RC

41_Z

imm

erm

ann.

pdf

TS

RC

2014

(68)

- D

ocum

ent n

ot p

eer-

revi

ewed

highly time-resolved two-dimensional mapping of the ...distance between pbl and µ-probe [mm] mass...

Documents