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Page 1: Moritz J. D. Mann, Michael Kundel, - CIREScires.colorado.edu/jimenez-group/UsrMtgs/UsersMtg14/Moritz_Mann... · Moritz J. D. Mann, Michael Kundel, Anne-Kathrin Bernhammer and Thorsten
Page 2: Moritz J. D. Mann, Michael Kundel, - CIREScires.colorado.edu/jimenez-group/UsrMtgs/UsersMtg14/Moritz_Mann... · Moritz J. D. Mann, Michael Kundel, Anne-Kathrin Bernhammer and Thorsten

Moritz J. D. Mann, Michael Kundel,

Anne-Kathrin Bernhammer and Thorsten Hoffmann Institute of Inorganic and Analytical Chemistry, Johannes Gutenberg University Mainz

Online Quantification of Gaseous Amines using the

HR-ToF-AMS and artificially generated Particles

September 8, 2013 | Moritz Mann | Online Quantification of Gaseous Amines using the HR-ToF-AMS | 2 / 13

Page 3: Moritz J. D. Mann, Michael Kundel, - CIREScires.colorado.edu/jimenez-group/UsrMtgs/UsersMtg14/Moritz_Mann... · Moritz J. D. Mann, Michael Kundel, Anne-Kathrin Bernhammer and Thorsten

• Atmospheric short chain aliphatic amines take part in nucleation processes

• Formation of thermodynamically stable clusters (TSC)

• Ternary composites are suggested, e.g. H2SO4-amine-H2O

(Kulmala, Pirjola, Mäkelä, Nature 2000, 404, 66)

• Amine gas treating / “gas sweetening”

• Removal of CO2 and SO2 of gases by washing with aqueous amine solutions

• CO2 capture and storage

• Is there amine left in the cleaned air?

Motivation for the Measurement of Amines

September 8,

2013 3 / 13 | Moritz Mann | Online Quantification of Gaseous Amines using the HR-ToF-AMS |

Page 4: Moritz J. D. Mann, Michael Kundel, - CIREScires.colorado.edu/jimenez-group/UsrMtgs/UsersMtg14/Moritz_Mann... · Moritz J. D. Mann, Michael Kundel, Anne-Kathrin Bernhammer and Thorsten

Ambient concentrations of gas-phase Amines: (Ge, Wexler, Clegg, Atmospheric Environment 2011, 45, 524-546)

• Monomethylamine (MMA) 10 – 289 pptv

• Dimethylamine (DMA) 0 – 76 pptv

• Trimethylamine (TMA) 0 – 108 pptv

• Highest concentrations are achieved in agriculture areas

Animal husbandry, biomass burning and the ocean are

main sources of atmospheric short chain aliphatic amines. (Schade, Crutzen, Journal of Atmospheric Chemistry 1995, 22(3), 319-346)

Atmospheric Concentrations and Sources

September 8,

2013 | Moritz Mann | Online Quantification of Gaseous Amines using the HR-ToF-AMS | 4 / 13

Page 5: Moritz J. D. Mann, Michael Kundel, - CIREScires.colorado.edu/jimenez-group/UsrMtgs/UsersMtg14/Moritz_Mann... · Moritz J. D. Mann, Michael Kundel, Anne-Kathrin Bernhammer and Thorsten

Enrichment factor 106-107 particle phase vs. gas phase (Canagaratna, et al., Mass Spectrom. Rev. 2007, 26, 185-222)

Aerodyne’s HR-ToF-AMS

September 8,

2013 | Moritz Mann | Online Quantification of Gaseous Amines using the HR-ToF-AMS | 5 / 13

Page 6: Moritz J. D. Mann, Michael Kundel, - CIREScires.colorado.edu/jimenez-group/UsrMtgs/UsersMtg14/Moritz_Mann... · Moritz J. D. Mann, Michael Kundel, Anne-Kathrin Bernhammer and Thorsten

Gaseous compound trapping in artificially-generated particles

The GTRAP

September 8,

2013

Amine-filled

permeation tube

| Moritz Mann | Online Quantification of Gaseous Amines using the HR-ToF-AMS | 6 / 13

Page 7: Moritz J. D. Mann, Michael Kundel, - CIREScires.colorado.edu/jimenez-group/UsrMtgs/UsersMtg14/Moritz_Mann... · Moritz J. D. Mann, Michael Kundel, Anne-Kathrin Bernhammer and Thorsten

Properties of the System

Example of a mass spectrum

containing 126 ppb TMA

m/z 58 and m/z 59 are used

as a marker

Responding qualities

of the system are

shown on the right

Sig

na

l

time

September 8, 2013 | Moritz Mann | Online Quantification of Gaseous Amines using the HR-ToF-AMS | 7 / 13

Page 8: Moritz J. D. Mann, Michael Kundel, - CIREScires.colorado.edu/jimenez-group/UsrMtgs/UsersMtg14/Moritz_Mann... · Moritz J. D. Mann, Michael Kundel, Anne-Kathrin Bernhammer and Thorsten

Properties of the System σ

(backgro

und

)

Time resolution vs. LOD:

Longer averaging period results

less background and therefore a

better limit of detection. Drewnick et al., Atmos. Meas. Tech. 2009, 2, 33-46

September 8,

2013

3 min

| Moritz Mann | Online Quantification of Gaseous Amines using the HR-ToF-AMS | 8 / 13

LODMMA = 420 ppt

LODDMA = 87 ppt

LODTMA = 188 ppt

LODDEA = 451 ppt

LODTEA = 70 ppt

Page 9: Moritz J. D. Mann, Michael Kundel, - CIREScires.colorado.edu/jimenez-group/UsrMtgs/UsersMtg14/Moritz_Mann... · Moritz J. D. Mann, Michael Kundel, Anne-Kathrin Bernhammer and Thorsten

Experiments on the Emission of Plants

Ambient air

4 L/min

Chenopodium vulvaria (Stinking Goosefoot)

September 8, 2013 | Moritz Mann | Online Quantification of Gaseous Amines using the HR-ToF-AMS | 9 / 13

Page 10: Moritz J. D. Mann, Michael Kundel, - CIREScires.colorado.edu/jimenez-group/UsrMtgs/UsersMtg14/Moritz_Mann... · Moritz J. D. Mann, Michael Kundel, Anne-Kathrin Bernhammer and Thorsten

September 8,

2013

TMA emission profile of

Chenopodium vulvaria at different

Ozone concentrations and light

conditionings:

• No reaction on Ozone was found

• Significant reaction on light

How does the Amine emission of

plants depend on different

environmental conditions?

10 / 13

backgro

und

without

pla

nt,

0 p

pm

Ozone

| Moritz Mann | Online Quantification of Gaseous Amines using the HR-ToF-AMS |

Page 11: Moritz J. D. Mann, Michael Kundel, - CIREScires.colorado.edu/jimenez-group/UsrMtgs/UsersMtg14/Moritz_Mann... · Moritz J. D. Mann, Michael Kundel, Anne-Kathrin Bernhammer and Thorsten

Further Applications for GTRAP

September 8, 2013 | Moritz Mann | Online Quantification of Gaseous Amines using the HR-ToF-AMS | 11 / 13

M. Kundel, et al., Anal. Chem. 2012, 84, 1439-1445 GTRAP

Page 12: Moritz J. D. Mann, Michael Kundel, - CIREScires.colorado.edu/jimenez-group/UsrMtgs/UsersMtg14/Moritz_Mann... · Moritz J. D. Mann, Michael Kundel, Anne-Kathrin Bernhammer and Thorsten

Further Applications for GTRAP

September 8, 2013 | Moritz Mann | Online Quantification of Gaseous Amines using the HR-ToF-AMS | 12 / 13

Outlook: Total quantification of particulate peroxides

• ROOR (s) + HI (g) 2 ROH + I2

Peroxide

aerosol

HI (g)

Flow tube

Particles

ROH + I2

Charcoal

denuder

overflow

ToF-AMS

Motivation:

• up to 85% of the SOA mass formed from pinene oxidation can be peroxides

(H2O2, ROOH, ROOR) (Docherty and Zieman, 2005);

• Poor understanding of the peroxide forming chemistry, also relevant for

toxicological studies (SOA-health)

• Measurements have been done with traditional offline techniques

(wet chemistry – iodometric titration)

Page 13: Moritz J. D. Mann, Michael Kundel, - CIREScires.colorado.edu/jimenez-group/UsrMtgs/UsersMtg14/Moritz_Mann... · Moritz J. D. Mann, Michael Kundel, Anne-Kathrin Bernhammer and Thorsten

Any questions?

Thanks for your attention!

September 8, 2013

And thanks to Prof. Dr. Thorsten Hoffmann

and the research group!

| Moritz Mann | Online Quantification of Gaseous Amines using the HR-ToF-AMS | 13