moritz j. d. mann, michael kundel, -...
TRANSCRIPT
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
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• 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
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2013 3 / 13 | Moritz Mann | Online Quantification of Gaseous Amines using the HR-ToF-AMS |
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
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Enrichment factor 106-107 particle phase vs. gas phase (Canagaratna, et al., Mass Spectrom. Rev. 2007, 26, 185-222)
Aerodyne’s HR-ToF-AMS
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Gaseous compound trapping in artificially-generated particles
The GTRAP
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Amine-filled
permeation tube
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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
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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
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2013
3 min
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LODMMA = 420 ppt
LODDMA = 87 ppt
LODTMA = 188 ppt
LODDEA = 451 ppt
LODTEA = 70 ppt
Experiments on the Emission of Plants
Ambient air
4 L/min
Chenopodium vulvaria (Stinking Goosefoot)
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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 |
Further Applications for GTRAP
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M. Kundel, et al., Anal. Chem. 2012, 84, 1439-1445 GTRAP
Further Applications for GTRAP
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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)
Any questions?
Thanks for your attention!
September 8, 2013
And thanks to Prof. Dr. Thorsten Hoffmann
and the research group!
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