Online Quantification of Gaseous Amines using the HR-ToF-AMS and artificially generated Particles

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2 Online Quantification of Gaseous Amines using the HR-ToF-AMS and artificially generated Particles Moritz J. D. Mann, Michael Kundel, Anne-Kathrin Bernhammer and Thorsten Hoffmann Institute of Inorganic and Analytical Chemistry, Johannes Gutenberg University Mainz September 8, 2013 Moritz Mann Online Quantification of Gaseous Amines using the HR-ToF-AMS 2 / 13

3 September 8, 2013 Moritz Mann Online Quantification of Gaseous Amines using the HR-ToF-AMS 3 / 13 Motivation for the Measurement of Amines Atmospheric short chain aliphatic amines take part in nucleation processes Formation of thermodynamically stable clusters (TSC) Ternary composites are suggested, e.g. H 2 SO 4 -amine-h 2 O (Kulmala, Pirjola, Mäkelä, Nature 2000, 404, 66) Amine gas treating / gas sweetening Removal of CO 2 and SO 2 of gases by washing with aqueous amine solutions CO 2 capture and storage Is there amine left in the cleaned air?

4 September 8, 2013 Moritz Mann Online Quantification of Gaseous Amines using the HR-ToF-AMS 4 / 13 Atmospheric Concentrations and Sources Ambient concentrations of gas-phase Amines: (Ge, Wexler, Clegg, Atmospheric Environment 2011, 45, ) Monomethylamine (MMA) pptv Dimethylamine (DMA) 0 76 pptv Trimethylamine (TMA) 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), )

5 September 8, 2013 Moritz Mann Online Quantification of Gaseous Amines using the HR-ToF-AMS 5 / 13 Aerodyne s HR-ToF-AMS Enrichment factor particle phase vs. gas phase (Canagaratna, et al., Mass Spectrom. Rev. 2007, 26, )

6 September 8, 2013 Moritz Mann Online Quantification of Gaseous Amines using the HR-ToF-AMS 6 / 13 The GTRAP Gaseous compound trapping in artificially-generated particles Amine-filled permeation tube

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

8 September 8, 2013 Moritz Mann Online Quantification of Gaseous Amines using the HR-ToF-AMS 8 / 13 Properties of the System Time resolution vs. LOD: σ (background) Longer averaging period results less background and therefore a better limit of detection. Drewnick et al., Atmos. Meas. Tech. 2009, 2, LOD MMA = 420 ppt LOD DMA = 87 ppt LOD TMA = 188 ppt LOD DEA = 451 ppt LOD TEA = 70 ppt 3 min

9 September 8, 2013 Moritz Mann Online Quantification of Gaseous Amines using the HR-ToF-AMS 9 / 13 Experiments on the Emission of Plants Ambient air 4 L/min Chenopodium vulvaria (Stinking Goosefoot)

10 background without plant, 0 ppm Ozone September 8, 2013 Moritz Mann Online Quantification of Gaseous Amines using the HR-ToF-AMS 10 / 13 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?

11 September 8, 2013 Moritz Mann Online Quantification of Gaseous Amines using the HR-ToF-AMS 11 / 13 Further Applications for GTRAP M. Kundel, et al., Anal. Chem. 2012, 84, GTRAP

12 September 8, 2013 Moritz Mann Online Quantification of Gaseous Amines using the HR-ToF-AMS 12 / 13 Further Applications for GTRAP Outlook: Total quantification of particulate peroxides ROOR (s) + HI (g) 2 ROH + I 2 HI (g) Flow tube Peroxide aerosol Charcoal denuder overflow ToF-AMS Particles ROH + I 2 Motivation: up to 85% of the SOA mass formed from pinene oxidation can be peroxides (H 2 O 2, 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)

13 Thanks for your attention! Any questions? And thanks to Prof. Dr. Thorsten Hoffmann and the research group! September 8, 2013 Moritz Mann Online Quantification of Gaseous Amines using the HR-ToF-AMS 13