Atmospheric Chemistry and Physics Discussions
www.atmos-chem-phys-discuss.net
1680-7367
1680-7375
8
2
2008
10.5194/acpd-8-4727-2008
http://www.atmos-chem-phys-discuss.net/8/4727/2008/
http://www.atmos-chem-phys-discuss.net/8/4727/2008/acpd-8-4727-2008.html
http://www.atmos-chem-phys-discuss.net/8/4727/2008/acpd-8-4727-2008.pdf
4727
4764
2008-03-05
Gas/particle partitioning of carbonyls in the photooxidation of isoprene and 1,3,5-trimethylbenzene
R. M. Healy
J. C. Wenger
j.wenger@ucc.ie
A. Metzger
J. Duplissy
M. Kalberer
J. Dommen
Department of Chemistry and Environmental Research Institute, University College Cork, Cork, Ireland
Laboratory of Atmospheric Chemistry, Paul Scherrer Institut, Villigen, Switzerland
Department of Chemistry and Applied Biosciences, ETH Zurich, 8093 Zurich, Switzerland
A new denuder-filter sampling technique has been used to investigate the
gas/particle partitioning behaviour of the carbonyl products from the
photooxidation of isoprene and 1,3,5-trimethylbenzene. A series of
experiments was performed in two atmospheric simulation chambers at
atmospheric pressure and ambient temperature in the presence of NO<sub>x</sub> and
at a relative humidity of approximately 50%. The denuder and filter were
both coated with the derivatizing agent
O-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine (PFBHA) to enable the efficient
collection of gas- and particle-phase carbonyls respectively. The tubes and
filters were extracted and carbonyls identified as their oxime derivatives
by GC-MS. The carbonyl products identified in the experiments accounted for
around 5% and 10% of the mass of secondary organic aerosol formed from
the photooxidation of isoprene and 1,3,5-trimethylbenzene respectively.
<br><br>
Experimental gas/particle partitioning coefficients were determined for a
wide range of carbonyl products formed from the photooxidation of isoprene
and 1,3,5-trimethylbenzene and compared with the theoretical values based on
standard absorptive partitioning theory. Photooxidation products with a
single carbonyl moiety were not observed in the particle phase, but
dicarbonyls, and in particular, glyoxal and methylglyoxal, exhibited
gas/particle partitioning coefficients several orders of magnitude higher
than expected theoretically. These findings support the importance of
heterogeneous chemistry as a pathway for SOA formation and growth during the
atmospheric degradation of anthropogenic and biogenic hydrocarbons.
Asher, W. E., Pankow, J. F., Erdakos, G. B., and Seinfeld, J. H.: Estimating the vapor pressures of multi-functional oxygen-containing organic compounds using group contribution methods, Atmos. Environ., 36(9), 1483–1498, 2002.
Barsanti, K. C. and Pankow, J. F.: Thermodynamics of the formation of atmospheric organic particulate matter by accretion reactions - Part 1: aldehydes and ketones, Atmos. Environ., 38(26), 4371–4382, 2004.
Barsanti, K. C. and Pankow, J. F.: Thermodynamics of the formation of atmospheric organic particulate matter by accretion reactions – Part 2: Dialdehydes, methylglyoxal, and diketones, Atmos. Environ., 39(35), 6597–6607, 2005.
Barsanti, K. C. and Pankow, J. F.: Thermodynamics of the formation of atmospheric organic particulate matter by accretion reactions – Part 3: Carboxylic and dicarboxylic acids, Atmos. Environ., 40(34), 6676–6686, 2006.
Carter, W. P. L.: Condensed atmospheric photooxidation mechanisms for isoprene, Atmos. Environ., 30(24), 4275–4290, 1996.
Claeys, M., Graham, B., Vas, G., et al.: Formation of secondary organic aerosols through photooxidation of isoprene, Science, 303(5661), 1173–1176, 2004.
Cocker, D. R., Mader, B. T., Kalberer, M., Flagan, R. C., and Seinfeld, J. H.: The effect of water on gas-particle partitioning of secondary organic aerosol: II. m-xylene and 1,3,5-trimethylbenzene photooxidation systems, Atmos. Environ., 35(35), 6073–6085, 2001.
Dommen, J., Metzger, A., Duplissy, J., et al.: Laboratory observation of oligomers in the aerosol from isoprene/NOx photooxidation, Geophys. Res. Lett., 33(13), L13805, doi:10.1029/2006, 2006.
Edney, E. O., Kleindienst, T. E., Jaoui, M., et al.: Formation of 2-methyl tetrols and 2-methylglyceric acid in secondary organic aerosol from laboratory irradiated isoprene/NO<sub>x</sub>/SO<sub>2</sub>/air mixtures and their detection in ambient PM$_2.5$ samples collected in the eastern United States, Atmos. Environ., 39(29), 5281–5289, 2005.
Fan, J. and Zhang, R.: Atmospheric Oxidation Mechanism of Isoprene, Environ. Chem., 1, 140–149, 2004.
Forstner, H. J. L., Flagan, R. C., and Seinfeld, J. H.: Secondary organic aerosol from the photooxidation of aromatic hydrocarbons: Molecular composition, Environ, Sci. Technol., 31(5), 1345–1358, 1997.
Fuzzi, S., Andreae, M. O., Huebert, B. J., et al.: Critical assessment of the current state of scientific knowledge, terminology, and research needs concerning the role of organic aerosols in the atmosphere, climate, and global change, Atmos. Chem. Phys., 6, 2017–2038, 2006.
Hamilton, J. F., Lewis, A. C., Reynolds, J. C., Carpenter, L. J., and Lubben, A.: Investigating the composition of organic aerosol resulting from cyclohexene ozonolysis: low molecular weight and heterogeneous reaction products, Atmos. Chem. Phys., 6, 4973–4984, 2006.
Hamilton, J. F., Webb, P. J., Lewis, A. C., and Reviejo, M. M.: Quantifying small molecules in secondary organic aerosol formed during the photo-oxidation of toluene with hydroxyl radicals, Atmos. Environ., 39(38), 7263–7275, 2005.
Hastings, W. P., Koehler, C. A., Bailey, E. L., and DeHaan, D. O.: Secondary Organic Aerosol Formation by Glyoxal Hydration and Oligomer Formation: Humidity Effects and Equilibrium Shifts during Analysis, Environ. Sci. Technol., 39(22), 8728–8735, 2005.
Hilal, S. H., Karickhoff, S. W., and Carreira, L. A.: A rigorous test for SPARC's chemical reactivity models: Estimation of more than 4300 ionization pK(a)s, Quantitative Structure-Activity Relationships, 14(4), 348–355, 1995.
Jang, M. S., Czoschke, N. M., Lee, S., and Kamens, R. M.: Heterogeneous atmospheric aerosol production by acid-catalyzed particle-phase reactions, Science, 298(5594), 814–817, 2002.
Jang, M. S. and Kamens, R. M.: Characterization of secondary aerosol from the photooxidation of toluene in the presence of NO<sub>x</sub> and 1-propene, Environ. Sci. Technol., 35(18), 3626–3639, 2001.
Jenkin, M. E.: Modelling the formation and composition of secondary organic aerosol from alpha- and beta-pinene ozonolysis using MCM v3. Atmos. Chem. Phys., 4: 1741-1757, 2004.
Johnson, D., Jenkin, M. E., Wirtz, K., and Martin-Reviejo, M.: Simulating the formation of secondary organic aerosol from the photooxidation of aromatic hydrocarbons, Environ. Chem., 2(1), 35–48, 2005.
Johnson, D., Utembe, S. R., Jenkin, M. E., et al.: Simulating regional scale secondary organic aerosol formation during the TORCH 2003 campaign in the southern UK, Atmos. Chem. Phys., 6, 403–418, 2006.
Kalberer, M., Paulsen, D., Sax, M., et al.: Identification of polymers as major components of atmospheric organic aerosols, Science, 303(5664), 1659–1662, 2004.
Kamens, R., Jang, M., Chien, C. J., and Leach, K.: Aerosol formation from the reaction of alpha-pinene and ozone using a gas-phase kinetics aerosol partitioning model, Environ. Sci. Technol., 33(9), 1430–1438, 1999.
Kamens, R. M. and Jaoui, M.: Modeling aerosol formation from alpha-pinene plus NOx in the presence of natural sunlight using gas-phase kinetics and gas-particle partitioning theory, Environ. Sci. Technol., 35(7), 1394–1405, 2001.
Kanakidou, M., Seinfeld, J. H., Pandis, S. N., et al.: Organic aerosol and global climate modelling: a review, Atmos. Chem. Phys., 5, 1053–1123, 2005.
Kleindienst, T. E., Edney, E. O., Lewandowski, M., Offenberg, J. H., and Jaoui, M.: Secondary organic carbon and aerosol yields from the irradiations of isoprene and alpha-pinene in the presence of NO<sub>x</sub> and SO<sub>2</sub>: Environ. Sci. Technol., 40(12), 3807–3812, 2006.
Kroll, J. H., Ng, N. L., Murphy, S. M., Flagan, R. C., and Seinfeld, J. H.: Secondary organic aerosol formation from isoprene photooxidation, Environ. Sci. Technol., 40(6), 1869–1877, 2006.
Liggio, J., Li, S. M., and McLaren, R.: Heterogeneous reactions of glyoxal on particulate matter: Identification of acetals and sulfate esters, Environ. Sci. Technol., 39(6), 1532–1541, 2005a.
Liggio, J., Li, S. M., and McLaren, R.: Reactive uptake of glyoxal by particulate matter, J. Geophys. Res.-Atmos., 110(D10), D10304, doi:10.1029/2004/JD005113, 2005b.
Loeffler, K. W., Koehler, C. A., Paul, N. M., and DeHaan, D. O.: Oligomer Formation in Evaporating Aqueous Glyoxal and Methyl Glyoxal Solutions, Environ. Sci. Technol., 40(20), 6318–6323, 2006.
Ng, N. L., Kroll, J. H., Chan, A. W. H., et al.: Secondary organic aerosol formation from m-xylene, toluene, and benzene, Atmos. Chem. Phys., 7(14), 3909–3922, 2007.
Ng, N. L., Kroll, J. H., Keywood, M. D., et al.: Contribution of first- versus second-generation products to secondary organic aerosols formed in the oxidation of biogenic hydrocarbons, Environ. Sci. Technol., 40(7), 2283–2297, 2006.
Odum, J. R., Hoffmann, T., Bowman, F., et al.: Gas/particle partitioning and secondary organic aerosol yields, Environ. Sci. Technol., 30(8), 2580–2585, 1996.
Odum, J. R., Jungkamp, T. P. W., Griffin, R. J., Flagan, R. C., and Seinfeld, J. H.: The atmospheric aerosol-forming potential of whole gasoline vapor, Science, 276(5309), 96–99, 1997.
Pankow, J. F.: An Absorption-Model of Gas-Particle Partitioning of Organic-Compounds in the Atmosphere, Atmos. Environ., 28(2), 185–188, 1994a.
Pankow, J. F.: An Absorption-Model of the Gas Aerosol Partitioning Involved in the Formation of Secondary Organic Aerosol, Atmos. Environ., 28(2), 189–193, 1994b.
Paulsen, D., Dommen, J., Kalberer, M., et al.: Secondary organic aerosol formation by irradiation of 1,3,5-trimethylbenzene-NO<sub>x</sub>-H<sub>2</sub>O in a new reaction chamber for atmospheric chemistry and physics, Environ. Sci. Technol., 39(8), 2668–2678, 2005.
Pöschl, U.: Atmospheric aerosols: Composition, transformation, climate and health effects, Angewandte Chemie-International Edition, 44(46), 7520–7540, 2005.
Smith, D. F., Kleindienst, T. E., and McIver, C. D.: Primary product distributions from the reaction of OH with m-, p-xylene, 1,2,4- and 1,3,5-trimethylbenzene, J. Atmos. Chem., 34(3), 339–364, 1999.
Spaulding, R. S., Schade, G. W., Goldstein, A. H., and Charles, M. J.: Characterization of secondary atmospheric photooxidation products: Evidence for biogenic and anthropogenic sources, J. Geophys. Res.-Atmos., 108(D8), 4247, doi:10.1029/2002JD002478, 2003.
Surratt, J. D., Murphy, S. M., Kroll, J. H., et al.: Chemical composition of secondary organic aerosol formed from the photooxidation of isoprene, J. Phys. Chem. A, 110(31), 9665–9690, 2006.
Temime, B., Healy, R. M., and Wenger, J. C.: A Denuder-Filter Sampling Technique for the Detection of Gas and Particle Phase Carbonyl Compounds, Environ. Sci. Technol., 41(18), 6514–6520, 2007.
Tolocka, M. P., Jang, M., Ginter, J. M., et al.: Formation of oligomers in secondary organic aerosol, Environ. Sci. Technol., 38(5), 1428–1434, 2004.
Yu, J. Z., Cocker, D. R., Griffin, R. J., Flagan, R. C., and Seinfeld, J. H.: Gas-phase ozone oxidation of monoterpenes: Gaseous and particulate products. J. Atmos. Chem., 34(2), 207–258, 1999.
Yu, J. Z., Jeffries, H. E., and Lelacheur, R. M.: Identifying Airborne Carbonyl-Compounds in Isoprene Atmospheric Photooxidation Products by Their PFBHA Oximes Using Gas-Chromatography Ion-Trap Mass-Spectrometry, Environ. Sci. Technol., 29(8), 1923–1932, 1995.
Yu, J. Z., Jeffries, H. E., and Sexton, K. G.: Atmospheric photooxidation of alkylbenzenes, 1 Carbonyl product analyses, Atmos. Environ., 31(15), 2261–2280, 1997.
Zahardis, J., LaFranchi, B. W., and Petrucci, G. A.: Direct observation of polymerization in the oleic acid-ozone heterogeneous reaction system by photoelectron resonance capture ionization aerosol mass spectrometry, Atmos. Environ., 40(9), 1661–1670, 2006.