References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-8-1423-2008

Unambiguous identification of esters as oligomers in secondary organic aerosol formed from cyclohexene and cyclohexene/α-pinene ozonolysis

Müller

¹ Reinnig

M.-C.

¹ Warnke

¹ Hoffmann

Th.

Johannes Gutenberg-Universität, Institut für anorganische Chemie und analytische Chemie, Duesbergweg 10–14, 55128 Mainz, Germany

11 03 2008

8 5 1423 1433

This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

This article is available from http://www.atmos-chem-phys.net/8/1423/2008/acp-8-1423-2008.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/8/1423/2008/acp-8-1423-2008.pdf

The build-up of oligomeric compounds during secondary organic aerosol (SOA) formation is subject of atmospheric research since several years. New particle formation and especially the SOA mass yield might be influenced significantly by oligomer formation. However, the chemical nature of observed oligomers and their formation pathways are still unclear. In this paper, the structural characterization of certain dimeric compounds (esters) formed during the ozonolysis of cyclohexene and cyclohexene/α-pinene mixtures are presented. The identification is based on the comparison of the mass spectra and the retention times (LC) of the oligomeric products with synthesized reference compounds. Cyclohexene is used here as a model compound for terpenes as globally most important SOA precursors, since it possesses a simpler structure than the biogenic alkenes and therefore offers the possibility to get access to reference compounds for certain of its oxidation products. In addition to cyclohexene, the formation of esters could also be observed in experiments with α-pinene as reactant.

References 1

Alves, C., Pio, C. and Duarte, A.: The organic composition of air particulate matter from rural and urban Portuguese areas, Phys. Chem. Earth B, 24, 705–709, 1999.

Anttila, P., Hyotylainen, T., Heikkila, A., Jussila, M., Finell, J., Kulmala, M., and Riekkola, M. L.: Determination of organic acids in aerosol particles from a coniferous forest by liquid chromatography-mass spectrometry, J. Sep. Sci., 28, 337–346, 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, 6676–6686, 2006.

Baumann, M. G. D., Batterman, S. A., and Zhang, G. Z.: Terpene emissions from particleboard and medium-density fiberboard products, Forest Prod. J., 49, 49–56, 1999.

Bonn, B. and Moortgat, G. K.: New particle formation during alpha- and beta-pinene oxidation by O3, OH and NO3, and the influence of water vapour: particle size distribution studies, Atmos. Chem. Phys., 2, 183–196, 2002.

Bowman, F. M., Odum, J. R., Seinfeld, J. H., and Pandis, S. N.: Mathematical model for gas-particle partitioning of secondary organic aerosol, Atmos. Environ., 31, 3921–3931, 1997.

Claeys, M., Graham, B., Vas, G., Wang, W., Vermeylen, R., Pashynska, V., Cafmeyer, J., Guyon, P., Andreae, M. O., Artaxo, P., and Maenhaut, W.: Formation of secondary organic aerosols through photooxidation of isoprene, Science, 303, 1173–1176, 2004.

DeTar, D. F. and Weis, C.: Diacyl peroxide reactions III. The behaviour of optically active 3-Phenyl-2-propyl free radical, J. Am. Chem. Soc., 79, 3045–3049, 1957.

Docherty, K. S., Wu, W., Lim, Y. B., and Ziemann, P. J.: Contributions of organic peroxides to secondary aerosol formed from reactions of monoterpenes with O3, Environ. Sci. Technol., 39, 4049–4059, 2005.

Finlayson-Pitts, B. J. and Pitts, J. N. J.: Chemistry of the Upper and Lower Atmosphere, Academic Press, San Diego, 969 pp., 2000.

Gao, S., Keywood, M., Ng, N. L., Surratt, J., Varutbangkul, V., Bahreini, R., Flagan, R. C., and Seinfeld, J. H.: Low-molecular-weight and oligomeric components in secondary organic aerosol from the ozonolysis of cycloalkenes and alpha-pinene, J. Phys. Chem. A, 108, 10 147–10 164, 2004.

Glasius, M., Duane, M., and Larsen, B. R.: Determination of polar terpene oxidation products in aerosols by liquid chromatography-ion trap mass spectrometry, J. Chromatogr. A, 833, 121–135, 1999.

Glasius, M., Lahaniati, M., Calogirou, A., Di Bella, D., Jensen, N. R., Hjorth, J., Kotzias, D., and Larsen, B. R.: Carboxylic acids in secondary aerosols from oxidation of cyclic monoterpenes by ozone, Environ. Sci. Technol., 34, 1001–1010, 2000.

Greene, F. D.: Reaction of Hydratropoyl Chloride with Sodium Peroxide, J. Am. Chem. Soc., 77, 4869–4873, 1955.

Grossert, J. S., Fancy, P. D., and White, R. L.: Fragmentation pathways of negative ions produced by electrospray ionization of acyclic dicarboxylic acids and derivatives, Can. J. Chem., 83, 1878–1890, 2005.

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.

Hinds, W. C.: Aerosol Technology, John Wiley & Sons, Inc., New York, 438 pp., 1999.

Hodgson, A. T., Beal, D., and McIlvaine, J. E. R.: Sources of formaldehyde, other aldehydes and terpenes in a new manufactured house, Indoor Air, 12, 235–242, 2002.

Hoffmann, T., Bandur, R., Marggraf, U., and Linscheid, M.: Molecular composition of organic aerosols formed in the alpha- pinene/O3 reaction: Implications for new particle formation processes, J. Geophys. Res., 103, 25 569–25 578, 1998.

Hoffmann, T., Bandur, R., and Seinfeld, J. H.: Experimental and theoretical studies on the aerosol formation potential of natural VOCs, Proceedings of the Workshop on Biogenic Hydrocarbons in the Atmospheric Boundary Layer, Amer. Meteor. Soc., August 24–27, 1997, University of Virginia, Charlottesville, Virginia, 131–134, 1997.

Holmes, N. S.: A review of particle formation events and growth in the atmosphere in the various environments and discussion of mechanistic implications, Atmos. Environ., 41, 2183–2201, 2007.

Iinuma, Y., Böge, O., Gnauk, T., and Herrmann, H.: Aerosol-chamber study of the a-pinene/O3 reaction: influence of particle acidityon aerosol yields and products, Atmos. Environ., 38, 761–773, 2004.

Joutsensaari, J., Toivonen, T., Vaattovaara, P., Vesterinen, M., Vepsalainen, J., and Laaksonen, A.: Time-resolved growth behavior of acid aerosols in ethanol vapor with a tandem-DMA technique, J. Aerosol Sci., 35, 851–867, 2004.

Kalberer, M., Paulsen, D., Sax, M., Steinbacher, M., Dommen, J., Prevot, A. S. H., Fisseha, R., Weingartner, E., Frankevich, V., Zenobi, R., and Baltensperger, U.: Identification of polymers as major components of atmospheric organic aerosols, Science, 303, 1659–1662, 2004.

Kalberer, M., Yu, J., Cocker, D. R., Flagan, R. C., and Seinfeld, J. H.: Aerosol formation in the cyclohexene-ozone system, Environ. Sci. Technol., 34, 4894–4901, 2000.

Kavouras, I. G., Mihalopoulos, N., and Stephanou, E. G.: Formation and gas/particle partitioning of monoterpenes photo- oxidation products over forests, Geophys. Res. Lett., 26, 55–58, 1999.

Kharasch, M. S., Kuderna, J., and Nudenberg, W.: Formation of optically active esters in the decomposition of optically active diacyl peroxides in solution, J. Org. Chem., 19, 1283–1289, 1954.

Koch, S., Winterhalter, R., Uherek, E., Kolloff, A., Neeb, P., and Moortgat, G. K.: Formation of new particles in the gas-phase ozonolysis of monoterpenes, Atmos. Environ., 34, 4031–4042, 2000.

Lack, D. A., Tie, X. X., Bofinger, N. D., Wiegand, A. N., and Madronich, S.: Seasonal variability of secondary organic aerosol: A global modeling study, J. Geophys. Res., 109, D03203, doi:10.1029/2003JD003418, 2004.

Larsen, B. R., Di Bella, D., Glasius, M., Winterhalter, R., Jensen, N. R., and Hjorth, J.: Gas-phase OH oxidation of monoterpenes: Gaseous and particulate products, J. Atmos. Chem., 38, 231–276, 2001.

Odum, J. R., Hoffmann, T., Bowman, F., Collins, D., Flagan, R. C., and Seinfeld, J. H.: Gas/particle partitioning and secondary organic aerosol yields, Environ. Sci. Technol., 30, 2580–2585, 1996.

Sarwar, G., Olson, D. A., Corsi, R. L., and Weschler, C. J.: Indoor fine particles: The role of terpene emissions from consumer products, J. Air Waste Manage. Assoc., 54, 367–377, 2004.

Seinfeld, J. H. and Pandis, S. N.: Atmospheric chemistry and physics, John Wiley & Sons Inc., New York, 1326 pp., 1998.

Surratt, J. D., Murphy, S. M., Kroll, J. H., Ng, N. L., Hildebrandt, L., Sorooshian, A., Szmigielski, R., Vermeylen, R., Maenhaut, W., Claeys, M., Flagan, R. C., and Seinfeld, J. H.: Chemical composition of secondary organic aerosol formed from the photooxidation of isoprene, J. Phys. Chem. A, 110, 9665–9690, 2006.

Tobias, H. J. and Ziemann, P. J.: Thermal desorption mass spectrometric analysis of organic aerosol formed from reactions of 1-tetradecene and O3 in the presence of alcohols and carboxylic acids, Environ. Sci. Technol., 34, 2105–2115, 2000.

Tolocka, M. P., Jang, M., Ginter, J. M., Cox, F. J., Kamens, R. M., and Johnston, M. V.: Formation of oligomers in secondary organic aerosol, Environ. Sci. Technol., 38, 1428–1434, 2004.

Tsigaridis, K. and Kanakidou, M.: Global modelling of secondary organic aerosol in the troposphere: a sensitivity analysis, Atmos. Chem. Phys., 3, 1849–1869, 2003.

Warnke, J., Bandur, R., and Hoffmann, T.: Capillary-HPLC-ESI-MS/MS method for the determination of acidic products from the oxidation of monoterpenes in atmospheric aerosol samples, Anal. Bioanal. Chem., 385, 34–45, 2006.

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, 207–258, 1999.

Ziemann, P.: Evidence for low-volatility diacyl peroxides as a nucleating agent and major component of aerosol formed from reactions of O3 with cyclohexene and homologous compounds, J. Phys. Chem. A, 106, 4390–4402, 2002.

Ziemann, P. J.: Formation of alkoxyhydroperoxy aldehydes and cyclic peroxyhemiacetals from reactions of cyclic alkenes with O3 in the presence of alcohols, J. Phys. Chem. A, 107, 2048–2060, 2003.