References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-6-5009-2006

Formation of secondary organic aerosol and oligomers from the ozonolysis of enol ethers

Sadezky

¹ ² Chaimbault

³ Mellouki

² Römpp

¹ Winterhalter

¹ Le Bras

² Moortgat

G. K.

Max-Planck-Institute for Chemistry, Atmospheric Chemistry Department, P.O. Box 3060, 55020 Mainz, Germany

Laboratoire de Combustion et de Systèmes Réactifs, CNRS, 1C Avenue de la Recherche Scientifique, 45071 Orléans Cedex 2, France

Institut de Chimie Organique et Analytique, UMR 6005, BP 6759, University of Orléans, 45067 Orléans Cedex 2, France

31 10 2006

6 12 5009 5024

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Formation of secondary organic aerosol has been observed in the gas phase ozonolysis of a series of enol ethers, among them several alkyl vinyl ethers (AVE, ROCH=CH2), such as ethyl, propyl, n-butyl, iso-butyl, t-butyl vinyl ether, and ethyl propenyl ether (EPE, C2H5OCH=CHCH3). The ozonolysis has been studied in a 570 l spherical glass reactor at ambient pressure (730 Torr) and room temperature (296 K). Gas phase reaction products were investigated by in-situ FTIR spectroscopy, and secondary organic aerosol (SOA) formation was monitored by a scanning mobility particle sizer (SMPS). The chemical composition of the formed SOA was analysed by a hybrid mass spectrometer using electrospray ionization (ESI). The main stable gas phase reaction product is the respective alkyl formate ROC(O)H, formed with yields of 60 to 80%, implying that similar yields of the corresponding excited Criegee Intermediates (CI) CH2O2 for the AVE and CH3CHO2 for EPE are generated. Measured SOA yields are between 2 to 4% for all enol ethers. Furthermore, SOA formation is strongly reduced or suppressed by the presence of an excess of formic acid, which acts as an efficient CI scavenger. Chemical analysis of the formed SOA by ESI(+)/MS-TOF allows to identify oligomeric compounds in the mass range 200 to 800 u as its major constituents. Repetitive chain units are identified as CH2O2 (mass 46) for the AVE and C2H4O2 (mass 60) for EPE and thus have the same chemical compositions as the respective major Criegee Intermediates formed during ozonolysis of these ethers. The oligomeric structure and chain unit identity are confirmed by HPLC/ESI(+)/MS-TOF and ESI(+)/MS/MS-TOF experiments, whereby successive and systematic loss of a fragment with mass 46 for the AVE (and mass 60 for EPE) is observed. It is proposed that the oligomer has the following basic structure of an oligoperoxide, -[CH(R)-O-O]n-, where R=H for the AVE and R=CH3 for the EPE. Oligoperoxide formation is thus suggested to be another, so far unknown reaction of stabilized Criegee Intermediates in the gas phase ozonolysis of oxygen-containing alkenes leading to SOA formation.

References 1

Barton, M., Ebdon, J. R., Foster, A. B., and Rimmer, S.: Ozonolysis of tetramethylethylene: Characterization of cyclic and open-chain oligoperoxidic products, J. Org. Chem., 69, 6967–6973, 2004.

Bonn, B., Schuster, G., and Moortgat, G. K.: Influence of water vapor on the process of new particle formation during monoterpene ozonolysis, J. Phys. Chem. A, 106, 2869–2881, 2002.

Bunnelle, W. H.: Preparation, properties, and reactions of carbonyl oxides, Chem. Rev., 91, 335–362, 1991.

Calvert, J. G., Atkinson R., Kerr J. A., Madronich S., Moortgat G. K., Wallington, T. J., and Yarwood, G.: The mechanisms of atmospheric oxidation of the alkenes, Oxford University Press, 2000.

Chaimbault, P., Elfakir, C., and Lafosse, M.: Comparison of the retention behavior of polyethoxylated alcohols on porous graphitic carbon and polar as well as apolar-bonded silica phases, J. Chromatogr. A, 797, 83–91, 1998.

Criegee, R.: The course of ozonation of unsaturated compounds, Record Chem. Prog., 18, 111–120, 1957.

Finlayson, B. J., Pitts, J. N., and Akimoto, H.: Production of vibrationnally excited OH in chemiluminescent ozone-olefin reactions, Chem. Phys. Lett., 12, 495–498, 1972.

Docherty, K. S. and Ziemann, P. J.: Effects of stabilized Criegee Intermediate and OH radical scavengers on aerosol formation from reactions of β-pinene with O3, Aerosol Sci. Technol., 37, 877-891, 2003.

Gao, S., Nga, L. N., Keywood, M., Varutbangkul, V., Bahreini, R., Nenes, A., He, J., Yoo, K. Y., Beauchamp, J. L., Hodyss, R. P., Flagan, R. C., and Seinfeld, J. H.: Particle phase acidity and oligomer formation in secondary organic aerosol, Env. Sci. Technol., 38, 6582–6589, 2004.

George, C., Sidebottom, H., Mellouki, A., Barnes, I., Pilling, M., Herrmann, H., Wortham, H., Kirchner, F., Wirtz, K., and \mboxZetzsch, C.: Multiphase chemistry of oxygenated species in the atmosphere, Final report, EVK2-CT-2001-00114, July, 2005.

Horie, O., Neeb, P., and Moortgat, G. K.: The reactions of the Criegee Intermediate CH3CHOO in the gas-phase ozonolysis of 2-butene isomers, Int. J. Chem. Kin., 29, 461–468, 1997.

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.

Keul, H., Choi, H. S., and Kuczkowski, R. L.: Ozonolysis of enol ethers. Formation of 3-alkoxy-1,2-dioxolanes by concerted addition of a carbonyl oxide to an enol ether, J. Org. Chem., 50, 3365–3371, 1985.

Keywood, M. D., Kroll, J. H., Varutbangkul, V., Bahreini, R., Flagan, R. C. and Seinfeld, J. H.: Secondary organic aerosol formation from cyclohexene ozonolysis: Effect of OH scavenger and the role of radical chemistry, Environ. Sci. Technol., 38, 3343–3350, 2004.

Klotz, B., Barnes, I., and Imamura, T.: Product study of the gas-phase reactions of O3, OH and NO3 radicals with methyl vinyl ether, Phys. Chem. Chem. Phys., 6, 1725–1734, 2004.

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.

Lockley, J. E., Ebdon, J. R., Rimmer, S., and Tabner, B. J.: Polymerization of methyl methacrylate initiated by ozonates of tetramethylethene, Polymer, 42, 1797–1807, 2001.

Neeb, P., Horie, O., and Moortgat, G. K.: The ethene-ozone reaction in the gas phase, J. Phys. Chem. A, 102, 6778–6785, 1998.

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.

Pankow, J. F.: An absorption model of gas/particle partitioning involved in the formation of secondary organic aerosol, Atmos. Environ., 28, 189–193, 1994.

Römpp, A.: Analysis of organic compounds in atmospheric aerosol by liquid chromatography-high resolution mass spectrometry (LC/MS/MS-TOF): method development and applications, PhD thesis, Johannes-Gutenberg University of Mainz, 2003.

Sadezky, A.: Ozonolyse d'éthers insaturés: Etudes des mécanismes en phase gazeuse et de la formation d'aérosol organique secondaire, PhD thesis, University of Orléans, 2005.

Seinfeld, J. H. and Pandis, S. N.: Atmospheric chemistry and physics: From air pollution to climate change, John Wiley & Sons Inc., New York, p. 738, 1998.

Seinfeld, J. H. and Pankow, J. F.: Organic atmospheric particular material, Annu. Rev. Phys. Chem., 54, 121–140, 2003.

Thamm, J., Wolff, S., Turner, W. V., Gäb, S., Thomas, W., Zabel, F., Fink, E. H., and Becker, K. H.: Proof of the formation of hydroperoxymethyl formate in the ozonolysis of ethene: Synthesis and FTIR spectra of the authentic compound, Chem. Phys. Lett., 258, 155–158, 1996.

Thiault, G., Thévenet, R., Mellouki, A., and Le Bras, G.: OH and O3 initiated oxidation of ethyl vinyl ether, Phys. Chem. Chem. Phys., 4, 613–619, 2002.

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.

Winterhalter, R., Neeb, P., Grossmann, D., Kolloff, A., Horie, O., and Moortgat, G. K.: Products and mechanism of the gas phase reaction of ozone with $\beta $-pinene, J. Atmos. Chem., 35, 165–197, 2000.

Zahardis, J., LaFranchi, B. W., and Petrucci, G. A.: Photoelectron resonance capture ionization-aerosol mass spectrometry of the ozonolysis products of oleic acid particles: Direct measure of higher molecular weight oxygenates, J. Geophys. Res., 110, D08307, doi:10.1029/2004JD005336, 2005.

Ziemann, P. J.: 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.