Atmos. Chem. Phys. Discuss., 3, 4359-4391, 2003
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Measurements of photo-oxidation products from the reaction of a series of alkyl-benzenes with hydroxyl radicals during EXACT using comprehensive gas chromatography
J. F. Hamilton1, A. C. Lewis2, C. Bloss1, V. Wagner1, A. P. Henderson3, B. T. Golding3, K. Wirtz4, M. Martin-Reviejo4, and M. J. Pilling1
1University of Leeds, Department of Chemistry, Woodhouse Lane, Leeds, LS2 9JT, UK
2University of York, Department of Chemistry, Heslington, York, YO10 5DD, UK
3School of Natural Sciences – Chemistry, Bedson Building, University of Newcastle upon Tyne, Newcastle upon Tyne NEI 7RU, UK
4Fundaci´on Centro de Estudios Ambientales del Mediterráneo (CEAM), EUPHORE laboratories, C/Charles Darwin, 14 Parc Technológico, Paterna, Valencia, Spain

Abstract. Photo-oxidation products from the reaction of a series of alkyl-benzenes, (benzene, toluene, p-xylene and 1,3,5-trimethyl-benzene) with hydroxyl radicals in the presence of  NOx have been investigated using comprehensive gas chromatography (GCXGC). A GCXGC system has been developed which utilises valve modulation and independent separations as a function of both volatility and polarity. A number of carbonyl-type compounds were identified during a series of reactions carried out at the European Photoreactor (EUPHORE), a large volume outdoor reaction chamber in Valencia, Spain. Two litre chamber air samples were cryo-focused, with a sampling frequency of 30 min, allowing the evolution of species to be followed over oxidation periods of 3–6 h. To facilitate product identification, several carbonyl compounds, which were possible products of the photo-oxidation, were synthesised and used as reference standards.

For toluene reactions, observed oxygenated intermediates found included the co-eluting pair a-angelicalactone/4-oxo-2-pentenal, maleic anhydride, citraconic anhydride, benzaldehyde and p-methyl benzoquinone. In the p-xylene experiment, the products identified were E/Z-hex-3-en-2,5-dione and citraconic anhydride. For 1,3,5-TMB reactions, the products identified were 3,5-dimethylbenzaldehyde, 3,5-dimethyl-3H-furan-2-one and 3-methyl-5-methylene-5H-furan-2-one. Preliminary quantification was carried out on identified compounds using liquid standards. Comparison of FTIR and GCXGC for the measurement of the parent aromatics generally showed good agreement.

Citation: Hamilton, J. F., Lewis, A. C., Bloss, C., Wagner, V., Henderson, A. P., Golding, B. T., Wirtz, K., Martin-Reviejo, M., and Pilling, M. J.: Measurements of photo-oxidation products from the reaction of a series of alkyl-benzenes with hydroxyl radicals during EXACT using comprehensive gas chromatography, Atmos. Chem. Phys. Discuss., 3, 4359-4391, doi:10.5194/acpd-3-4359-2003, 2003.
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