Gas/particle partitioning of carbonyls in the photooxidation of isoprene and 1,3,5-trimethylbenzene

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Healy, Robert M.
Wenger, John C.
Metzger, Axel
Duplissy, Jonathan
Kalberer, Markus
Dommen, Josef
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Copernicus Publications on behalf of the European Geosciences Union (EGU)
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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 NOx 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. 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 and particle-phase chemical reactions for SOA formation and growth during the atmospheric degradation of anthropogenic and biogenic hydrocarbons.
Atmospheric modeling , Carbonyl compound , Filter , Gas , Isoprene , Particle motion , Partition coefficient , Partitioning , Photooxidation , Sampling
Healy, R.M., Wenger, J.C., Metzger, A., Duplissy, J., Kalberer, M. and Dommen, J. (2008) 'Gas/particle partitioning of carbonyls in the photooxidation of isoprene and 1,3,5-trimethylbenzene', Atmospheric Chemistry and Physics, 8(12), pp. 3215-3230. doi:10.5194/acp-8-3215-2008