Atmos. Chem. Phys. Discuss., 12, 2435-2482, 2012
www.atmos-chem-phys-discuss.net/12/2435/2012/
doi:10.5194/acpd-12-2435-2012
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under the Creative Commons Attribution 3.0 License.
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This discussion paper has been under review for the journal Atmospheric Chemistry and Physics (ACP). Please refer to the corresponding final paper in ACP.
The effect of photochemical ageing and initial precursor concentration on the composition and hygroscopic properties of β-caryophyllene secondary organic aerosol
M. R. Alfarra1,2, J. F. Hamilton3, K. P. Wyche4, N. Good1,*, M. W. Ward3, T. Carr4, M. H. Barley1, P. S. Monks4, M. E. Jenkin5, and G. B. McFiggans1
1Centre for Atmospheric Science, School of Earth Atmospheric and Environmental Sciences, University of Manchester, UK
2National Centre for Atmospheric Science (NCAS), School of Earth Atmospheric and Environmental Sciences, University of Manchester, UK
3Department of Chemistry, University of York, UK
4Atmospheric Chemistry Group, Department of Chemistry, University of Leicester, UK
5Atmospheric Chemistry Services, Okehampton, Devon, UK
*now at: Centre for Atmospheric and Instrumentation Research Science & Technology Research Institute, University of Hertfordshire, UK

Abstract. The effect of photochemical ageing and initial precursor concentration on the composition and hygroscopic properties of secondary organic aerosol (SOA) formed during the chamber photo-oxidation of β-caryophyllene/NOx mixtures were investigated. Nucleation of β-caryophyllene SOA particles occurred almost immediately after oxidation was initiated and led to the formation of fresh SOA with a relatively simpler composition than has been reported for monoterpenes. The SOA yield values ranged from 9.5–26.7% and 30.4–44.5% using a DMPS and an AMS mass based measurements, respectively. A total of 20 compounds were identified in the SOA by LC-MS, with the most abundant compounds identified as β-caryophyllonic acid and β-caryophyllinic acid/β-nocaryophyllonic acid. The O:C and H:C elemental ratios of products identified in the condensed phase ranged from 0.20 to 1.00 and 1.00 to 2.00, with average values of 0.39 and 1.58, respectively. The increase in the O:C ratio was associated with a decrease in the saturation concentration of the identified compounds. The compounds identified in the lower initial concentration experiments were more oxidised compared to those that were found to be more abundant in the higher initial concentration experiments with average O:C ratios of 0.51 and 0.27, respectively. Photochemical ageing led to a more complex SOA composition with a larger contribution coming from lower molar mass, higher generation products, where both double bonds had been oxidised. This effect was more evident in the experiments conducted using the lower initial precursor concentration; a finding confirmed by the temporal behaviour of key organic mass fragment measured by an Aerosol Mass Spectrometer. Although the composition changed with both initial precursor concentration and ageing, this had no significant measurable effect on the hygroscopic properties of the SOA formed. The latter finding might have been influenced by the difference in pre-treatment of the semivolatile-containing particles prior to their measurements.

Citation: Alfarra, M. R., Hamilton, J. F., Wyche, K. P., Good, N., Ward, M. W., Carr, T., Barley, M. H., Monks, P. S., Jenkin, M. E., and McFiggans, G. B.: The effect of photochemical ageing and initial precursor concentration on the composition and hygroscopic properties of β-caryophyllene secondary organic aerosol, Atmos. Chem. Phys. Discuss., 12, 2435-2482, doi:10.5194/acpd-12-2435-2012, 2012.
 
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