ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-12-6417-2012 The effect of photochemical ageing and initial precursor concentration on the composition and hygroscopic properties of β-caryophyllene secondary organic aerosol Alfarra M. R. 1 2 Hamilton J. F. 3 Wyche K. P. 4 Good N. 1 7 Ward M. W. 3 Carr T. 4 Barley M. H. 1 Monks P. S. 4 Jenkin M. E. 5 Lewis A. C. 6 McFiggans G. B. 1 Centre for Atmospheric Science, School of Earth Atmospheric and Environmental Sciences, University of Manchester, UK National Centre for Atmospheric Science (NCAS), School of Earth Atmospheric and Environmental Sciences, University of Manchester, UK Department of Chemistry, University of York, UK Atmospheric Chemistry Group, Department of Chemistry, University of Leicester, UK Atmospheric Chemistry Services, Okehampton, Devon, UK National Centre for Atmospheric Science, University of York, Heslington, York, UK now at: Centre for Atmospheric and Instrumentation Research, University of Hertfordshire, UK 24 07 2012 12 14 6417 6436 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/12/6417/2012/acp-12-6417-2012.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/12/6417/2012/acp-12-6417-2012.pdf

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/NO<sub>x</sub> 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 differential mobility particle sizer (DMPS) and an aerosol mass spectrometer (AMS) mass based measurements, respectively. A total of 20 compounds were identified in the SOA by LC-MS/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.

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