Articles | Volume 18, issue 7
Atmos. Chem. Phys., 18, 4673–4693, 2018
Atmos. Chem. Phys., 18, 4673–4693, 2018

Research article 06 Apr 2018

Research article | 06 Apr 2018

Ozonolysis of α-phellandrene – Part 2: Compositional analysis of secondary organic aerosol highlights the role of stabilised Criegee intermediates

Felix A. Mackenzie-Rae1, Helen J. Wallis2, Andrew R. Rickard2,3, Kelly L. Pereira2, Sandra M. Saunders1, Xinming Wang4,5, and Jacqueline F. Hamilton2 Felix A. Mackenzie-Rae et al.
  • 1School of Molecular Sciences, The University of Western Australia, Crawley WA 6009, Australia
  • 2Wolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, York, YO10 5DD, UK
  • 3National Centre for Atmospheric Science, University of York, York, YO10 5DD, UK
  • 4State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China
  • 5Center for Excellence in Regional Atmospheric Environment, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 361021, China

Abstract. The molecular composition of the water-soluble fraction of secondary organic aerosol (SOA) generated from the ozonolysis of α-phellandrene is investigated for the first time using high-pressure liquid chromatography coupled to high-resolution quadrupole–Orbitrap tandem mass spectrometry. In total, 21 prominent products or isomeric product groups were identified using both positive and negative ionisation modes, with potential formation mechanisms discussed. The aerosol was found to be composed primarily of polyfunctional first- and second-generation species containing one or more carbonyl, acid, alcohol and hydroperoxide functionalities, with the products significantly more complex than those proposed from basic gas-phase chemistry in the companion paper (Mackenzie-Rae et al., 2017). Mass spectra show a large number of dimeric products are also formed. Both direct scavenging evidence using formic acid and indirect evidence from double bond equivalency factors suggest the dominant oligomerisation mechanism is the bimolecular reaction of stabilised Criegee intermediates (SCIs) with non-radical ozonolysis products. Saturation vapour concentration estimates suggest monomeric species cannot explain the rapid nucleation burst of fresh aerosol observed in chamber experiments; hence, dimeric species are believed to be responsible for new particle formation, with detected first- and second-generation products driving further particle growth in the system. Ultimately, identification of the major constituents and formation pathways of α-phellandrene SOA leads to a greater understanding of the atmospheric processes and implications of monoterpene emissions and SCIs, especially around eucalypt forests where α-phellandrene is primarily emitted.

Short summary
Native to Australasia, the remarkable adaptability, rapid growth rates and high quality wood of eucalypt trees has led to them the most widely planted hardwood forest trees in the world. In contrast to boreal and tropical forests, there has been little study of aerosol formation in these regions. Here, we study the secondary organic aerosol formation from the very fast reaction of α-phellandrene, emitted from eucalypts, and identify key products and reaction pathways.
Final-revised paper