ABSTRACT OF THE DISSERTATION
Chemistry of Secondary Organic Aerosol Formation From the Reaction of Hydroxyl Radicals With Aromatic Compounds
Christen Michelle Strollo Gordon
Doctor of Philosophy, Graduate Program in Chemistry
University of California, Riverside, August 2013
Dr. Paul J. Ziemann, Chairperson
Secondary Organic Aerosol (SOA) can have significant impacts on visibility, human health, and global climate, and a more detailed understanding of the roles of both gas-phase and heterogeneous/multiphase chemistry is needed to develop air quality models that accurately represent the formation of SOA from the oxidation of aromatic hydrocarbons. The objective of this dissertation is to investigate the mechanisms and products of SOA formation from the OH radical-initiated reaction of aromatics in an environmental chamber. This is done using a combination of thermal desorption particle beam mass spectrometry, functional group and CHON elemental analysis, and UV spectroscopy. Chapter 2 investigates the variability of SOA yields measured for reactions of m-xylene and other methylbenzenes as a function of humidity, seed particle, OH source, NOx concentration, light intensity, and mass loading. The most significant factor that determined SOA yields was the amount of m-xylene reacted. The chapter concludes with a discussion of a series of experiments conducted to isolate the contribution to SOA formation of specific primary gas-phase products of the m-xylene reaction. Chapter 3 examines the formation of SOA from the oxidation of 3-methylfuran, which produces among other compounds an α,β-unsaturated dicarbonyl that is also a major product of the oxidation of m-xylene. We have determined that SOA forms from the heterogeneous/multiphase oligomerization of primary reaction products to form esters, hemiacetals, and acetals, and not through second-generation reactions. Chapter 4 discusses the chemical composition of SOA formed from the reaction of m-xylene and how the variables detailed in Chapter 2 affect the composition. Experiments were carried out with deuterated m-xylene to confirm that SOA is dominated by hemiacetals formed from C8 ring-opened primary products and their second-generation products. Finally, Chapter 5 shows that SOA formed from the oxidation of benzaldehyde in the absence of NOx is largely composed of oligomeric products formed through heterogeneous/multiphase reactions involving benzoic acid, peroxybenzoic acid, phenol, and benzaldehyde.