Atmos. Chem. Phys. Discuss., 10, 2915-2943, 2010
www.atmos-chem-phys-discuss.net/10/2915/2010/
doi:10.5194/acpd-10-2915-2010
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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.
Insights into secondary organic aerosol formed via aqueous-phase reactions of phenolic compounds based on high resolution mass spectrometry
Y. Sun1, Q. Zhang1, C. Anastasio2, and J. Sun3
1Department of Environmental Toxicology, University of California, Davis, CA 95616, USA
2Department of Land, Air & Water Resources, University of California, Davis, CA 95616, USA
3College of Architecture and Environment, Sichuan University, Chengdu, Sichuan, 610065, China

Abstract. Recent work has shown that aqueous-phase reactions of phenolic compounds – phenol (C6H6O), guaiacol (C7H8O2), and syringol (C8H10O3) – can form secondary organic aerosol (SOA) at high yields. Here we examine the chemical characteristics of this SOA and its formation mechanisms using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-AMS), an Ion Chromatograph (IC), and a Total Organic Carbon (TOC) analyzer. The phenolic SOA are highly oxygenated with oxygen-to-carbon (O/C) ratios in the range of 0.80–1.06 and carbon oxidation states (=2×O/C–H/C) between −0.14 and +0.47. The organic mass-to-carbon (OM/OC) ratios determined by the HR-AMS (=2.21–2.55) agree well with values determined based on the SOA mass measured gravimetrically and the OC mass from the TOC analyzer. Both the O/C and OM/OC ratios of the phenolic SOA are similar to the values observed for ambient low-volatility oxygenated/secondary OA (LV-OOA). Oxalate is a minor, but ubiquitous, component of the SOA formed from all three phenolic precursors, accounting for 1.4–5.2% of the SOA mass, with generally higher yields in experiments with H2O2 added as an ·OH source compared to without. The AMS spectra show evidence for the formation of syringol and guaiacol dimers and higher oligomers via C–C and C–O coupling of phenoxyl radicals, which are formed through oxidation pathways such as abstraction of the phenolic hydrogen atom or ·OH addition to the aromatic ring. This latter pathway leads to hydroxylation of the aromatic ring, which is one mechanism that increases the degree of oxidation of the SOA products. Compared to direct photochemical reactions of the phenols, ·OH-initiated reactions favor the formation of smaller oxidation products but less dimers or higher oligomers. Two unique and prominent ions in the syringol and guaiacol SOA spectra, m/z 306 (C16H18O6+) and m/z 246 (C14H14O4+), respectively, are observed in ambient aerosols significantly influenced by wood combustion and fog processing. Our results indicate that cloud and fog processing of phenolic compounds, especially in areas with active biomass burning, might represent an important pathway for the formation of low-volatility and highly oxygenated organic species, which would remain in particle phase after fog/cloud evaporation and affect the hygroscopicity and radiative impacts of ambient OA.

Citation: Sun, Y., Zhang, Q., Anastasio, C., and Sun, J.: Insights into secondary organic aerosol formed via aqueous-phase reactions of phenolic compounds based on high resolution mass spectrometry, Atmos. Chem. Phys. Discuss., 10, 2915-2943, doi:10.5194/acpd-10-2915-2010, 2010.
 
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