Abstract
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 Chromatography system (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 the particle phase after fog/cloud evaporation and affect the chemical and optical properties of atmospheric particles.
Highlights
Organic aerosols (OA) account for a significant fraction of fine particulate mass in the atmosphere (Saxena and Hildemann, 1996; Kanakidou et al, 2005; Zhang et al, 2007) and likely play important roles in affecting the radiative balance of the Earth and air quality
The actual mass yields of SOA under ambient atmospheric conditions are likely higher because semi-volatile species probably more extensively evaporate during our drying procedure than in ambient particles
Since almost no original phenolic compounds were detected in the solids left in the Al cup after drying, we are confident that the organic materials analyzed for this study are the low-volatility SOA products
Summary
Organic aerosols (OA) account for a significant fraction of fine particulate mass in the atmosphere (Saxena and Hildemann, 1996; Kanakidou et al, 2005; Zhang et al, 2007) and likely play important roles in affecting the radiative balance of the Earth and air quality. Gas-phase oxidation of volatile organic compounds (VOCs) and subsequent gas-to-particle partitioning, recent studies have shown that reactions in atmospheric aqueous phases may represent an important pathway for SOA production (Blando and Turpin, 2000; Kanakidou et al, 2005; Kroll and Seinfeld, 2008; Hallquist et al, 2009). In this work we describe the chemical characteristics of the low-volatility, aqueous-phase reaction products of phenol (C6H6O, MW=94), 2-methoxyphenol (guaiacol, C7H8O2, MW=124), and 2,6-dimethoxyphenol (syringol, C8H10O3, MW=154), which represent the three basic structures of phenols emitted from wood combustion (Simoneit et al, 1993). We characterize the composition of the phenolic SOA, and elucidate the mechanisms responsible for its formation, based on analysis with an Aerodyne High-Resolution Timeof-Flight Aerosol Mass Spectrometer (HR-AMS) in conjunction with measurements of total organic carbon (TOC) and small organic acids
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