Trends in the oxidation and relative volatility of chamber-generated secondary organic aerosol

The relationship between the oxidation state and relative volatility of secondary organic aerosol (SOA) from the oxidation of a wide range of hydrocarbons is investigated using a fast-stepping, scanning thermodenuder interfaced with a high-resolution time-of-flight aerosol mass spectrometer (AMS). SOA oxidation state varied widely across the investigated range of parent hydrocarbons but was relatively stable for replicate experiments using a single hydrocarbon precursor. On average, unit mass resolution indicators of SOA oxidation (e.g., AMS f ₄₃ and f ₄₄) are consistent with previously reported values. Linear regression of H:C vs. O:C obtained from parameterization of f ₄₃ and f ₄₄ and elemental analysis of high-resolution spectra in Van Krevelen space both yield a slope of ~-0.5 across different SOA types. A similar slope was obtained for a distinct subset of toluene/NO _x reactions in which the integrated oxidant exposure was varied to alter oxidation. The relative volatility of different SOA types displays similar variability and is strongly correlated with SOA oxidation state ( $\stackrel{-}{\mathrm{OS}}$ ). On average, relatively low oxidation and volatility were observed for aliphatic alkene (including terpenes) and n-alkane SOA while the opposite is true for mono- and polycyclic aromatic hydrocarbon SOA. Effective enthalpy for total chamber aerosol obtained from volatility differential mobility analysis is also highly correlated with $\stackrel{-}{\mathrm{OS}}$ c indicating a primary role for oxidation levels in determining the volatility of chamber SOA. Effective enthalpies for chamber SOA are substantially lower than those of neat organic standards but are on the order of those obtained for partially oligomerized glyoxal and methyl glyoxal.