Organic aerosol in the summertime southeastern United States: components and their link to volatility distribution, oxidation state and hygroscopicity

The volatility distribution of the organic aerosol (OA) and its sources during the Southern Oxidant and Aerosol Study (SOAS; Centreville, Alabama) was constrained using measurements from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a thermodenuder (TD). Positive matrix factorization (PMF) analysis was applied on both the ambient and thermodenuded high-resolution mass spectra, leading to four factors: more oxidized oxygenated OA (MO-OOA), less oxidized oxygenated OA (LO-OOA), an isoprene epoxydiol (IEPOX)-related factor (isoprene-OA) and biomass burning OA (BBOA). BBOA had the highest mass fraction remaining (MFR) at 100 °C, followed by the isoprene-OA, and the LO-OOA. Surprisingly the MO-OOA evaporated the most in the TD. The estimated effective vaporization enthalpies assuming an evaporation coefficient equal to unity were 58 ± 13 kJ mol −1 for the LO-OOA, 89 ± 10 kJ mol −1 for the MO-OOA, 55 ± 11 kJ mol −1 for the BBOA, and 63 ± 15 kJ mol −1 for the isoprene-OA. The estimated volatility distribution of all factors covered a wide range including both semi-volatile and low-volatility components. BBOA had the lowest average volatility of all factors, even though it had the lowest O  :  C ratio among all factors. LO-OOA was the more volatile factor and its high MFR was due to its low enthalpy of vaporization according to the model. The isoprene-OA factor had intermediate volatility, quite higher than suggested by a few other studies. The analysis suggests that deducing the volatility of a factor only from its MFR could lead to erroneous conclusions. The oxygen content of the factors can be combined with their estimated volatility and hygroscopicity to provide a better view of their physical properties.