On the link between hygroscopicity, volatility, and oxidation state of ambient and water-soluble aerosols in the southeastern United States

Abstract. The formation of secondary organic aerosols (SOAs) combined with the partitioning of semivolatile organic components can impact numerous aerosol properties including cloud condensation nuclei (CCN) activity, hygroscopicity, and volatility. During the summer 2013 Southern Oxidant and Aerosol Study (SOAS) field campaign in a rural site in the southeastern United States, a suite of instruments including a CCN counter, a thermodenuder (TD), and a high-resolution time-of-flight aerosol mass spectrometer (AMS) were used to measure CCN activity, aerosol volatility, composition, and oxidation state. Particles were either sampled directly from ambient or through a particle-into-liquid sampler (PILS), allowing the investigation of the water-soluble aerosol component. Ambient aerosols exhibited size-dependent composition with larger particles being more hygroscopic. The hygroscopicity of thermally denuded aerosols was similar between ambient and PILS-generated aerosols and showed limited dependence on volatilization. Results of AMS three-factor positive matrix factorization (PMF) analysis for the PILS-generated aerosols showed that the most hygroscopic components are most likely the most and the least volatile features of the aerosols. No clear relationship was found between organic hygroscopicity and the oxygen-to-carbon ratio; in fact, isoprene-derived organic aerosols (isoprene-OAs) were found to be the most hygroscopic factor, while at the same time being the least oxidized and likely most volatile of all PMF factors. Considering the diurnal variation of each PMF factor and its associated hygroscopicity, isoprene-OA and more-oxidized oxygenated organic aerosols are the prime contributors to hygroscopicity and co-vary with less-oxidized oxygenated organic aerosols in a way that induces the observed diurnal invariance in total organic hygroscopicity. Biomass burning organic aerosols contributed little to aerosol hygroscopicity, which is expected since there was little biomass burning activity during the sampling period examined.