Effect of solubility limitation on hygroscopic growth and cloud drop activation of SOA particles produced from traffic exhausts

Hygroscopicity measurements of secondary organic aerosol (SOA) particles often show inconsistent results between the supersaturated and subsaturated regimes, with higher activity as cloud condensation nucleus (CCN) than indicated by hygroscopic growth. In this study, we have investigated the discrepancy between the two regimes in the Lund University (LU) smog chamber. Various anthropogenic SOA were produced from mixtures of different precursors: anthropogenic light aromatic precursors (toluene and m-xylene), exhaust from a diesel passenger vehicle spiked with the light aromatic precursors, and exhaust from two different gasoline-powered passenger vehicles. Three types of seed particles were used: soot aggregates from a diesel vehicle, soot aggregates from a flame soot generator and ammonium sulphate (AS) particles. The hygroscopicity of seed particles with condensed, photochemically produced, anthropogenic SOA was investigated with respect to critical supersaturation (s_c) and hygroscopic growth factor (gf) at 90% relative humidity. The hygroscopicity parameter κ was calculated for the two regimes: κ_sc and κ_gf, from measurements of s_c and gf, respectively. The two κ showed significant discrepancies, with a κ_gf /κ_sc ratio closest to one for the gasoline experiments with ammonium sulphate seed and lower for the soot seed experiments. Empirical observations of s_c and gf were compared to theoretical predictions, using modified Köhler theory where water solubility limitations were taken into account. The results indicate that the inconsistency between measurements in the subsaturated and supersaturated regimes may be explained by part of the organic material in the particles produced from anthropogenic precursors having a limited solubility in water.