Cloud droplet activation of secondary organic aerosol is mainly controlled by molecular weight, not water solubility

Aerosol particles strongly influence global climate by modifying the properties of clouds. An accurate assessment of the aerosol impact on climate requires knowledge of the concentration of cloud condensation nuclei (CCN), a subset of aerosol particles that can activate and form cloud droplets in the atmosphere. Atmospheric particles typically consist of a myriad of organic species, which frequently dominate the particle composition. As a result, CCN concentration is often a strong function of the hygroscopicity of organics in the particles. Earlier studies showed organic hygroscopicity increases nearly linearly with oxidation level. Such an increase in hygroscopicity is conventionally attributed to higher water solubility for more oxidized organics. By systematically varying the water content of activating droplets, we show that for the majority of secondary organic aerosols (SOAs), essentially all organics are dissolved at the point of droplet activation. Therefore, for droplet activation, the organic hygroscopicity is not limited by solubility but is dictated mainly by the molecular weight of organic species. Instead of increased water solubility as previously thought, the increase in the organic hygroscopicity with oxidation level is largely because (1) SOAs formed from smaller precursor molecules tend to be more oxidized and have lower average molecular weight and (2) during oxidation, fragmentation reactions reduce average organic molecule weight, leading to increased hygroscopicity. A simple model of organic hygroscopicity based on molecular weight, oxidation level, and volatility is developed, and it successfully reproduces the variation in SOA hygroscopicity with oxidation level observed in the laboratory and field studies.