Aerosol Hygroscopicity at High (99 to 100%) Relative Humidities

The hygroscopicity of an aerosol largely determines its influence on climate and, for smaller particles, atmospheric lifetime. While much aerosol hygroscopicity data is available at lower relative humidities (RH) and under cloud formation conditions (RH>100%), relatively little data is available at high RH (99 to 100%). We measured the size of droplets at high RH that had formed on particles composed of one of seven compounds with dry diameters between 0.1 and 0.5 μm. We report the hygroscopicity of these compounds using a parameterization of the Kelvin term, in addition to a standard parameterization (κ) of the Raoult term. For inorganic compounds, hygroscopicity could reliably be predicted using water activity data (measured in macroscopic solutions) and assuming a surface tension of pure water. In contrast, most organics exhibited a slight to mild increase in hygroscopicity with droplet diameter. This trend was strongest for sodium dodecyl sulfate (SDS), the most surface-active compound studied. The results suggest that partitioning of surface-active compounds away from the bulk solution, which reduces hygroscopicity, dominates any increases in hygroscopicity due to reduced surface tension. These experiments were only performed on single-component aerosols, however, and therefore surface activity might still enhance the hygroscopicity of particles containing both inorganic and organic components. Furthermore, we saw no evidence that micellization limits SDS activity in micron-sized solution droplets, as observed in macroscopic solutions. These results suggest that while the high-RH hygroscopicity of inorganic compounds can be reliably predicted using readily available data, surface-activity parameters obtained from macroscopic solutions with organic solutes may be inappropriate for calculations of the hygroscopicity of micron-sized droplets.