Atmos. Chem. Phys. Discuss., 9, 15595-15640, 2009
© Author(s) 2009. This work is distributed
under the Creative Commons Attribution 3.0 License.
Review Status
This discussion paper has been under review for the journal Atmospheric Chemistry and Physics (ACP). Please refer to the corresponding final paper in ACP.
Aerosol hygroscopicity at high (99 to 100%) relative humidities
C. R. Ruehl1, P. Y. Chuang1, and A. Nenes2
1Earth & Planetary Sciences, University of California, Santa Cruz, USA
2Earth & Atmospheric Sciences, Georgia Institute of Technology, Atlanta, USA

Abstract. 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 (99.2 to 99.9%). 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, and calculated the hygroscopicity of these compounds. We use a parameterization of the Kelvin term, in addition to a standard parameterization (κ) of the Raoult term, to express the hygroscopicity of surface-active compounds.

For inorganic compounds, hygroscopicity could reliably be predicted using water activity data 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. This is opposite to what is typically assumed for soluble surfactants. 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.

Citation: Ruehl, C. R., Chuang, P. Y., and Nenes, A.: Aerosol hygroscopicity at high (99 to 100%) relative humidities, Atmos. Chem. Phys. Discuss., 9, 15595-15640, doi:10.5194/acpd-9-15595-2009, 2009.
Search ACPD
Discussion Paper
    Final Revised Paper