Abstract. Atmospheric aerosol particles typically consist of inorganic salts and organic material. The inorganic compounds as well as their hygroscopic properties are well defined, but the effect of organic compounds on cloud droplet activation is still poorly characterized. The focus of the present study is the organic compounds that are surface active i.e. tend to concentrate on droplet surface and decrease the surface tension. Gibbsian surface thermodynamics was used to find out how partitioning between droplet surface and the bulk of the droplet affects the surface tension and the surfactant bulk concentration in droplets large enough to act as cloud condensation nuclei. Sodium dodecyl sulfate (SDS) was used together with sodium chloride to investigate the effect of surfactant partitioning on the Raoult effect (solute effect). While accounting for the surface to bulk partitioning is known to lead to lowered bulk surfactant concentration and thereby to increased surface tension compared to a case in which the partitioning is neglected, the present results show that the partitioning also alters the Raoult effect, and that the change is large enough to further increase the critical supersaturation and hence decrease cloud droplet activation. The fraction of surfactant partitioned to droplet surface increases with decreasing droplet size, which suggests that surfactants might enhance the activation of larger particles relatively more thus leading to less dense clouds. Cis-pinonic acidammonium sulfate aqueous solutions were studied in order to study the partitioning with compounds found in the atmosphere and to find out the combined effects of dissolution and partitioning behavior. The results show that the partitioning consideration presented in this paper alters the shape of the Köhler curve when compared to calculations in which the partitioning is neglected either completely or in the Raoult effect. In addition, critical supersaturation was measured for SDS particles with dry radii of 25-60 nm using a static paralCorrespondence to: R. Sorjamaa (riikka.sorjamaa@uku.fi) lel plate Cloud Condensation Nucleus Counter. The experimentally determined critical supersaturations agree very well with theoretical calculations taking the surface to bulk partitioning fully into account and are much higher than those calculated neglecting the partitioning.

A B S T R A C T 12 COONa] in the diameter range 33-140 nm at 296 K using a static thermal gradient diffusion cloud condensation nucleus counter. These fatty acid sodium salts are surface active molecules which have all been identified in atmospheric aerosol particles. Experimental critical supersaturations increased systematically with increasing carbon chain length and were in the range 0.96-1.34% for particles with a dry diameter of 40 nm. The experimental data were modelled using Köhler theory modified to account for partitioning of the surface active fatty acid sodium salts between the droplet bulk and surface as well as Köhler theory including surface tension reduction without accounting for surfactant partitioning and Köhler theory using the surface tension of pure water. It was found that Köhler theory using the reduced surface tension with no account for surfactant partitioning underpredicts experimental critical supersaturations significantly, whereas Köhler theory modified to account for surfactant partitioning and Köhler theory using the surface tension of pure water reproduced the experimental data well.

Abstract. Cloud droplet activation of wettable insoluble compounds has been studied theoretically by assuming that droplet growth happens through multilayer adsorption. The idea is to include an adsorption isotherm in Köhler theory instead of the solute term. This makes it possible to describe the equilibrium growth of insoluble particles and to find out their critical saturation ratios. The critical saturation ratios calculated in this way are comparable to those of completely soluble particles at certain ranges of adsorption isotherm parameter values. The results indicate that adsorption could cause wettable insoluble compounds to activate in atmospheric conditions. However, more data on the adsorption parameters for wettable organic substances is needed to confirm this conclusion.

Abstract. Atmospheric aerosol particles typically consist of inorganic salts and organic material. The inorganic compounds as well as their hygroscopic properties are well defined, but the effect of organic compounds on cloud droplet activation is still poorly characterized. The focus of the present study is in the organic compounds that are surface active i.e. they concentrate on droplet surface and decrease droplet surface tension. Gibbsian surface thermodynamics were used to find out how partitioning in binary and ternary aqueous solutions affects the droplet surface tension and the droplet bulk concentration in droplets large enough to act as cloud condensation nuclei. Sodium dodecyl sulfate was used as a model compound together with sodium chloride to find out the effect the correct evaluation of surfactant partitioning has on the solute effect (Raoult effect). While the partitioning is known to lead to higher surface tension compared to a case in which partitioning is neglected, the present results show that the partitioning also alters the solute effect, and that the change is large enough to further increase the critical supersaturation and hence decrease the droplet activation. The fraction of surfactant partitioned to droplet surface increases with decreasing droplet size, which suggests that surfactants might enhance the activation of larger particles relatively more thus leading to less dense clouds. Cis-pinonic acid-ammonium sulfate aqueous solution was studied in order to relate the partitioning to more realistic atmospheric situation and to find out the combined effects of dissolution and partitioning behaviour. The results show that correct partitioning consideration alters the shape of the Köhler curve when compared to a situation in which the partitioning is neglected either completely or in the Raoult effect.

[1] Humic like substances (HULIS) are a class of compounds that are suspected to have an effect on cloud droplet activation properties of atmospheric aerosols because they decrease the surface tension of aqueous solutions quite efficiently. Surface active organic compounds have a tendency of concentrating on the surfaces of liquid droplets. If the total amount of surface active compound is small enough, partitioning of the substance on the surface depletes it from the droplet interior, decreasing the Raoult effect and increasing the Kelvin effect. Thus, the surface partitioning causes an increase of the critical supersaturation (Köhler curve maximum), and the effect gets stronger with decreasing size of the cloud condensation nucleus. In this study, the effects of HULIS on the activation of cloud droplets was studied by cloud parcel model calculations. Model results indicate that if the surface partitioning is not taken into account, the number of activated droplets can be highly overestimated. The simulations were made using particles containing 10-80% mass fraction of HULIS, while the remaining fraction of the particle was ammonium sulfate. The calculations indicated that the surface tension effects of humic-like compounds on the cloud activation become significant only when the weight fraction of the organics is very high. In contrast, if the surface partitioning is not taken into account, already a small weight fraction of organics will lead to significant increase in number of cloud droplets.