Establishing the impact of model surfactants on cloud condensation nuclei activity of sea spray aerosol mimics

Surface-active compounds present in aerosols can increase their cloud condensation nuclei (CCN) activation efficiency by reducing the surface tension (sigma) in the growing droplets. However, the importance of this effect is poorly constrained by measurements. Here we present estimates of droplet surface tension near the point of activation derived from direct measurement of droplet diameters using a continuous flow streamwise thermal gradient chamber (CFSTGC). The experiments used sea spray aerosol (SSA) mimics composed of NaCl coated by varying amounts of (i) oleic acid, palmitic acid or myristic acid, (ii) mixtures of palmitic acid and oleic acid, and (iii) oxidized oleic acid. Significant reductions in a relative to that for pure water were observed for these mimics at relative humidity (RH) near activation (similar to 99.9 %) when the coating was sufficiently thick. The calculated surface pressure (pi = sigma(H2O )- sigma(observed)) values for a given organic compound or mixture collapse onto one curve when plotted as a function of molecular area for different NaCl seed sizes and measured RH. The observed critical molecular area (A(0)) for oleic acid determined from droplet growth was similar to that from experiments conducted using macroscopic solutions in a Langmuir trough. However, the observations presented here suggest that oleic acid in microscopic droplets may exhibit larger pi values during monolayer compression. For myristic acid, the observed A(0) compared well to macroscopic experiments on a fresh subphase, for which dissolution has an important impact. A significant kinetic limitation to water uptake was observed for NaCl particles coated with pure palmitic acid, likely as a result of palmitic acid (with coating thicknesses ranging from 67 to 132 nm) being able to form a solid film However, for binary palmitic-acid-oleic-acid mixtures there was no evidence of a kinetic limitation to water uptake. Oxidation of oleic acid had a minor impact on the magnitude of the surface tension reductions observed, potentially leading to a slight reduction in the effect compared to pure oleic acid. A CCN counter was also used to assess the impact on critical supersaturations of the substantial sigma reductions observed at very high RH. For the fatty-acid-coated NaCl particles, when the organic fraction (epsilon(org)) was > 0.90 small depressions in critical supersaturation were observed. However, when epsilon(org) <0.90 the impact on critical supersaturation was negligible. Thus, for the fatty acids considered here, the substantial sigma reductions observed at high RH values just below activation have limited impact on the ultimate critical supersaturation. A surface film model is used to establish the properties that surface-active organic molecules must have if they are to ultimately have a substantial impact on the activation efficiency of SSA. To influence activation, the average properties of surface-active marine-derived organic molecules must differ substantially from the long-chain fatty acids examined, having either smaller molecular volumes or larger molecular areas. The model results also indicate that organic-compound-driven surface tension depression can serve to buffer the critical supersaturation against changes to the organic-to-salt ratio in particles in which the organic fraction is sufficiently large.