Salting out, non-ideality and synergism enhance surfactant efficiency in atmospheric aerosols

In Earth’s atmosphere, the surface tension of sub-micron aerosol particles is suspected to affect their efficiency in becoming cloud droplets. But this quantity cannot be measured directly and is inferred from the chemical compounds present in aerosols. Amphiphilic surfactants have been evidenced in aerosols but experimental information on the surface properties of their mixtures with other aerosol components is lacking. This work explores experimentally the surface properties of aqueous mixtures of amphiphilic surfactants (SDS, Brij35, TritonX100, TritonX114, and CTAC) with inorganic salts (NaCl, (NH(4))(2)SO(4)) and soluble organic acids (oxalic and glutaric acid) using pendant droplet tensiometry. Contrary to what could be expected, inorganic salts and organic acids systematically enhanced the efficiency of the surfactants rather than reduced it, by further lowering the surface tension and, in some cases, the CMC. Furthermore, all the mixtures studied were strongly non-ideal, some even displaying some synergism, thus demonstrating that the common assumption of ideality for aerosol mixtures is not valid. The molecular interactions between the mixture components were either in the bulk (salting out), in the mixed surface monolayer (synergy on the surface tension) or in the micelles (synergy on the CMC) and need to be included when describing such aerosol mixtures.