Measuring the Surface Tension of Atmospheric Particles and Relevant Mixtures to Better Understand Key Atmospheric Processes.

Aerosol and aqueous particles are ubiquitous in Earth's atmosphere and play key roles in geochemical processes such as natural chemical cycles, cloud and fog formation, air pollution, visibility, climate forcing, etc. The surface tension of atmospheric particles can affect their size distribution, condensational growth, evaporation, and exchange of chemicals with the atmosphere, which, in turn, are important in the above-mentioned geochemical processes. However, because measuring this quantity is challenging, its role in atmospheric processes was dismissed for decades. Over the last 15 years, this field of research has seen some tremendous developments and is rapidly evolving. This review presents the state-of-the-art of this subject focusing on the experimental approaches. It also presents a unique inventory of experimental adsorption isotherms for over 130 mixtures of organic compounds in water of relevance for model development and validation. Potential future areas of research seeking to better determine the surface tension of atmospheric particles, better constrain laboratory investigations, or better understand the role of surface tension in various atmospheric processes, are discussed. We hope that this review appeals not only to atmospheric scientists but also to researchers from other fields, who could help identify new approaches and solutions to the current challenges.

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, (NH4)2SO4) 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.

Surface tension models for binary aqueous solutions: a review and intercomparison.

The liquid-air surface tension of aqueous solutions is a fundamental quantity in multi-phase thermodynamics and fluid dynamics and thus relevant in many scientific and engineering fields. Various models have been proposed for its quantitative description. This Perspective gives an overview of the most popular models and their ability to reproduce experimental data of ten binary aqueous solutions of electrolytes and organic molecules chosen to be representative of different solute types. In addition, we propose a new model which reproduces sigmoidal curve shapes (Sigmoid model) to empirically fit experimental surface tension data. The surface tension of weakly surface-active substances is well reproduced by all models. In contrast, only few models successfully model the surface tension of aqueous solutions with strongly surface-active substances. For substances with a solubility limit, usually no experimental data is available for the surface tension of supersaturated solutions and the pure liquid solute. We discuss ways in which these can be estimated and emphasize the need for further research. The newly developed Sigmoid model best reproduces the surface tension of all tested solutions and can be recommended as a model for a broad range of binary mixtures and over the entire concentration range.