Phase, morphology, and hygroscopicity of mixed oleic acid/sodium chloride/water aerosol particles before and after ozonolysis.

Aerosol optical tweezers are used to probe the phase, morphology, and hygroscopicity of single aerosol particles consisting of an inorganic component, sodium chloride, and a water insoluble organic component, oleic acid. Coagulation of oleic acid aerosol with an optically trapped aqueous sodium chloride droplet leads to formation of a phase-separated particle with two partially engulfed liquid phases. The dependence of the phase and morphology of the trapped particle with variation in relative humidity (RH) is investigated by cavity enhanced Raman spectroscopy over the RH range <5% to >95%. The efflorescence and deliquescence behavior of the inorganic component is shown to be unaffected by the presence of the organic phase. Whereas efflorescence occurs promptly (<1 s), the deliquescence process requires both dissolution of the inorganic component and the adoption of an equilibrium morphology for the resulting two phase particle, occurring on a time-scale of <20 s. Comparative measurements of the hygroscopicity of mixed aqueous sodium chloride/oleic acid droplets with undoped aqueous sodium chloride droplets show that the oleic acid does not impact on the equilibration partitioning of water between the inorganic component and the gas phase or the time response of evaporation/condensation. The oxidative aging of the particles through reaction with ozone is shown to increase the hygroscopicity of the organic component.

The morphology of aerosol particles consisting of hydrophobic and hydrophilic phases: hydrocarbons, alcohols and fatty acids as the hydrophobic component.

The morphology of bi-phase aerosol particles containing phase separated hydrophobic and hydrophilic components is considered, comparing simulations based on surface and interfacial tensions with measurements made by aerosol optical tweezers. The competition between the liquid phases adopting core-shell and partially engulfed configurations is considered for a range of organic compounds including saturated and unsaturated hydrocarbons, aromatics, alcohols, ketones, carboxylic acids, esters and amines. When the solubility of the organic component and the salting-out of the organic component to the surface by the presence of concentrated inorganic solutes in the aqueous phase are considered, it is concluded that the adoption of a partially engulfed structure predominates, with the organic component forming a surface lens. The aqueous surface can be assumed to be stabilised by a surface enriched in the organic component. The existence of acid-base equilibria can lead to the dissociation of organic surfactants and to significant lowering of the surface tension of the aqueous phase, further supporting the predominance of partially engulfed structures. Trends in morphology from experimental measurements and simulations are compared for mixed phased droplets in which the organic component is decane, 1-octanol or oleic acid with varying relative humidity. The consequences of partially engulfed structures for aerosol properties are considered.

Comparative thermodynamic studies of aqueous glutaric acid, ammonium sulfate and sodium chloride aerosol at high humidity.

Aerosol optical tweezers are used to simultaneously characterize and compare the hygroscopic properties of two aerosol droplets, one containing inorganic and organic solutes and the second, referred to as the control droplet, containing a single inorganic salt. The inorganic solute is either sodium chloride or ammonium sulfate and the organic component is glutaric acid. The time variation in the size of each droplet (3-7 microm in radius) is recorded with 1 s time resolution and with nanometre accuracy. The size of the control droplet is used to estimate the relative humidity with an accuracy of better than +/-0.09%. Thus, the Kohler curve of the multicomponent inorganic/organic droplet, which characterizes the variation in equilibrium droplet size with relative humidity, can be determined directly. The measurements presented here focus on high relative humidities, above 97%, in the limit of dilute solutes. The experimental data are compared with theoretical treatments that, while ignoring the interactions between the inorganic and organic components, are based upon accurate representations of the activity-concentration relationships of aqueous solutions of the individual salts. The organic component is treated by a parametrized fit to experimental data or by the UNIFAC model and the water activity of the equilibrium solution droplet is calculated using the approach suggested by Clegg, Seinfeld and Brimblecombe or the Zdanovskii-Stokes-Robinson approximation. It is shown that such an experimental strategy, comparing directly droplets of different composition, enables highly accurate measurements of the hygroscopic properties, allowing the theoretical treatments to be rigorously tested. Typical deviations of the experimental measurements from theoretical predictions are shown to be around 1% in equilibrium size, comparable to the variation between the theoretical frameworks considered.

In situ comparative measurements of the properties of aerosol droplets of different chemical composition.

Aerosol optical tweezers can be used to manipulate multiple aerosol particles simultaneously. When coupled with spontaneous and stimulated Raman scattering, the composition, size and phase partitioning of different chemical components within a liquid droplet can be investigated. In combination, these two techniques suggest the possibility of a new strategy for characterising the thermodynamic behaviour of aerosols and the kinetics of mass transfer between the gas and condensed phases. We demonstrate here that two droplets can be characterised simultaneously, examining specifically the variation in wet particle size with relative humidity, recording the changes in size with nanometre accuracy. In a further demonstration, we use the size of a sodium chloride droplet to determine the relative humidity of the gas phase, allowing the variation in hygroscopicity of a second aqueous glutaric acid/sodium chloride droplet to be studied. We suggest that such a comparative approach can provide new insights into aerosol dynamics.