ABSTRACT
The photoemission of iodide from aqueous aerosol particle surfaces measures the surface concentration of iodide in predominantly supersaturated NaCl aerosol particles. Using the Langmuir model to describe the adsorption to the surface of aqueous iodide anions, the standard Gibbs free energy of adsorption is -15 kJ/mol in these systems. The presence of charged surfactants on the particle surfaces changes the adsorption behavior of iodide. The addition of sodium docecylsulfate (SDS) reduces the coverage of iodide, consistent with a competitive adsorption scenario. For surfaces coated with C12-, C14-, or C16-trimethylammonium chloride, the addition of iodide results in the formation of iodide-surfactant ion pairs at the surface with enhanced photoemission. The adsorption free energy for iodide in these systems is -21 kJ/mol. The results demonstrate the surface enhancement of iodide in supersaturated, atmospherically relevant conditions and demonstrate important differences between single-salt solutions and mixtures in the limit of high concentration.
ABSTRACT
The reactions of NO(y) species in the atmosphere with sea spray aerosol replace halogen anions with nitrate. These experiments show the effect of increasing the nitrate content of model sea spray aerosol particles on the morphology changes and the phase transitions driven by changes in relative humidity (RH). The components of the model particles include H2O, Na+, Mg2+, Cl-, NO3-, and SO4(2-). Tandem differential mobility analyzer (TDMA) measurements yield the water content and efflorescence relative humidity (ERH) of these particles, and probe molecule spectroscopic measurements reveal subsequent phase transitions and partially characterize the salt composition on the surface of dry particles. The results show three effects of increasing the nitrate composition: decreasing the EFH (46 to 29%), production of a metastable aqueous layer on the surface of effloresced particles, and decreasing the sulfate content near the surface of dry particles. For the mixtures studied here, the initial crystallization event forms a core of NaCl. For particles that contain a substantial metastable aqueous layer following efflorescence, probe molecule spectroscopy shows a second crystallization at a lower RH. This subsequent phase transition is likely the formation of Na2SO4. Homogeneous nucleation theory (HNT) using a semiempirical formulation predicts the ERH of all mixtures within 2.0% RH, with a mean absolute deviation of 1.0%. The calculations suggest that structures associated with highly concentrated or supersaturated magnesium ions strongly affect the interfacial tension between the NaCl crystal nucleus and the droplet from which it forms.
