A high-resolution study of surfactant partitioning and kinetic limitations for two-component internally mixed aerosols

Atmospheric aerosols serve as cloud condensation nuclei (CCN), altering cloud properties and ultimately affecting climate through their effect on the radiative balance. Aerosol CCN activity depends in part on aerosol composition and surfactant compounds are of particular interest because surfactants are enriched at the water/air interface, resulting in a radial concentration gradient within the aqueous droplet. Accurate treatment of the surfactant concentration gradient complicates the otherwise straightforward predictions of CCN activity for aerosols of known composition. To accurately evaluate predictions made by theory, laboratory studies investigating the relationship between critical supersaturation and dry diameter of particles that include surfactants require significant reduction in measurement uncertainty for both water-uptake and CCN measurements. Furthermore, uncertainties remain regarding kinetic limitations to surfactant partitioning that could result in deviation from predictions based on equilibrium thermodynamics. This study attempts to address some of these issues through high-resolution analysis of CCN activity of two-component mixed surfactant/non-surfactant aerosols at different internal mixing ratios performed with and without a water-uptake time delay to ascertain whether or not the observed effects are kinetically limited. We present new data for the aerosols consisting of 1) the ionic surfactant sodium dodecyl sulfate (SDS) with ammonium sulfate, 2) SDS with sodium chloride and 3) the strong non-ionic fluorosurfactant Zonyl with an organic proxy glucose. As a point of reference we also evaluated the mixture of ammonium sulfate with glucose. Aerosol activation diameters were determined using CCN analysis in conjunction with scanning mobility size classification and high sheath-to-aerosol flow ratios. This resulted in CCN-derived kappa values that could be determined within +/-5% relative error. To test whether dynamic surfactant partitioning leads to kinetic limitations on the partitioning process we introduced a pre-humidification step at RH ~80% followed by a 30s to 6 min delay before CCN analysis. Data were evaluated against various theoretical models using activity coefficients at RH near cloud-droplet activation (99%) determined with an improved high accuracy tandem differential mobility analyzer technique. Results confirm previous studies that show that surfactants do not enhance cloud droplet activation relative to what would be predicted from water activity alone. The data obtained with and without time delay were indistinguishable within measurement uncertainty, suggesting that dynamic surface tension need not be considered in Köhler theory. With the exception of the SDS system, linear mixing rules can well-approximate CCN activity, although some non-linearity in the mixing rules were detected by the measurement system.