Uptake of Pyrene onto Fatty Acid Coated NaCl Aerosol Particles.

Abstract

Photoelectric charging experiments monitor the uptake of pyrene onto NaCl aerosol particles coated with either oleic acid or myristic acid. In both cases, thin coatings produce a small net decrease in pyrene uptake. In the larger coverage limit, the uptake of the myristic acid coated particles remains nearly constant whereas the oleic acid coated particles exhibit greater uptake rates than the bare NaCl particles. Fitting the results with a multilayer kinetic model yields uptake rate coefficients as well as parameters that describe the distribution of organic molecules on the aerosol particle surface. The model accounts for the decrease in uptake associated with thin coatings of oleic acid through a concomitant reduction in surface area. The adsorption rate constants for the myristic and oleic acid coated surfaces are 50 and 80 times faster, respectively, than for NaCl. The desorption rates for pyrene on the fatty acid surfaces are faster, as well. For myristic acid coatings, the fast desorption (over 400 times the rate of desorption from NaCl) results in slower net adsorption, whereas for oleic acid (approximately 12 times the desorption rate from NaCl), the net uptake rate increases with coverage. The results also suggest that both myristic acid and oleic acid spread incompletely on the aerosol surfaces under the conditions of these experiments. In the optimized kinetic model, the fatty acids cover approximately 50% of the surface when the nominal coating thickness is approximately 6 nm. The surface is over 90% covered with a nominal coating thickness of 20 nm, which is approximately 10% of particle diameter in these experiments. Very thin oleic acid coatings reduce the surface area of particles consistent with the preferential coverage of highly corrugated or porous regions.