The effect of varying levels of surfactant on the reactive uptake of N₂O₅ to aqueous aerosol

Abstract. Recent observations have detected surface active organics in atmospheric aerosols. We have studied the reaction of N₂O₅ on aqueous natural seawater and NaCl aerosols as a function of sodium dodecyl sulfate (SDS) concentration to test the effect of varying levels of surfactant on gas-aerosol reaction rates. SDS was chosen as a proxy for naturally occurring long chain monocarboxylic acid molecules, such as palmitic or stearic acid, because of its solubility in water and well-characterized surface properties. Experiments were performed using a newly constructed aerosol flow tube coupled to a chemical ionization mass spectrometer for monitoring the gas phase, and a differential mobility analyzer/condensation particle counter for determining aerosol surface area. We find that the presence of ~3.5wt% SDS in the aerosol, which corresponds to a monolayer surface coverage of ~2×10¹⁴ molecules cm^-2, suppresses the N₂O₅ reaction probability, γ^N₂O₅, by approximately a factor of ten, independent of relative humidity. Consistent with this observation is a similar reduction in the rate of ClNO₂ product generation measured simultaneously. However, the product yield remains nearly constant under all conditions. The degree of suppression is strongly dependent on SDS content in the aerosol, with no discernable effect at 0.1wt% SDS, but significant suppression at what we predict to be submonolayer coverages with 0.3–0.6wt% SDS on NaCl and natural seawater aerosols, respectively.