N2O5 reaction on submicron sea salt aerosol:: Kinetics, products, and the effect of surface active organics

The reaction of N2O5 on sea salt aerosol is a sink for atmospheric nitrogen oxides and a source of the Cl radical. We present room-temperature measurements of the N2O5 loss rate on submicron artificial seawater (ASW) aerosol, performed with an entrained aerosol flow tube coupled to a chemical ionization mass spectrometer, as a function of aerosol phase (aqueous or partially crystalline), liquid water content, and size. We also present an analysis of the product growth kinetics showing that ClNO2 is produced at a rate equal to N2O5 loss, with an estimated lower limit yield of 50% at 50% relative humidity (RH). The reaction probability for N2O5, gamma(N2O5), depends strongly on the particle phase, being 0.005 +/- 0.004 on partially crystalline ASW aerosol at 30% RH and 0.03 +/- 0.008 on aqueous ASW aerosol at 65% RH. At 50% RH, N2O5 loss is relatively insensitive to particle size for radii greater than 100 nm, and gamma(N2O5) displays a statistically insignificant increase from 0.022 to similar to 0.03 for aqueous ASW aerosol over the RH range of 43-70%. We find that the presence of millimolar levels of hexanoic acid in the aerosol bulk decreases the gamma(N2O5) at 70% RH by a factor of 3-4 from similar to 0.025 to 0.008 +/- 0.004. This reduction is likely due to the partitioning of hexanoic acid to the gas-aerosol interface at a surface coverage that we estimate to be equivalent to a monolayer. This result is the first evidence that a monolayer coating of aqueous organic surfactant can slow the reactive uptake of atmospheric trace gases to aerosol.