Effect of the Aerosol-Phase State on Secondary Organic Aerosol Formation from the Reactive Uptake of Isoprene-Derived Epoxydiols (IEPDX)

Acid-catalyzed reactions between gas- and particle-phase constituents are critical to atmospheric secondary organic aerosol (SOA) formation. The aerosol-phase state is thought to influence the reactive uptake of gas-phase precursors to aerosol particles by altering diffusion rates within particles. However, few experimental studies have explored the precise role of the aerosol-phase state on reactive uptake processes. This laboratory study systematically examines the reactive uptake coefficient (gamma) of trans-beta-isoprene epoxydiol (trans-beta-IEPDX), the predominant IEPOX isomer, on acidic sulfate particles coated with SOA derived from a-pinene ozonolysis. gamma(IEPOX) is obtained for core-shell particles, the morphology of which was confirmed by microscopy, as a function of SOA coating thickness and relative humidity. gamma(IEPOX) is reduced, in some cases by half of the original value, when SOA coatings are present prior to uptake, especially when coating thicknesses are >15 nm. The diurnal trend of IEPOX lost to acid-catalyzed reactive uptake yielding SOA compared with other known atmospheric sinks (gas-phase oxidation or deposition) is derived by modeling the experimental coating effect with field data from the southeastern United States. IEPOX-derived SOA is estimated to be reduced by 16-27% due to preexisting organic coatings during the afternoon (12:00 to 7:00 p.m., local time), corresponding to the period with the highest level of production.