Reactive uptake of NO3, N2O5, NO2, HNO3, and O3 on three types of polycyclic aromatic hydrocarbon surfaces.

We investigated the reactive uptake of NO3, N2O5, NO2, HNO3, and O3 on three types of solid polycyclic aromatic hydrocarbons (PAHs) using a coated wall flow tube reactor coupled to a chemical ionization mass spectrometer. The PAH surfaces studied were the 4-ring systems pyrene, benz[a]anthracene, and fluoranthene. Reaction of NO3 radicals with all three PAHs was observed to be very fast with the reactive uptake coefficient, gamma, ranging from 0.059 (+0.11/-0.049) for benz[a]anthracene at 273 K to 0.79 (+0.21/-0.67) for pyrene at room temperature. In contrast to the NO3 reactions, reactions of the different PAHs with the other gas-phase species (N2O5, NO2, HNO3, and O3) were at or below the detection limit (gamma <or= 6.6 x 10(-5)) in all cases, illustrating that these reactions are at best slow. For NO3 we also investigated the time dependence of the reactive uptake to determine if the surface-bound PAH molecules were active participants in the reaction (i.e., reactants). Reaction of NO3 on all three PAH surfaces slowed down at 263 K after long NO3 exposure times, suggesting that the PAH molecules were reactants. Additionally, NO2 and HNO3 were identified as major gas-phase products. Our results show that under certain atmospheric conditions, NO3 radicals can be a more important sink for PAHs than NO2, HNO3, N2O5, or O3 and impact tropospheric lifetimes of surface-bound PAHs.