Mineral oxides change the atmospheric reactivity of soot: NO2 uptake under dark and UV irradiation conditions

Abstract

The heterogeneous reactions between trace gases and aerosol surfaces have been widely studied over the past decades, revealing the crucial role of these reactions in atmospheric chemistry. However, existing knowledge on the reactivity of mixed aerosols is limited, even though they have been observed in field measurements. In the current study, the heterogeneous interaction of NO2 with solid surfaces of Al2O3 covered with kerosene soot was investigated under dark conditions and in the presence of UV light. Experiments were performed at 293 K using a low-pressure flow-tube reactor coupled with a quadrupole mass spectrometer. The steady-state uptake coefficient, γss, and the distribution of the gas-phase products were determined as functions of the Al2O3 mass; soot mass; NO2 concentration, varied in the range of (0.2-10) × 1012 molecules cm-3; photon flux; and relative humidity, ranging from 0.0032% to 32%. On Al2O3/soot surfaces, the reaction rate was substantially increased, and the formation of HONO was favored compared with that on individual pure soot and pure Al2O3 surfaces. Uptake of NO2 was enhanced in the presence of H 2O under both dark and UV irradiation conditions, and the following empirical expressions were obtained: γss,BET,dark = (7.3 ± 0.9) × 10-7 + (3.2 ± 0.5) × 10 -8 × RH and γss,BET,UV = (1.4 ± 0.2) × 10-6 + (4.0 ± 0.9) × 10-8 × RH. Specific experiments, with solid sample preheating and doping with polycyclic aromatic hydrocarbons (PAHs), showed that UV-absorbing organic compounds significantly affect the chemical reactivity of the mixed mineral/soot surfaces. A mechanistic scheme is proposed, in which Al2O3 can either collect electrons, initiating a sequence of redox reactions, or prevent the charge-recombination process, extending the lifetime of the excited state and enhancing the reactivity of the organics. Finally, the atmospheric implications of the observed results are briefly discussed. © 2013 American Chemical Society.