Theoretical investigation on the role of mineral dust aerosol in atmospheric reaction: A case of the heterogeneous reaction of formaldehyde with NO2 onto SiO2 dust surface

Abstract

The role of mineral dusts on the heterogeneous reaction of formaldehyde with NO2 was investigated using a quantum chemical approach. SiO2 was selected as a model of mineral dust to investigate the heterogeneous reaction mechanism and kinetics because the mineral dust is comprised of ∼60% of SiO2. Compared with NO2, formaldehyde was easily adsorbed onto SiO2 model, indicating SiO2 was a sink for formaldehyde. Further data showed that the presence of SiO2 reduced the reaction barrier, but did not change reaction mechanism. The kinetics calculation using the canonical variational transition state theory plus small curvature tunneling correction showed that the presence of SiO2 could accelerate the atmospheric reaction rate of formaldehyde with NO2 to produce HONO. The effect of the altitudes was also considered, and the heterogeneous reaction rate decreased with increasing the altitude due to the atmospheric temperature decrease, suggesting that the degradation of atmospheric HCHO onto available mineral dusts might be competitive with the corresponding homogeneous reaction, especially in dusty urban and desert environments. This work can lay the foundation on the atmospheric heterogeneous reaction of VOCs, probe the role of mineral dust and establish the atmospheric transformation models, to better understand pollution mechanism.