Heterogeneous uptake of NO2 by sodium acetate droplets and secondary nitrite aerosol formation

Abstract

The high NO₃^- concentration in fine particulate matters (PM_2.5) during heavy haze events has attracted much attention, but the formation mechanism of nitrates remains largely uncertain, especially concerning heterogeneous uptake of NO_X by aqueous phase. In this work, the heterogeneous uptake of NO₂ by sodium acetate (NaAc) droplets with different NO₂ concentrations and relative humidity (RH) conditions is investigated by microscopic Fourier transform infrared spectrometer (micro-FTIR). The IR feature changes of aqueous droplets indicate the acetate depletion and nitrite formation in humid environment. This implies that acetate droplets can provide the alkaline aqueous circumstances caused by acetate hydrolysis and acetic acid (HAc) volatilization for nitrite formation during the NO₂ heterogeneous uptake. Meanwhile, the nitrite formation will exhibit a pH neutralizing effect on acetate hydrolysis, further facilitating HAc volatilization and acetate depletion. The heterogeneous uptake coefficient increases from 5.2 × 10^-6 to 1.27 × 10^-5 as RH decreases from 90% to 60% due to the enhanced HAc volatilization. Furthermore, no obvious change in uptake coefficient with different NO₂ concentrations is observed. This work may provide a new pathway for atmospheric nitrogen cycling and secondary nitrite aerosol formation.

Keywords: Heterogeneous uptake; NaAc droplets; Nitrite; Uptake coefficient.