Relative humidity driven nocturnal HONO formation mechanism in autumn haze events of Beijing

Abstract Nitrous acid (HONO), a key precursor of hydroxyl radicals (OH), is one of the factors affecting atmospheric chemistry and air quality. Currently, the proposed sources of HONO are not able to fully explain observed HONO concentrations. In this study, a comprehensive field observation of HONO was conducted in the autumn of 2021 in urban Beijing. The box model using a default Master Chemical Mechanism (MCM) was unable to reproduce the observed HONO concentrations with a normalized mean bias (NMB) of −92.8%. The NMB improved to −46.1% after the inclusion of seven additional HONO formation pathways. Several factors like vehicle emission factor (1.23%) and nocturnal NO2 heterogeneous uptake coefficient on the ground surface (8.25 × 10−6) were calculated based on observational data. The enhancement factor for nocturnal NO2 heterogeneous conversion was established as a function of relative humidity (RH) and incorporated into the model, which compensated for the missing nocturnal HONO sources and well-reproduced the observed HONO concentrations, with an NMB of −5.1%. The major source of HONO at night was found to be the heterogeneous reaction of NO2 on the ground surface, contributing up to 85.6%. During the daytime, it was the homogeneous reaction of NO with OH, accounting for 41.8%. The daytime primary source of OH was mainly the photolysis of HONO, which constituted 73.6% and therefore promoted the formation of secondary pollutants and exacerbated haze events.