Enhanced nitrous acid (HONO) formation via NO2 uptake and its potential contribution to heavy haze formation during wintertime

Abstract

A full understanding of the sources of atmospheric nitrous acid (HONO) in the polluted urban atmosphere remains a challenge. In this study, ambient HONO and relevant species were measured during January 2019 at an urban site in Beijing, China, and a budget analysis of HONO was conducted using a box model combined with field observations. Large nighttime “missing sources” of HONO were identified on heavily polluted days based on traditional sources, which had a significant correlation with the relative humidity, ammonia (NH3), and aerosol surface area, and the promotional effect of NH3 for nitrogen dioxide (NO2) uptake on the wet aerosol surface was discussed. Then, an updated parameterization scheme for quantifying the enhanced heterogeneous reactions of NO2 on aerosol surfaces is proposed, and the missing nighttime sources of HONO could be substantially compensated after the new scheme was incorporated. Further evaluation on the contributions of HONO to hydroxyl radicals was conducted, and the authors found that the photolysis of HONO played a dominant role in the primary OH production on the polluted days (78%–90%). The study reveals great potential of an NH3-enhanced uptake coefficient of NO2 on the aerosol surface in the nocturnal HONO budget, and highlights the significance of HONO in the strong atmospheric oxidation capability during episodes with a heavily polluted atmosphere.摘要本文研究了重污染过程中气态亚硝酸 (HONO) 的关键来源并基于化学箱模型对其源汇过程进行了闭合分析. 结果显示, 现有的HONO 源汇机制并不能解释观测期间出现的高HONO事件, 尤其是重污染过程夜间存在大量的HONO "未知源". 本文提出了一套新的HONO 源汇参数化方案, 可以较好的模拟观测期间HONO日间和夜间来源, 并进一步评估了HONO 对羟基自由基 (OH) 的贡献, 发现 HONO 光解主导了重污染天OH生成 (78%–90%). 研究结果揭示了华北城市富氨大气环境促进 NO2在气溶胶表面的摄取和非均相反应进而主导了夜间HONO生成, 凸显了HONO化学对于重污染过程维持大气氧化能力的重要作用.