[A-AS07] Atmospheric Chemistry

[AAS07-18] Rapid hydrolysis of NO2 at high ionic strengths of deliquesced aerosol particles

*Gen Masao¹, Haotian Zheng^2,3,4, Yele Sun⁵, Wanyun Xu⁶, Nan Ma⁷, Hang Su⁸, Yafang Cheng⁸, Shuxiao Wang^2,3, Jia Xing^2,3, Shuping Zhang^2,3, Likun Xue⁹, Chaoyang Xue¹⁰, Yujing Mu¹¹, Xiao Tian¹², Atsushi Matsuki¹³, Shaojie Song^4,12,14 (1.Tohoku University, 2.Tsinghua University, 3.State Environmental Protection Key Laboratory of Sources and Control of Air Pollution Complex, 4.CMA-NKU Cooperative Laboratory for Atmospheric Environment Health Research, 5.Institute of Atmospheric Physics, Chinese Academy of Sciences, 6.Chinese Academy of Meteorological Sciences, 7.Jinan University, 8.Max Planck Institute for Chemistry, 9.Shandong University, 10.CNRS – Université Orléans – CNES, 11.Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences, 12.Nankai University, 13.Kanazawa University, 14.Harvard University)

Keywords:NO2 hydrolysis, Aerosol, Ionic strength, Multiphase reactions

Nitrogen dioxide (NO₂) hydrolysis in deliquesced aerosol particles forms nitrous acid and nitrate and thus impacts air quality, climate, and nitrogen cycle. Traditionally, it is considered to proceed far too slowly in the atmosphere. However, the significance of this process is highly uncertain because kinetic studies have only been made in dilute aqueous solutions, and not under high ionic strength conditions of the aerosol particles. Here, we use laboratory experiments, air quality models, and field measurements to examine the effect of ionic strength on the reaction kinetics of NO₂ hydrolysis. We find that high ionic strengths (I) enhance the reaction rate constants (kI) by more than two orders of magnitude compared to that at infinite dilution (k_I=0), yielding log₁₀(k_I/k_I=0) = 0.058I. A state-of-the-art air quality model shows that the enhanced NO₂ hydrolysis reduces the negative bias in the simulated concentrations of nitrous acid by 27% on average when compared to field observations over the North China Plain. Rapid NO₂ hydrolysis also enhances the levels of nitrous acid in other polluted regions such as North India and further promotes atmospheric oxidation capacity. This study highlights the need to evaluate various reaction kinetics of atmospheric aerosols with high ionic strengths.