Exploring the amplified role of HCHO in the formation of HMS and O3 during the co-occurring PM2.5 and O3 pollution in a coastal city of southeast China

Abstract

Abstract. To develop effective strategies for controlling both PM2.5 and O3 levels, it is crucial to understand their synergistic mechanisms and key precursors and the atmospheric physiochemical processes involved. In this study, a wintertime co-occurring O3 and PM2.5 pollution event in a coastal city in southeast China was investigated based on high-time-resolution measurements of criteria air pollutants and chemical compositions of PM2.5, and O3 precursors, such as NOx, HCHO, and volatile organic compounds (VOCs). The results of this study revealed the characteristics of positively correlated PM2.5 and MDA8 O3 concentrations, and an increase in atmospheric oxidation capacity (AOC) during the cold seasons. Strong correlations (R2= 0.415–0.477) between HCHO, Fe, Mn, and sulfate concentrations were observed, suggesting the influence of catalyzed oxidation processes in the coastal city. Through an observation-based model (OBM) analysis coupled with the Regional Atmospheric Chemistry Mechanism, version 2 (RACM2) and the Chemical Aqueous-Phase Radical Mechanism, version 3.0 (CAPRAM 3.0), we found that high concentrations of precursors (SO2 and HCHO), high relative humidity, and moderately acidic pH conditions enhanced the heterogeneous formation of hydroxymethanesulfonate (HMS) in PM2.5. Furthermore, by employing an OBM coupled to the Master Chemical Mechanism (OBM-MCM), we verified that disabling the HCHO mechanism could decrease daytime net O3 production rates by reducing the production rates of HO2 + NO. These results were consistent with the daily values of AOC, OH, HO2, and RO2 concentrations. This study contributes to a better understanding of the significance of HCHO in photochemical reactions and the formation of HMS in a coastal city.