Incorporation of multi-phase halogen chemistry into the Community Multiscale Air Quality (CMAQ) model

Abstract

Halogen radicals (Cl, Br, and I) significantly influence atmospheric oxidation capacity, affecting both O3 formation and destruction. However, understanding of halogen chemistry remains limited. To better investigate comprehensive atmospheric halogen chemistry, we incorporated halogen processes into the Community Multi-scale Air Quality (CMAQ) model: (i) emissions of Cl2, HCl, Br2, and HBr from anthropogenic sources and Br2, I2, HOI, and halocarbons from natural sources and (ii) 177 multi-phase halogen reactions. Model performance was evaluated against observed ClNO2 levels and by comparison with reported ranges of BrO and IO levels. The updated model showed significant improvements in simulating ClNO2 mixing ratios, with the index of agreement (IOA) increasing from 0.41 to 0.66 and mean bias (MB) decreasing from -159.36 to -25.07 ppt at supersites. Furthermore, simulated BrO and IO levels fell within the ranges reported in previous studies. We found that these improvements were driven by four key reactions: (i) ClO self-reaction, (ii) heterogeneous HOBr chemistry, (iii) NO2 uptake, and (iv) revised N2O5 parameterization. Based on our modeling system, we found that the presence of halogen radicals led to changes in the net Ox production rate (P(Ox)), which increased from 3.08 to 3.33 ppbh-1 on land and decreased from 0.21 to 0.07 ppbh-1 over ocean. It was noted that levels of OH, HCHO, and NOx also increased by similar to 0.007 ppt (5.5 %), similar to 0.03 ppb (1.6 %), and similar to 0.29 ppb (2.9 %), respectively, while levels of HO2 and volatile organic compounds (VOCs) decreased by similar to 0.45 ppt (5.3 %) and similar to 0.71 ppb (5.9 %). These results highlight the importance of accurately representing halogen processes in regional air quality models.