Atmospheric gaseous hydrochloric and hydrobromic acid in urban Beijing, China: detection, source identification and potential atmospheric impacts

Gaseous hydrochloric (HCl) and hydrobromic acid (HBr) are vital halogen species that play essential roles in tropospheric physicochemical processes. Yet, the majority of the current studies on these halogen species were conducted in marine or coastal areas. Detection and source identification of HCl and HBr in inland urban areas remain scarce, thus limiting the full understanding of halogen chemistry and potential atmospheric impacts in the environments with limited influence from the marine sources. Here, both gaseous HCl and HBr were concurrently measured in urban Beijing, China, during winter and early spring of 2019. We observed significant HCl and HBr concentrations ranging from a minimum value at 1 x 10(8) molecules cm(-3) (4 ppt) and 4 x 10(7) molecules cm 3 (1 ppt) up to 6 x 10(9) molecules cm(-3) (222 ppt) and 1 x 10(9) molecules cm(-3) (37 ppt), respectively. The HCl and HBr concentrations are enhanced along with the increase of atmospheric temperature, UVB and levels of gaseous HNO3. Based on the air mass analysis and high correlations of HCl and HBr with the burning indicators (HCN and HCNO), gaseous HCl and HBr are found to be related to anthropogenic burning aerosols. The gas-particle partitioning may also play a dominant role in the elevated daytime HCl and HBr. During the daytime, the reactions of HCl and HBr with OH radicals lead to significant production of atomic Cl and Br, up to 2 x 10(4) molecules cm(-3) s(-1) and 8 x 10(4) molecules cm(-3) s(-1), respectively. The production rate of atomic Br (via HBr + OH) is 2-3 times higher than that of atomic Cl (via HCl + OH), highlighting the potential importance of bromine chemistry in the urban area. On polluted days, the production rates of atomic Cl and Br are faster than those on clean days. Furthermore, our observations of elevated HCl and HBr may suggest an important recycling pathway of halogen species in inland megacities and may provide a plausible explanation for the widespread halogen chemistry, which could affect the atmospheric oxidation in China.

Automated summary

This study focused on measuring gaseous HCl and HBr in urban Beijing during winter and early spring of 2019, identifying factors affecting their concentrations, such as atmospheric temperature, UVB, gaseous HNO3, and burning aerosols. The researchers found that gas-particle partitioning and reactions with OH radicals led to significant production of atomic Cl and Br during the day. On polluted days, the production rates of atomic Cl and Br were faster than on clean days, suggesting an important recycling pathway of halogen species in inland megacities.