Investigating the evolution of summertime secondary atmospheric pollutants in urban Beijing

Understanding the formation of tropospheric ozone (O₃) and secondary particulates is essential for controlling secondary pollution in megacities. Intensive observations were conducted to investigate the evolution of O₃, nitrate (NO₃^-), sulfate (SO₄^2-) and oxygenated organic aerosols ((OOAs), a proxy for secondary organic aerosols) and the interactions between O₃, NO_x oxidation products (NO_z) and OOA in urban Beijing in August 2012. The O₃ concentrations exhibited similar variations at both the urban and urban background sites in Beijing. Regarding the O₃ profile, the O₃ concentrations increased with increasing altitude. The peaks in O₃ on the days exceeding the 1h or 8h O₃ standards (polluted days) were substantially wider than those on normal days. Significant increases in the NO_z mixing ratio (i.e., NO_y - NO_x) were observed between the morning and early afternoon, which were consistent with the increasing oxidant level. A discernable NO₃^- peak was also observed in the morning on the polluted days, and this peak was attributed to vertical mixing and strong photochemical production. In addition, a SO₄^2- peak at 18:00 was likely caused by a combination of local generation and regional transport. The OOA concentration cycle exhibited two peaks at approximately 10:00 and 19:00. The OOA concentrations were correlated well with SO₄^2- ([OOA]=0.55×[SO₄^2-]+2.1, r²=0.69) because they both originated from secondary transformations that were dependent on the ambient oxidization level and relative humidity. However, the slope between OOA and SO₄^2- was only 0.35, which was smaller than the slope observed for all of the OOA and SO₄^2- data, when the RH ranged from 40 to 50%. In addition, a photochemical episode was selected for analysis. The results showed that regional transport played an important role in the evolution of the investigated secondary pollutants. The measured OOA and O_x concentrations were well correlated at the daily scale, whereas the hourly OOA and O_x concentrations were insignificantly correlated in urban Beijing. The synoptic situation and the differences in the VOC oxidation contributing to O₃ and SOAs may have resulted in the differences among the correlations between OOA and O_x at different time scale. We calculated OOA production rates using the photochemical age (defined as -log₁₀(NO_x/NO_y)) in urban plumes. The CO-normalized OOA concentration increased with increasing photochemical age, with production rates ranging from 1.1 to 8.5μgm^-3ppm^-1h^-1 for the plume from the NCP.