Vertical distribution of atmospheric particulate matters within urban boundary layer in southern China: size-segregated chemical composition and secondary formation through cloud processing and heterogeneous reactions

Abstract. Great progress has been made recently in the understanding of the sources and formation mechanisms of atmospheric aerosols at the ground level. However, vertical profiles and sources of size-resolved particulate matter within the urban boundary layer are still lacking. In this study, vertical distribution characteristics of size-segregated particles were investigated at three observation platforms (ground, 118 m and 488 m) on the 610-meter-high Canton Tower in Guangzhou, China. Size-segregated aerosol samples were simultaneously collected at the three levels on the Canton Tower in autumn and winter, respectively. Major aerosol components, including water-soluble ions, organic carbon and elemental carbon, were measured. The results showed that daily average fine-particle concentrations generally decreased with height. Concentrations of sulfate and ammonium in fine particles displayed small vertical gradients and nitrate concentrations increased with height in autumn, while the above chemical components showed greater variations in winter than in autumn. The size distributions of sulfate and ammonium in both seasons were characterized by dominant unimodal droplet modes with a peak at the size range of 0.44–1.0 μm. In autumn, the nitrate size distribution was bi-modal, peaking at 0.44–1.0 μm and 2.5–10 μm, while it was unimodal in winter, implying that the formation mechanisms for nitrate particles were different in the two seasons. Our results suggest droplet mode sulfate and nitrate are likely formed from aqueous-phase reactions and coarse mode nitrate formation is attributed to heterogeneous reactions of gaseous nitric acid on existing sea-derived coarse particles in autumn at the measurement site. The results from pollution cases study further showed that atmospheric aqueous-phase and heterogeneous reactions together with adverse weather conditions, such as temperature inversion and calm wind, resulted in the autumn and winter haze pollution in the PRD region.