Tower-based profiles of wintertime secondary organic aerosols in the urban boundary layer over Guangzhou.

ABSTRACT

Secondary organic aerosol (SOA) accounts for a large fraction of fine particulate matter (PM2.5), but the lack of vertical observations of SOA in the urban boundary layer (UBL) limits a comprehensive understanding of its sources and formation mechanisms. In this study, PM2.5 samples were simultaneously collected at 3 m, 118 m, and 488 m on the Canton Tower in Guangzhou during winter. Typical SOA tracers, including oxidation products of isoprene (SOAI), monoterpene (SOAM), sesquiterpene (SOAS), and toluene (ASOA), were investigated alongside meteorological parameters and gaseous/particulate pollutants. Total concentrations of SOA tracers showed an increasing trend with height, with daytime levels exceeding nighttime levels. C5-alkene triols and 2-methylglyceric acid displayed a significant increase with height, potentially affected by nighttime chemistry in the residual layer, determining the overall vertical trend of SOAI tracers. Concentrations of later-generation SOAM (SOAM_S) tracers also increased with height, while those of first-generation SOAM (SOAM_F) tracers decreased, indicating relatively aged SOAM in the upper layers. SOAS and ASOA tracers exhibited higher enhancement under polluted conditions, likely impacted by biomass burning and anthropogenic emissions. The yields of SOAI tracers varied with temperature in the vertical profile. The formation of SOAM_F tracers was negatively correlated with relative humidity, liquid water content, and pH, affecting their vertical distributions. The effect of O3 on SOA formation enhanced significantly with height, influenced by air mass transport, and likely contributed to the higher yields of SOA in the upper layer. However, at ground level, SOA formation was primarily driven by high local emissions of both NOx and volatile organic compounds. We also observed the roles of SO2 in SOA generation, particularly at 118 m. This study demonstrates the vertical diurnal characteristics of SOA tracers in the UBL, highlighting the varying effects of meteorological conditions and anthropogenic pollutants on SOA formation at different heights.