Diurnal Variations in High Time-Resolved Molecular Distributions and Formation Mechanisms of Biogenic Secondary Organic Aerosols at Mt. Huang, East China

The molecular characteristics and formation mechanism of biogenic secondary organic aerosols (BSOAs) in the forested atmosphere are poorly known. Here, we report the temporal variations in and formation processes of BSOA tracers derived from isoprene, monoterpenes, and b caryophyllene in PM2.5 samples collected at the foot of Mt. Huang (483 m a. s. l) in East China during the summer of 2019 with a 3 h time resolution. The concentrations of nearly all of the detected species, including organic carbon (OC), elemental carbon (EC), levoglucosan, and SIA (sum of SO42-, NO3-, and NH4+), were higher at night (19:00-7:00 of the next day) than in the daytime (7:00-19:00). In addition, air pollutants that accumulated by the dynamic transport of the mountain breeze at night were also a crucial reason for the higher BSOA tracers. Most of the BSOA tracers exhibited higher concentrations at night than in the daytime and peaked at 1:00 to 4:00 or 4:00 to 7:00. Those BSOA tracers presented strong correlations with O-3 in the daytime rather than at night, indicating that BSOAs in the daytime were primarily derived from the photo-oxidation of BVOCs with O-3. The close correlations of BSOA tracers with SO42- and particle acidity (pH(is)) suggest that BSOAs were primarily derived from the acid-catalyzed aqueous-phase oxidation. Considering the higher relative humidity and LWC concentration at night, the promoted aqueous oxidation was the essential reason for the higher concentrations of BSOA tracers at night. Moreover, levoglucosan exhibited a robust correlation with BSOA tracers, especially beta-caryophyllinic acid, suggesting that biomass burning from long-distance transport exerted a significant impact on BSOA formation. Based on a tracer-based method, the estimated concentrations of secondary organic carbon (SOC) derived from isoprene, monoterpenes, and beta caryophyllene at night (0.90 +/- 0.57 mu gC m(-3)) were higher than those (0.53 +/- 0.34 mu gC m(-3)) in the daytime, accounting for 14.5 +/- 8.5% and 12.2 +/- 5.0% of OC, respectively. Our results reveal that the BSOA formation at the foot of Mt. Huang was promoted by the mountain-valley breezes and anthropogenic pollutants from long-range transport.

Automated summary

This study investigates the temporal variations and formation processes of biogenic secondary organic aerosol (BSOA) tracers in PM2.5 samples collected at the foot of Mt. Huang in East China during the summer of 2019. The concentrations of BSOA tracers were higher at night than in the daytime, mainly derived from the photo-oxidation of BVOCs and acid-catalyzed aqueous-phase oxidation. Increased humidity and liquid water content at night promoted the higher concentrations of BSOA tracers. Biomass burning from long-range transport also contributed to BSOA formation.