Size-Segregated Chemical Compositions of HULISs in Ambient Aerosols Collected during the Winter Season in Songdo, South Korea

The primary objective of this study was to investigate the molecular compositions of humic-like substances (HULISs) in size-resolved ambient aerosols, which were collected using an Anderson-type air sampler (eight size cuts between 0.43 and 11 μm) during the winter season (i.e., the heating period of 8−12 January 2018) in Songdo, South Korea. The aerosol samples collected during the pre- (preheating, 27 November−1 December 2017) and post-winter (postheating, 12−16 March 2018) periods were used as controls for the winter season samples. According to the concentrations of the chromophoric organics determined at an ultraviolet (UV) wavelength of 305 nm, most of the HULIS compounds were found to be predominantly enriched in particles less than 2.1 μm regardless of the sampling period, which shows that particulate matter (diameter less than 2.5 μm; PM2.5) aerosols were the dominant carriers of airborne organics. Ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (UHR FT−ICR MS) analysis of the aerosol-carried organic substances revealed that as the aerosol size increased the proportions of CHO and nitrogen-containing CHO (CHON) compounds decreased, while the proportion of sulfur-containing CHO (CHOS) species increased. In particular, the ambient aerosols during the heating period seemed to present more CHO and CHON and less CHOS molecules compared to aerosols collected during the pre- and postheating periods. The aerosols collected during the heating period also exhibited more aromatic nitrogen-containing compounds, which may have originated from primary combustion processes. Overall, the particle size distribution was likely influenced by source origins; smaller particles are likely from local sources, such as traffic and industries, and larger particles (i.e., aged particles) are likely derived from long-range transport generating secondary organic aerosols (SOAs) in the atmosphere. The results of the size-segregated particles can be utilized to understand particle formation mechanisms and shed light on their toxicity to human health.