Impact of biogenic secondary organic aerosol (SOA) loading on the molecular composition of wintertime PM2.5 in urban Tianjin: an insight from Fourier transform ion cyclotron resonance mass spectrometry

Biomass burning is one of the key sources of urban aerosols in the North China Plain, especially during winter, when the impact of secondary organic aerosols (SOAs) formed from biogenic volatile organic compounds (BVOCs) is generally considered to be minor. However, little is known about the influence of biogenic SOA loading on the molecular composition of wintertime organic aerosols. Here, we investigated the water-soluble organic compounds in fine particulate matter (PM2.5) from urban Tianjin by ultrahigh-resolution Fourier transform ion cyclotron resonanc mass spectrometry (FT-ICR MS). Our results show that most of the CHO and CHON compounds are derived from biomass burning which are poor in oxygen and contain aromatic rings that probably contribute to light-absorbing brown carbon (BrC) chromophores. Under moderate to high SOA-loading conditions, the nocturnal chemistry is more efficient than photooxidation to generate secondary CHO and CHON compounds with high oxygen content. Under low SOA loading, secondary CHO and CHON compounds with low oxygen content are mainly formed by photochemistry. Secondary CHO compounds are mainly derived from oxidation of monoterpenes. However, nocturnal chemistry may be more productive to sesquiterpene-derived CHON compounds. In contrast, the number- and intensity-weight of S-containing groups (CHOS and CHONS) increased significantly with the increase of biogenic SOA loading, which agrees with the fact that a majority of the S-containing groups are identified as organosulfates (OSs) and nitrooxy-organosulfates (nitrooxy-OSs) that are derived from the oxidation of BVOCs. Terpenes may be potential major contributors to organosulfates and nitrooxy-organosulfates. While the nocturnal chemistry is more beneficial to the formation of organosulfates and nitrooxy-organosulfates under low SOA loading. The SOA loading is an important factor that is associated with the oxidation degree, nitrate group content and chemodiversity of nitrooxy-organosulfates. Furthermore, our study suggests that the hydrolysis of nitrooxy-organosulfates is a possible pathway for the formation of organosulfates.

Automated summary

Biomass burning is a key source of urban aerosols in the North China Plain, with limited knowledge on the influence of biogenic SOA loading on the molecular composition of wintertime organic aerosols. Water-soluble organic compounds in PM2.5 from urban Tianjin were analyzed, revealing that biomass burning contributes to the majority of CHO and CHON compounds. The chemistry and level of biogenic SOA loading plays a significant role in the formation of secondary compounds, including CHO, CHON, CHOS, and CHONS. The hydrolysis of nitrooxy-organosulfates is identified as a possible pathway for the formation of organosulfates.