Effect of relative humidity on the molecular composition of secondary organic aerosols from α-pinene ozonolysis†

Secondary organic aerosols (SOAs) originating from the oxidation of biogenic volatile organic compounds such as monoterpenes by atmospheric oxidants (e.g. OH, ozone, and NO₃), constitute a widespread source of organic aerosols in the atmosphere. Among monoterpenes, α-pinene has the highest emission rates and its ozonolysis is often used as a canonical SOA system. However, the molecular composition of SOAs obtained from monoterpene ozonolysis as a function of relative humidity (RH) remains unclear. Herein, we investigated the real-time molecular composition of SOAs obtained from the ozonolysis of α-pinene using extractive electrospray ionization coupled with long time-of-flight mass spectrometry (EESI-LTOF-MS). We investigated the dependence of the molecular composition on RH in the presence and absence of seed aerosols. We characterized a large number of organic compounds, including less oxygenated and highly oxygenated organic molecules (HOMs). In the presence of a ammonium sulfate (AS) seed aerosol, the fractions of both monomers and dimers in the SOAs from α-pinene ozonolysis remained largely unchanged as RH increased from 3% to 84%, which can be attributed to a similar extent of increase in the absolute abundance of both dimers and monomers with increasing RH. The increase of the absolute abundance of monomers is likely due to the enhanced partitioning of less oxygenated semi-volatile monomer products (such as C₁₀H₁₆O_x≤6) at higher RH. The increase in the absolute abundance of dimers may be attributed to acid-catalyzed reactions, which is corroborated by a marked change in the distribution pattern of dimers. The average O/C of the most abundant product families in the SOAs, such as C₁₀H₁₆O_x, decreased with increasing RH due to the decreasing fractions of more oxygenated products (C₁₀H₁₆O_x>6). However, the elemental composition (O/C and H/C) of the total SOA remained stable with increasing RH. In contrast, in the absence of the seed aerosol, an increase in the monomer fraction and a decrease in the dimer fraction were observed with increasing RH. These changes were attributed to a combination of different extents of condensation enhancement of monomer and dimer vapors by increasing RH and different vapor wall losses of monomers and dimers. Our results provide new insights into the RH-dependent molecular chemical composition of α-pinene SOAs. We also highlight the necessity to characterize the composition of SOAs at the molecular level.