Temperature and acidity dependence of secondary organic aerosol formation from α -pinene ozonolysis with a compact chamber system

摘要

Secondary organic aerosols (SOAs) affect human health and climate change prediction; however, the factors (e.g., temperature, acidity of pre-existing particles, and oxidants) influencing their formation are not sufficiently resolved. Using a compact chamber, the temperature and acidity dependence of SOA yields and chemical components in SOA from α -pinene ozonolysis were systematically investigated under 278, 288, and 298?K temperatures using neutral ((NH 4 ) 2 SO 4 ) and acidic (H 2 SO 4 + ((NH 4 ) 2 SO 4 )) seed aerosols. SOA components with m / z ?less than 400 were analyzed using negative electrospray ionization liquid-chromatography time-of-flight mass spectrometry. Based on the slightly negative temperature dependence of the SOA yields, the enthalpies of vaporization under neutral and acidic seed conditions were estimated to be 25 and 44?kJ?mol ?1 , respectively. In addition, SOA yields increased with an increase in the acidity of seed particles (solid/near-solid state) at low SOA mass loadings, when compared with the seed particle amounts. Acidity dependence analysis of the chemical formula, molecular mass, and O:C ratio of the detected compounds indicated the enhanced formation of multiple oligomers in the wide molecular mass range with a wide range of O:C ratios under acidic seed conditions. The peak abundances of some chemical compounds increased with an increase in the acidity of seed particles (e.g., m / z ? 197, 311, 313, 339, 355, and 383), while decreases in the peak abundances of some chemical compounds were observed (e.g., m / z ?171, 185, 215, 343, and 357). The acidity dependence could be explained by acid-catalyzed heterogeneous reactions or acid-catalyzed decomposition of hydroperoxides. In addition, organosulfate (OS) formation was observed under acidic seed conditions. Six out of the 11 detected OSs were potentially formed via the aldehyde + HSO 4 - pathway.