Evaporation Kinetics of Organic Aerosols: Species-wise Measurements and Estimates

Abstract:

A large fraction of atmospheric fine particulate matters (PM_2.5) are organic aerosols (OA) that can form from primary emission (primary OA) or oxidation of more volatile organic compounds (secondary OA). Most OA are semi-volatile that can evaporate from particle phase to gas phase. OA evaporation strongly impacts aerosol mass loading, aerosol oxidation state, and aerosol properties in the atmosphere. In this study, we use four semi-volatile long-chain n-alkanes (n-octadecane, n-eicosane, n-docosane, and n-tetracosane) and α-pinene-derived OA as surrogates for primary and secondary OA, respectively. The evaporation of these OA components was examined in a flow reactor. Two soft ionization mass spectrometry techniques were used to measure evaporation kinetics of individual OA constituents: on-line direct analysis in real time-mass spectrometry (DART-MS) (used for secondary OA) and off-line two-dimensional gas chromatograph coupled to a high-resolution time-of-flight mass spectrometer (GC×GC/HTOF-MS) with vacuum ultraviolet (VUV) photoionization (used for primary OA). The semi-volatile n-alkanes can be oxidized in both phases, following different reaction schemes and leading to multigenerational oxygenated products with different isomeric distributions. Here the evaporation kinetic of primary OA surrogates was determined based on chemical analysis and kinetic simulations. The evaporation of α-pinene-derived OA was characterized based on the DART-MS mass spectra change upon heating. Results for both systems suggest slow evaporation compared to the gas-particle partitioning theory, especially when the OA are solid. The species-wise measurements using novel techniques provide insights into the detailed evaporation kinetics for atmospheric relevant systems.