Chlorine-initiated oxidation of n-alkanes under high NOx conditions: Insights into secondary organic aerosol composition and volatility using a FIGAERO-CIMS

Chlorine-initiated oxidation of n-alkanes (C8-12) under high nitrogen oxides conditions was investigated. Observed secondary organic aerosol yields (0.16 to 1.65) are higher than those for OH-initiated oxidation of C8-12 alkanes (0.04 to 0.35). A High-Resolution Time-of-Flight Chemical Ionization Mass Spectrometer coupled to a Filter Inlet for Gases and AEROsols (FIGAERO-CIMS) was used to characterize the gas- and particle-phase molecular composition. Chlorinated organics were observed, which likely originated from chlorine addition to the double bond present on the heterogeneously produced dihydrofurans. A two-dimensional thermogram representation was developed to visualize composition and relative volatility of organic aerosol components using unit-mass resolution data. Evidence of oligomer formation, thermal fragmentation and thermal decomposition was observed. Aerosol yield and oligomer formation were suppressed under humid conditions (35 to 67 % RH) relative to dry conditions (under 5 % RH). The temperature at peak desorption signal, Tmax, a proxy for aerosol volatility, was shown to change with aerosol filter loading, which should be constrained when evaluating aerosol volatilities using the FIGAERO-CIMS. Results suggest that long-chain anthropogenic alkanes could contribute significantly to ambient aerosol loading over their atmospheric lifetime.