Secondary Organic Aerosol Formation from High-NOx Photo-Oxidation of Low Volatility Precursors: n-Alkanes

Smog chamber experiments were conducted to investigate secondary organic aerosol (SOA)formation from photo-oxidation of low-volatility precursors; n-alkanes were chosen as a model system. The experiments feature atmospherically relevant organic aerosol concentrations (C-OA). Under high-NO, conditions SOA yields increased with increasing carbon number (lower volatility) for n-decane, n-dodecane, n-pentadecane, and n-heptadecane, reaching a yield of 0.51 for heptaclecane at a C-OA of 15.4 mu g m(-3). As with other photooxidation systems, aerosol yield increased with UV intensity. Due to the log-linear relationship between n-alkane carbon number and vapor pressure as well as a relatively consistent product distribution it was possible to develop an empirical parametrization for SOA yields for n-alkanes between C-12 and C-17. This parametrization was implemented using the volatility basis set framework and is designed for use in chemical transport models. For C-OA < 2 mu g m(-3), the SOA mass spectrum, as measured with an aerosol mass spectrometer, had a large contribution from m/z44, indicative of highly oxygenated products. At higher C-OA, the mass spectrum was dominated by m/z 30, indicative of organic nitrates. The data support the conclusion that lower volatility organic vapors are important SOA precursors.