title: Secondary organic aerosol formation from high-NO(x) photo-oxidation of low volatility precursors: n-alkanes.
abstract: 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(x) 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 heptadecane at a C(OA) of 15.4 microg m(-3). As with other photo-oxidation 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 microg m(-3), the SOA mass spectrum, as measured with an aerosol mass spectrometer, had a large contribution from m/z 44, 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.
authors.affiliation: Center for Atmospheric Particle Studies, Carnegie Mellon University, USA.
authors.forename: Albert A
authors.initials: AA
authors.lastname: Presto
authors.forename: Marissa A
authors.initials: MA
authors.lastname: Miracolo
authors.forename: Neil M
authors.initials: NM
authors.lastname: Donahue
authors.forename: Allen L
authors.initials: AL
authors.lastname: Robinson
mesh_terms: D000336:Aerosols / Q000138:chemical synthesis*; D000393:Air Pollutants / Q000032:analysis / Q000138:chemical synthesis*; D000473:Alkanes / Q000737:chemistry*; D001272:Atmosphere / Q000737:chemistry; D004784:Environmental Monitoring; D009589:Nitrogen Oxides / Q000737:chemistry*; D010083:Oxidants, Photochemical / Q000737:chemistry; D010084:Oxidation-Reduction; D012905:Smog / Q000032:analysis; D055549:Volatile Organic Compounds / Q000032:analysis / Q000138:chemical synthesis
chemical_list: D000336:Aerosols; D000393:Air Pollutants; D000473:Alkanes; D009589:Nitrogen Oxides; D010083:Oxidants, Photochemical; D012905:Smog; D055549:Volatile Organic Compounds