Analysis of Secondary Organic Aerosol Compounds from the Photooxidation of <i>d</i>-Limonene in the Presence of NO<i>_X</i> and their Detection in Ambient PM_2.5

Abstract

Chemical analysis of secondary organic aerosol (SOA) from the photooxidation of a d-limonene/NOx/air mixture was carried out. SOA, generated in a smog chamber, was collected on Zefluor filters. To determine the structural characteristics of the compounds, the filter samples were solvent extracted and derivatized using analytical techniques that characterize functional groups contained in the compound: BF3-methanol derivatization was used for carboxylic groups, BSTFA for acidic and nonacidic hydroxyl groups, and PFBHA for ketone and aldehyde groups. The resulting derivative compounds were analyzed by GC-MS in the methane Cl and El modes. GC-MS analysis showed the occurrence of 103 oxygenated organic compounds in the filter extracts, 28 of which were identified. The major components include five tracer compounds previously identified from the photooxidation of alpha-pinene/NOx or beta-pinene/NOx systems, C4-C6 linear dicarboxylic acids, ketolimononaldehyde, limonic acid, and ketolimonic acid. Time profiles, yields, and proposed reaction schemes are provided for selected compounds. The laboratory SOA yield was 0.51 at a SOA concentration of 1470 microg m(-3). To determine the contributions of SOA products from d-limonene to ambient PM2.5, an analysis was performed for eight ambient PM2.5 samples collected in the southeastern United States in summer 2003. GC-MS analysis showed the occurrence of 21 d-limonene SOA compounds, indicating the impact of d-limonene on the regional aerosol burden. Based on our analysis, two compounds (nos. 55 and 69), not observed from the photooxidation of alpha-pinene or beta-pinene, are candidate tracers for d-limonene in atmospheric particulate matter.