Physicochemical and oxidative characteristics of semi-volatile components of quasi-ultrafine particles in an urban atmosphere

This study examines the physicochemical and redox profiles of atmospheric semi-volatile compounds to evaluate their contribution to the oxidative potential of ambient particulate matter (PM). Concentrated ambient and thermodenuded quasi-ultrafine particles (<180 nm) were collected using the versatile aerosol concentration enrichment system (VACES) at an urban site near downtown Los Angeles. A thermodenuder (TD) was used to selectively remove the semi-volatile components of these aerosols over the temperature range of 50-200 °C. The oxidative potential of PM was measured by means of the DTT (dithiothreitol) assay. Detailed chemical analyses of PM samples, including organic and elemental carbon, water soluble elements, inorganic ions and PAHs (polycyclic aromatic hydrocarbons), were conducted to quantify the volatility profiles of different PM species, and also to investigate their effect on measured oxidative potential. Refractory constituents, such as metals and elemental carbon, were marginally affected by heating, while labile species such as organic carbon and PAHs showed progressive loss in concentration with increase in TD temperature. The DTT-measured oxidative potential of PM was significantly decreased as the aerosols were heated and their semi-volatile components were progressively removed (42 ± 5%, 47 ± 8% and 66 ± 6% decrease at 50, 100 and 200 °C, respectively). Thus, semi-volatile compounds present in quasi-ultrafine urban aerosols constitute a significant fraction of PM oxidative potential, which is associated with the cellular generation of reactive oxygen species. Regression analysis performed between chemical constituents and DTT activity showed that the oxidative potential was strongly correlated with organic carbon and PAHs (R ≥ 0.80; p ≤ 0.05).