Atmospheric Reactions Influence Seasonal PAH and Nitro-PAH Concentrations in the Los Angeles Basin

Abstract

Ambient measurements of polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs were carried out during August 2002 and January 2003 in Los Angeles, CA, a source site and in Riverside, CA, a downwind receptor site approximately 90 km to the east of Los Angeles. Atmospheric concentrations of PAHs and nitro-PAHs are of interest because both of these compound classes include potent mutagens and carcinogens. To augment our current understanding of atmospheric formation of nitro-PAHs, four sampling periods were employed to study the diurnal variations of these compounds. The PAH concentrations were highest in Los Angeles during January, as a result of traffic input at this source site undertightwintertime atmospheric inversions. In contrast, nitro-PAH levels were highest in Riverside during August, as a result of enhanced summertime photochemistry. Hydroxyl radical-initiated reactions produced nitro-PAHs in both seasons, while in winter little evidence for nitrate radical chemistry was seen. For the August samples, nitrate radical-initiated formation of nitro-PAHs is suggested by nitro-PAH isomer profiles not only at the downwind location as anticipated, but also atthe source site. In southern California, the contribution of atmospheric formation through gas-phase radical-initiated PAH reactions to the ambient burden of nitro-PAHs is dominant, with the semi-volatile nitro-PAHs being the most abundant and 2-nitrofluoranthene being the major particle-associated nitro-PAH.