Sources and transformations of particle-bound polycyclic aromatic hydrocarbons in Mexico City

Abstract. Understanding sources, concentrations, and transformations of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere is important because of their potent mutagenicity and carcinogenicity. The measurement of particle-bound PAHs by three different methods during the Mexico City Metropolitan Area field campaign in April 2003 presents a unique opportunity for characterization of these compounds and intercomparison of the methods. The three methods are (1) collection and analysis of bulk samples for time-integrated gas- and particle-phase speciation by gas chromatography/mass spectrometry; (2) aerosol photoionization for fast detection of PAHs on particles' surfaces; and (3) aerosol mass spectrometry for fast analysis of size and chemical composition. This research represents the first time aerosol mass spectrometry has been used to measure ambient PAH concentrations and the first time that fast, real-time methods have been used to quantify PAHs alongside traditional filter-based measurements in an extended field campaign. Speciated PAH measurements suggest that motor vehicles and garbage and wood burning are important sources in Mexico City. The diurnal concentration patterns captured by aerosol photoionization and aerosol mass spectrometry are generally consistent. Ambient concentrations of particle-phase PAHs typically peak at ~110 ng m^-3 during the morning rush hour and rapidly decay due to changes in source activity patterns and dilution as the boundary layer rises, although surface-bound PAH concentrations decay faster. The more rapid decrease in surface versus bulk PAH concentrations during the late morning suggests that freshly emitted combustion-related particles are quickly coated by secondary aerosol material in Mexico City's atmosphere and may also be transformed by heterogeneous reactions.