Analysis of nitrated polycyclic aromatic hydrocarbons by liquid chromatography with fluorescence and mass spectrometry detection: Air particulate matter, soot, and reaction product studies

Polycyclic aromatic hydrocarbons (PAH) and their nitrated derivatives (nitro-PAH) are environmental pollutants which pose a threat to human health even at low concentration levels. In this study, efficient analytical methods for the analysis of nitro-PAH and PAH (extraction, clean-up, chromatographic separation, and spectrometric detection) have been developed, characterized, and applied to aerosol samples. The separation and quantification of 12 nitro-PAH was carried out by reversed-phase high performance liquid chromatography (HPLC), on-line reduction, and fluorescence detection. The detection limits were in the range of 0.03-0.5 μg L^-1 (6-100 pg in the investigated sample aliquots), and the recovery rates from soot samples were 70-90%. Nitro-PAH and PAH concentrations have been determined for different types of soot and for urban, rural, and alpine fine air particulate matter (PM2.5). For the first time, trace amounts of nitro-PAH have been detected in a high-alpine clean air environment. The on-line reduction and fluorescence technique has been complemented by atmospheric pressure chemical ionization time-of-flight mass spectrometry (APCI-TOF-MS). The MS detection allowed the analysis of partially nitrated and oxygenated PAH in laboratory studies of the heterogeneous reaction of PAH on soot and glass fiber substrates with gaseous nitrogen oxides and ozone. It led to the tentative identification of a previously unknown nitrated derivative of the particularly toxic PAH benzo[a]pyrene (BaP-nitroquinone), and provides the first experimental evidence that PAH-nitroquinones can be formed by reaction of PAH with atmospheric photooxidants.