Determination of particulate phase polycyclic aromatic hydrocarbons and their nitrated and oxygenated derivatives using gas chromatography-mass spectrometry and liquid chromatography-tandem mass spectrometry

An analytical method has been developed for the quantitative determination of polycyclic aromatic hydrocarbons (PAHs) and their nitrated and oxygenated derivatives (nitro-and oxy-PAHs respectively) in particulate matter (PM) samples. The sample preparation procedure included only a simple and quick sonication-assisted extraction step, clean-up based on addition of water and centrifugation as well as pre-concentration under N-2 stream. The determination of 16 PAHs and 4 oxy-PAHs was carried out by gas chromatography-mass spectrometry, while liquid chromatography-tandem mass spectrometry was used in the case of the 11 investigated nitro-PAHs. The optimized method was fully evaluated in terms of trueness, precision (repeatability), limit of detection (LOD), limit of quantification (LOQ), sensitivity and linearity. The LOQ values ranged at pg m(-3) level for the investigated PAHs (42 pg m(-3)), oxy-PAHs (either 42 or 83 pg m(-3)) and nitro-PAHs (either 83 or 167 pg m(-3)) as well. The developed method was applied for the quantitative determination of PAHs, nitro-and oxy-PAHs in urban PM2.5 (particles with aerodynamic diameter smaller than 2.5 mu m) samples (n=36) collected in Budapest, Hungary. Almost 100% of the PM2.5 samples contained the investigated PAHs and oxy-PAHs in detectable and quantifiable amounts; however, the concentration of the nitro-PAHs was generally lower than the corresponding LOD/LOQ values. According to our results, during the 3-year long sampling campaign the concentration of benzo(a)pyrene never exceeded the limit value (1 ng m(-3)) set by the European Commission. (C) 2016 Elsevier B.V. All rights reserved.