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

J Chromatogr A. 2016 Nov 11:1472:88-98. doi: 10.1016/j.chroma.2016.10.021. Epub 2016 Oct 13.

Abstract

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 N2 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 pgm-3 level for the investigated PAHs (42pgm-3), oxy-PAHs (either 42 or 83pgm-3) and nitro-PAHs (either 83 or 167pgm-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 2.5μm) 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 (1ngm-3) set by the European Commission.

Keywords: Method validation; PAHs; Particulate matter; nitro-PAHs; oxy-PAHs.

MeSH terms

  • Benzo(a)pyrene / analysis
  • Benzo(a)pyrene / chemistry
  • Chromatography, Liquid
  • Cities
  • Gas Chromatography-Mass Spectrometry / methods*
  • Limit of Detection
  • Nitrates / chemistry*
  • Oxygen / chemistry*
  • Particulate Matter / chemistry*
  • Polycyclic Aromatic Hydrocarbons / analysis*
  • Polycyclic Aromatic Hydrocarbons / chemistry*
  • Tandem Mass Spectrometry / methods*
  • Time Factors

Substances

  • Nitrates
  • Particulate Matter
  • Polycyclic Aromatic Hydrocarbons
  • Benzo(a)pyrene
  • Oxygen