Sub-Parts-per-Billion Determination of Nitro-Substituted Polynuclear Aromatic Hydrocarbons in Airborne Particulate Matter and Soil by Electron Capture-Tandem Mass Spectrometry

A procedure for the determination of nitro-substiruted polynuclear aromatic hydrocarbons (nitro-PAH) on crude air-particulate and soil extracts is introduced. Elimination of purification and fractionation procedures was made possible by the use of both a selective ionization method, such as electron-capture chemical ionization, and a specific fragmentation process, in an experiment of tandem mass spectrometry (gas chromatography—electron capture tandem mass spectrometry). Different mass spectrometric procedures were compared. The best performance was observed when the nitro-PAH molecular ions [M]− were mass-selected by the first analyzer under multiple reaction monitoring conditions and then fragmented to NO2− (m/z 46). Detection limits were on the order of hundreds of femtograms, as determined in extracts of real environmental samples. This corresponds approximately to 5–15 pg of nitro-PAH per cubic meter of air sampled. Calibration curves were linear over 3 orders of magnitude. Applications to contamination from motor vehicle combustion and the iron industry are briefly discussed.