The application of polycyclic aromatic hydrocarbon (PAH) analysis by gas chromatography coupled with atmospheric pressure laser ionization and mass spectrometry (GC-APLI-MS) to environmental samples was investigated in the study. The limit of detection for 40 PAH in a standard mixture was 5-100 fg, demonstrating GC-APLI-MS to be a highly sensitive technique and more sensitive by a factor of 100-3,500 compared to GC-MS. Acenaphthylene and cyclopenta[cd]pyrene were not detectable <2,500 fg per injection. To make use of this very high PAH sensitivity, the technique was applied to samples of environmental interest with limited available sample amounts such as particulate matter (PM), soot and a sample from a bioaccumulation test with Lumbriculus variegatus. First, special sample preparation was necessary and ultrasonic extraction proved to be suitable, if a thorough clean-up was performed and plastic materials avoided. By GC-APLI-MS and GC-MS, 224 and 28 single PAH compounds were detected in PM, about 1,000 and 15 in birch soot, and 9 and 2 in worm tissue, respectively, revealing the enormous potential of the method. The selectivity of GC-APLI-MS was shown for a crude oil where >2,200 PAH were detected without any sample preparation.

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