Ultra-high sensitive PAH analysis of certified reference materials and environmental samples by GC-APLI-MS.

Due to several polycyclic aromatic hydrocarbons (PAHs) being highly carcinogenic and at the same time occurring at very low environmental concentrations up to the microgram per kilogram range, highly sensitive chemical analysis in various matrices is needed. Here, for the first time, a method using gas chromatography (GC) and atmospheric pressure laser ionization-mass spectrometry (APLI-MS), which is much more sensitive compared to common GC-MS, proved to produce reliable (certified reference materials) and comparable (GC-MS) results. PAHs and selected isomers of alkyl-PAHs were targeted, whereby 53 analytes could be quantified individually; for one pair, the sum had to be calculated. In combination with the selective and sensitive (1+1)-REMPI process of the APLI, limits of detection (LODs) between 5 and 50 fg/μL could be obtained. To prove the reliability of this method, four certified reference materials (SRM1649b urban dust, SRM 1941b organics in marine sediment, BCR 535 fresh water harbor sediment, and ERM CC013a contaminated soil from a former gas plant site) were analyzed. The results were in good accordance with the certified values. In addition, analytical results of three different environmental matrices (bituminous coal, suspended particulate matter from river and pine needles) were compared to values obtained with well-established GC-EI-MS. The results show that this method presents an excellent tool ready-to-use for the analysis of environmental samples with very low PAH content or very low sample amount.