SummaryThe composition and concentration of polycyclic aromatic compounds (PAC) in fuels, their combustion products and in the atmosphere remains a topic of considerable interest. Despite the wealth of literature on the identification of PAC, speciation at low concentrations remains difficult due to instrument limitation and the complexity of fuel and environmental samples. Consequently online sample preparation procedures (SPE, SFE, LC, etc.) are becoming an increasingly important step in the analysis procedure particularly where sample clean-up and fractionation are essential for improving analytical resolution. In this study a normal phase high pressure liquid chromatography-gas chromatography (LC-GC) system has been developed to provide quantitative analysis of samples, as diverse as coal liquids, petroleum fuels, diesel exhaust particulates and urban air particulates. Separation and identification of parent and alkylated PAH, heterocyclic, nitro-and oxy-PAC can be achieved by direct coupling to an atomic emission detector and a bench top mass spectrometer. For both systems the primary LC separation combined with the large sample volume transferred to GC vastly improves detection limits. Furthermore the complimentary nature of the two detectors used enables the positive identification of many unknowns.