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Multiple food research studies have shown that the polycyclic aromatic hydrocarbon (PAHs) are frequently found in processed cocoa products and chocolate. In a present study a method based on dopant-assisted atmospheric pressure photoionisation (DA-APPI) combined with a liquid chromatography/high-resolution mass spectrometer (HPLC–HRMS) for high-sensitivity analysis of four EU marker PAHs in dark chocolate samples was developed and fully validated according to the performance criteria set in EU guidelines. PAHs detection was achieved by HRMS in positive electrospray ionization mode with toluene used as a dopant to enhance the ionization efficiency of non-polar PAHs. The on-column instrument detection limits ranged from 0.8 to 1.2 pg for all four marker compounds. The method detection limits ranged from 0.016 to 0.024 μg kg −1  expressed on fat basis. The elaborated method was successfully applied to the analysis of four EU marker PAHs in dark chocolate samples. The presence of benzo[ a ]anthracene, benzo[ b ]fluoranthene and chrysene revealed at detectable levels in 100% of the samples, while benzo[ a ]pyrene was revealed in 77% of the samples, with its content ranging from 0.08 to 2.90 μg kg −1  fat.

journal of chromatographic science

Application of Dopant-Assisted Atmospheric Pressure Photoionisation HPLC–MS Method for the Sensitive Determination of Polycyclic Aromatic Hydrocarbons in Dark Chocolate