Evaluation of various mass spectrometry mode based on gas chromatography for quantifying the polycyclic aromatic hydrocarbon metabolites in human urine

•Improved mass spectrometry method for measuring PAH metabolites in human urine.•Using intra-class correlation to assess the reliability of different methods.•The validity of method was verified by participating in G-EQUAS program.•GC-AEI-MS/MS is suitable for large-scale human biomonitoring of urinary OH-PAHs. Hydroxyl polycyclic aromatic hydrocarbons (OH-PAHs) are frequently used as biomarkers to assess human exposure to polycyclic aromatic hydrocarbons (PAHs), which are typically present in minute concentrations in the human body. Although several studies have outlined methods for measuring OH-PAHs in human urine, these approaches may have limitations concerning the range of compounds detected, the sample volume required for pre-treatment, accuracy, and instrument maintenance costs. Advances in mass spectrometry technology have facilitated the use of various mass spectrometry modes based on gas chromatography. It is essential to evaluate different mass spectrometry modes to identify a more reliable and practical method for quantifying OH-PAHs in urine. Our comparative analysis of three gas chromatography-mass spectrometry modes revealed that advanced electron ionization (AEI) mode exhibited greater sensitivity for determination compared to electron ionization (EI) mode in tandem mass spectrometry. The method validation criteria were satisfied by GC-AEI-MS/MS, which demonstrated acceptable measurement errors (MEs) ranging from -23.0 % to 19.5 %, recoveries between 81.6 % and 112.1 %, and precision levels below 10.1 %. Furthermore, the reliability and accuracy of the GC-AEI-MS/MS method were corroborated through Intraclass Correlation Coefficient (ICC) evaluation (values > 0.75), participation in external proficiency testing programs (G-EQUAS), and analysis of certified reference materials, which exhibited a relative deviation of