Evaluation of gas chromatography-atmospheric pressure chemical ionization tandem mass spectrometry as an alternative to gas chromatography tandem mass spectrometry for the determination of polychlorinated biphenyls and polybrominated diphenyl ethers

Abstract

A method for the analysis of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in serum was developed using gas chromatography coupled to tandem mass spectrometry with atmospheric pressure chemical ionization (GC-APCI-MS/MS). The ionization and fragmentation performance of APCI were evaluated and compared with those of electron ionization (EI). In contrast to extensive fragmentation caused by EI with high energy, soft ionization achieved by APCI produced mass spectra dominated by molecular ions from the first stage of MS analysis. Better sensitivity and selectivity achieved by the GC-APCI-MS/MS method allowed to analyze serum samples with a low volume (100 μL). The limits of detection (LODs) ranged from 0.067 to 14 pg/mL for the analysis in serum samples. The developed method was evaluated at three spiking levels (0.05, 0.5 and 5 ng/mL for PCBs), showing good recoveries and repeatability. The recoveries ranged from 74.0% to 130.5%, and the relative standard deviations (RSDs) were less than 20%, for all analytes. The determination of PCBs and PBDEs in the human serum samples by GC-APCI-MS/MS was compared with gas chromatography-tandem mass spectrometry with EI (GC-EI-MS/MS). BDE-99 and BDE-100 were successfully quantified by GC-APCI-MS/MS, while these two PBDE congeners were not detected by GC-EI-MS/MS. The GC-APCI-MS/MS method had a clear advantage when analyzing compounds at low levels.