Determination of polybrominated diphenyl ethers and novel brominated flame retardants in human serum by gas chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry

The accurate detection of brominated flame retardants (BFRs) in humans is an area of high scientific interest and regulatory need due to their potential toxicity. The instrumental analysis of BFRs was commonly performed on gas chromatography-mass spectrometry (GC-MS) operating in electron ionization (EI) or negative chemical ionization (NCI) modes. However, soft ionization techniques, such as atmospheric pressure chemical ionization (APCI), may be more suitable for the analysis of BFRs because the BFRs show high fragmentation in EI and low selectivity in NCI. Additionally, accurate quantifications of BFRs in complex matrices is challenging due to their low concentrations and therefore, a highly sensitive technique is desperately needed. In this study, a new methodology based on gas chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry (GC-APCI-MS/MS) analysis was developed for the determination of thirteen BFRs (eight usually monitored polybrominated diphenyl ethers (PBDEs) congeners and five additional novel BFRs) in human serum. The primary task was to evaluate the potential of the GC-APCI-MS/MS technique for the trace analysis of BFRs in human serum. The results of the spiked recovery test using fetal bovine serum showed that mean recoveries of the analytes ranged from 83.4% to 118% with reduced swing differential signaling (RSDs) of ≤21.1%. The methodological limits of detection (mLOD) of the analytes ranged from 0.04 to 30 pg/mL, and these values were at least one order of magnitude lower than those estimated by the authors in a previous study using GC-NCI-MS or GC-EI-MS/MS, indicating that GC-APCI-MS/MS is more sensitive. Specially, compared to GC-NCI-MS and GC-EI-MS/MS, when GC-APCI-MS/MS was used for the detection of highly brominated BFRs, such as BDE-209 and decabromodiphenyl ethane (DBDPE), a notable improvement in sensitivity and reliability was obtained using a deactivated capillary column connected to the analytical column as the transfer line and maintaining a high temperature to improve the chromatographic behaviors. The developed methodology was successfully used for the analysis of BFRs in human serum collected from residents living in a BFR production area and Beijing.