Chinese Journal of Chromatography

Chinese Journal of Chromatography ›› 2011, Vol. 29 ›› Issue (12): 1165-1172.DOI: 10.3724/SP.J.1123.2011.01165

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Determination of three brominated flame retardants in human serum using solid-phase extraction coupled with ultra-performance liquid chromatography-tandem mass spectrometry and gas chromatography-mass spectrometry

XIAO Zhongxin1, FENG Jinfang2, SHI Zhixiong2*, LI Jingguang3, ZHAO Yunfeng3, WU Yongning2,3*   

  1. 1. Medical Experiment and Test Center, Capital Medical University, Beijing 100069, China; 2. School of Public Health and Family Medicine, Capital Medical University, Beijing 100069, China; 3. National Institute of Nutrition and Food Safety, Chinese Center for Disease Control and Prevention, Beijing 100021, China
  • Received:2011-07-19 Revised:2011-09-04 Online:2011-12-28 Published:2012-01-15

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Abstract: A solid-phase extraction (SPE) method for the simultaneous extraction of hexabromocyclododecanes (HBCDs)/tetrabromobisphenol A (TBBPA) and polybrominated diphenyl ethers (PBDEs) in human serum was developed. The extracts of HBCDs/TBBPA and PBDEs were determined using ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) and gas chromatography-negative chemical ionization/mass spectrometry (GC-NCI/MS), respectively. The samples with the spiked internal standards, 13C12-HBCD, 13C12-TBBPA, 3,3′,4,4′-tetrabromodiphenyl ether (BDE-77) and 13C12-decabromodiphenyl ether (BDE-209), were extracted using the mixture of methyl tert-butyl ether (MTBE) and hexane (1:1, v/v). Then the co-extracted lipid was removed by sulfuric acid treatment. The newly obtained extract was purified using SPE with an LC-Si column and two fractions of HBCDs/TBBPA and PBDEs were finally got. The determination of HBCDs/TBBPA was performed on a 50 mm BEH C18 column in the multi-reaction monitoring (MRM) mode and the determination of PBDEs was on a 15 m capillary column in the selected ion-monitoring (SIM) mode. The limits of detection (LODs, S/N=3) ranged from 1.81 to 42.16 pg/g . The average recoveries were from 80.3% to 108.8% at two spiked levels of 0.5 and 5 ng/g for HBCDs, 0.05 and 0.5 ng/g for TBBPA and BDE-209 with the relative standard deviations between 1.02% and 11.42%(n=5). The developed method has been successfully applied to the determination of the 12 analytes in 42 pooled human serum samples. The levels of TBBPA in the samples ranged from ＜LOD to 6.58 ng/g, that of α-HBCD diastereoisomer ranged from ＜LOD to 7.22 ng/g, which was the most abundant isomer comparing with β- and γ-HBCD. The total PBDEs found ranged from 2.90 to 89.69 ng/g. This method was validated to be accurate and sensitive for the analysis of HBCDs, TBBPA and PBDEs in serum samples.

Key words: gas chromatography-mass spectrometry (GC-MS), hexabromocyclododecane (HBCD), ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), polybrominated diphenyl ethers (PBDEs), serum, solid-phase extraction (SPE), tetrabromobisphenol A (TBBPA)