title: [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].
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, 13C(12)-HBCD, 13C(12)-TBBPA, 3, 3', 4, 4'-tetrabromodiphenyl ether (BDE-77) and 13C(12)-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 alpha-HBCD diastereoisomer ranged from < LOD to 7.22 ng/g, which was the most abundant isomer comparing with beta- and gamma-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.
authors.affiliation: Medical Experiment and Test Center, Capital Medical University, Beijing 100069, China.
authors.forename: Zhongxin
authors.initials: Z
authors.lastname: Xiao
authors.forename: Jinfang
authors.initials: J
authors.lastname: Feng
authors.forename: Zhixiong
authors.initials: Z
authors.lastname: Shi
authors.forename: Jingguang
authors.initials: J
authors.lastname: Li
authors.forename: Yunfeng
authors.initials: Y
authors.lastname: Zhao
authors.forename: Yongning
authors.initials: Y
authors.lastname: Wu
mesh_terms: D002851:Chromatography, High Pressure Liquid; D005411:Flame Retardants / Q000032:analysis*; D008401:Gas Chromatography-Mass Spectrometry; D055768:Halogenated Diphenyl Ethers / Q000097:blood; D006801:Humans; D006842:Hydrocarbons, Brominated / Q000097:blood*; D011075:Polybrominated Biphenyls / Q000097:blood; D052616:Solid Phase Extraction; D053719:Tandem Mass Spectrometry
chemical_list: D005411:Flame Retardants; D055768:Halogenated Diphenyl Ethers; D006842:Hydrocarbons, Brominated; D011075:Polybrominated Biphenyls; C089796:hexabromocyclododecane; C020806:tetrabromobisphenol A