Xiao Zhongxin, Feng Jinfang, Shi Zhixiong, Li Jingguang, Zhao Yunfeng, Wu Yongning
Medical Experiment and Test Center, Capital Medical University, Beijing 100069, China.
Se Pu. 2011 Dec;29(12):1165-72.
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.
建立了一种同时萃取人血清中六溴环十二烷（HBCDs）/四溴双酚A（TBBPA）和多溴二苯醚（PBDEs）的固相萃取（SPE）方法。分别采用超高效液相色谱 - 串联质谱法（UPLC - MS/MS）和气相色谱 - 负化学电离/质谱法（GC - NCI/MS）测定HBCDs/TBBPA和PBDEs的提取物。将添加了内标物13C(12)-HBCD、13C(12)-TBBPA、3,3',4,4'-四溴二苯醚（BDE - 77）和13C(12)-十溴二苯醚（BDE - 209）的样品用甲基叔丁基醚（MTBE）和己烷（1:1，v/v）的混合物萃取。然后通过硫酸处理去除共萃取的脂质。新获得的提取物用LC - Si柱进行固相萃取纯化，最终得到HBCDs/TBBPA和PBDEs的两个馏分。HBCDs/TBBPA的测定在50 mm BEH C18柱上以多反应监测（MRM）模式进行，PBDEs的测定在15 m毛细管柱上以选择离子监测（SIM）模式进行。检测限（LODs，S/N = 3）范围为1.81至42.16 pg/g。对于HBCDs，在0.5和5 ng/g两个加标水平下，平均回收率为80.3%至108.8%；对于TBBPA和BDE - 209，在0.05和0.5 ng/g加标水平下，平均回收率为80.3%至108.8%，相对标准偏差在1.02%至11.42%之间（n = 5）。所建立的方法已成功应用于42份混合人血清样品中12种分析物的测定。样品中TBBPA的含量范围为<LOD至6.58 ng/g，α - HBCD非对映异构体的含量范围为<LOD至7.22 ng/g，与β - HBCD和γ - HBCD相比，α - HBCD是含量最高的异构体。所检测到的总PBDEs含量范围为2.90至89.69 ng/g。该方法经验证对血清样品中HBCDs、TBBPA和PBDEs的分析准确且灵敏。
