摘要
建立了固相萃取同时提取、净化血清中四溴双酚A(TBBPA)、α,β,γ-六溴环十二烷(HBCD)和8种多溴联苯醚(PBDEs)同系物的样本前处理方法,并结合色谱-质谱分离分析技术检测人血清样本中该类化合物的含量。试样在加入各自的同位素内标物后以甲基叔丁基醚/正己烷(1∶1,v/v)混合溶剂进行萃取,再经浓硫酸去除脂肪后,以LC-Si固相萃取柱分离HBCD/TBBPA和PBDEs。采用分步检测的方式,在50 mm长BEH C18反相色谱柱上以超高效液相色谱-串联质谱(UPLC-MS/MS)的多反应监测模式(MRM)检测HBCD和TBBPA,在15 m长的毛细管柱上以气相色谱-负化学源质谱(GC-NCI/MS)的选择离子监测模式(SIM)检测PBDEs。以胎牛血清为空白基质,当HBCD、TBBPA和BDE-209的加标水平为0.5 ng/g和5 ng/g、三溴至七溴联苯醚的加标水平为0.05 ng/g和0.5 ng/g时,它们的平均加标回收率为80.3%～108.8%,相对标准偏差为1.02%～11.42%(n=5);以信噪比(S/N)为3计算,方法的检出限(LOD)为1.81～42.16 pg/g。采用该方法对实际样品进行测定,结果表明,本方法快速、准确、灵敏度高,能够满足血清中HBCD、TBBPA和PBDEs残留的同时提取及测定的要求。
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.
出处
《色谱》
CAS
CSCD
北大核心
2011年第12期1165-1172,共8页
Chinese Journal of Chromatography
基金
国家自然科学基金项目(21007043)
北京市自然科学基金项目(7122022)
关键词
固相萃取
超高效液相色谱-串联质谱
气相色谱-质谱
六溴环十二烷
四溴双酚A
多溴联苯醚
血清
solid-phase extraction（SPE）
ultra-performance liquid chromatography-tandem mass spectrometry（UPLC-MS/MS）
gas chromatography-mass spectrometry（GC-MS）
hexabromocyclododecane（HBCD）
tetrabromobisphenol A（TBBPA）
polybrominated diphenyl ethers（PBDEs）
serum
