建立了液液萃取耦合气相色谱/质谱联用(GC/MS/MS)分析斑马鱼卵中10种多溴联苯醚(PBDEs),12种甲氧基化多溴联苯醚(MeO-PBDEs)和9种羟基化多溴联苯醚(HO-PBDEs)不同极性组分的同步分析方法。优化了前处理步骤和色谱质谱条件,采用液液萃取法提取目标化合物,不必分离即可实现目标化合物的衍生化,使样品前处理时间大大缩短,实现了不同极性组分化合物的同步分析。采用干法制备酸性硅胶柱纯化,用15 mL正己烷和15 mL二氯甲烷正己烷(1:1,V/V)混合溶剂洗脱效果良好。31种化合物在4.0~500μg/L浓度范周内线性良好,相关系数均大于0.99,回收率在71.6%~133.0%之间;相对标准偏差低于21.5%;检出限在0.09~17.0 ng/g之间。本方法应用到斑马鱼亲子代间转移研究中,对实际样品的检测良好,并发现BDE-47,6-HO-BDE-47,6-MeO-BDE-47,2'-HO BDE-28和2'-MeC-BDE 28可通过母代斑马鱼暴露后,不同程度地转移到子代中。
An analytical method was developed for the simultaneous analysis of 10 kinds of PBDEs,12 MeO-PBDEs and 9 kinds of HO-PBDEs in zebrafish eggs by liquid-liquid extraction coupled with GC/ MS/MS.The conditions of extraction,chromatography and mass spectrometry were optimized.The target compounds were extracted through liquid-liquid extraction and derivatization of HO-PBDEs can be carried out without separation from extraction solution.Thus the pre-treatment time could be shortened and all target compounds could be analyzed simultaneously.Purification was conducted by dry packed acidic silica gel column.All compounds can be eluted with 15mL n-hexane and 15mL of dichloromethane and hexane(1:1,V/V) mixed solvent.Under optimized conditions,31 compounds had good linearity in concentration range from 4.0 to 500μg/L,with correlation coefficient(R~2 ) better than 0.9933,recoveries in the range of 71.6%—133.0%with relative standard deviations less than 21.5%,and the method and instrument detection limits varied from 0.09 to 17.0 ng/g.The presented method was applied for maternal transfer study of BDE-47,6-HOBDE-47, 6-Me()-BDE-47,2'-HO-BDE-28 and 2'-MeO-BDE-28 and turned out to be efficient for real sample analysis.After maternal exposure,the five compounds showed different maternal transfer potency in zebrafish,giving new consideration for the exposure assessment of such compounds.