凝胶渗透色谱-固相萃取结合色谱-质谱法测定乳制品中18种溴系阻燃剂

采用索氏提取、凝胶渗透色谱和固相萃取技术作为前处理方法,建立乳制品中6种新型溴系阻燃剂、8种多溴联苯醚、四溴双酚A和α、β、γ-六溴环十二烷异构体共18种溴系阻燃剂的同时提取与净化方法,并结合气相色谱-负化学源质谱法(GC-NCI/MS)和高效液相色谱-电喷雾电离-串联质谱法(HPLC-ESI-MS/MS)进行检测。奶样经冷冻干燥后以正己烷-丙酮(1：1, V/V)索氏提取,采用凝胶渗透色谱结合酸化硅胶柱净化,随后以LC-Si固相萃取柱分离气相和液相待测物。以GC-NCI/MS测定6种新型溴系阻燃剂和8种多溴联苯醚,以HPLC-MS/MS检测四溴双酚A和六溴环十二烷异构体,内标法定量。结果表明,以空白牛奶样品为加标基质,多数待测物平均回收率为80.1%~114.7%,方法具有良好的精密度(多数待测物相对标准偏差( RSD)在0.87%~14.9%)和灵敏度(检出限在0.2~119.2 pg/g之间),可满足乳制品中多种溴系阻燃剂同时提取、净化和检测需求。

Determination of 18 Brominated Flame Retardants in Dairy Product by Gel Permeation Chromatography-Solid Phase Extraction Coupled to Gas Chromatography-Mass Spectrometry and High Performance Liquid Chromatography-Tandem Mass Spectrometry

A novel method was developed for the simultaneous determination of 6 novel brominated flame retardants ( NBFRs) , 8 polybrominated diphenyl ethers ( PBDEs) , tetrabromobisphenolA ( TBBPA) and α,β,γ-hexabromocyclododecane (α, β, γ-HBCD ) in dairy product. Dairy product samples were extracted using soxhlet extraction with acetone/hexane (1:1, V/V). The removal of co-extracted materials was achieved by gel permeation chromatography followed by acidified silica treatment. The fractionation of the PBDEs/NBFRs and HBCD/TBBPA was performed using a Supelco LC-Si SPE cartridge. The detection of the PBDEs and NBFRs was then performed by GC-NCI/MS, and that of the HBCDs and the TBBPA was performed using HPLC-MS/MS. A recovery test was performed using a matrix spiking test and for most of the analytes the recoveries ranged from 80 . 1% to 114 . 7% with RSDs equal to or lower than 14 . 9%. The LODs were 0 . 2-119. 2 pg/g. This methodology was validated to be accurate and sensitive for the simultaneous pretreatment and analysis of brominated flame retardants in dairy product.