基于串联SPE净化和GC-HRMS技术测定母乳中溴代二噁英/呋喃
Determination of polybrominated dibenzo-p-dioxin/furans in human milk using tandem SPE purification and GC-HRMS
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摘要:
背景 溴代二噁英/呋喃（PBDD/Fs）主要来源于溴代阻燃剂的排放。随着近几十年来溴代阻燃剂的大量使用，环境中的溴代二噁英/呋喃的含量逐渐增高。
目的 建立快速、准确测定母乳中13种溴代二噁英/呋喃的气相-高分辨质谱（GC-HRMS）检测方法。
方法 将母乳冷冻干燥后，经加速溶剂萃取仪提取，分散固相萃取除脂，串联固相萃取净化和气相-高分辨质谱检测，同位素稀释法定量。
结果 本方法的检出限为0.002~0.012 pg/g（以50 g样品计）；具有良好的线性范围，决定系数（R2）>0.99；准确度和精密度实验结果显示，低浓度和高浓度的加标回收率分别为71.8%~101.8%、80.5%~97.8%，相对标准偏差（RSD） < 10%。基于本方法，测定了40份上海地区的母乳样品，PBDDs没有检出，PBDFs有2，3，7，8-四溴代二苯并呋喃（2，3，7，8-TetraBDF）、1，2，3，4，6，7，8-七溴代二苯并呋喃（1，2，3，4，6，7，8-HpBDF）和八溴代二苯并呋喃（OBDF）共3种化合物检出，检出率分别是72.5%、100%和67.5%。
结论 所建方法用于测定母乳样本中PBDD/Fs，结果表明该方法快速、准确、高效、可靠，为开展PBDD/Fs暴露风险评估和毒理学研究提供了方法学支持。
Abstract:Background The emissions of brominated flame retardants have been proved to be the major source of polybrominated dibenzo-p-dioxin/furans (PBDD/Fs). With the extensive use of brominated flame retardants in recent decades, the concentrations of PBDD/Fs in the environment increase gradually.
Objective This study aims to establish a rapid and accurate method for the determination of 13 PBDD/F congeners in human milk by gas chromatography-high resolution mass spectrometry (GC-HRMS).
Methods Lyophilized human milk was subject to accelerated solvent extraction, dispersive solid phase extraction (SPE) defatting, and tandem SPE purification successively, and consequently detected by GC-HRMS with isotopic dilution method.
Results This method showed low limits of detection (LOD, 0.002-0.012 ng/g, in 50 g milk sample), good linearity (correlation coefficients, R2 > 0.99), satisfactory accuracy (the recovery rates of lowconcentration spiked standard were 71.8%-101.8%, and the recovery rates of high-concentration spiked standard were 80.5%-97.8%), and high precision (relative standard deviations, RSD < 10%). Forty breast milk samples collected in Shanghai were determined by the method. PBDDs were not detected, and three PBDF congeners including 2, 3, 7, 8-tetrabromodibenzofuran (2, 3, 7, 8-TetraBDF), 1, 2, 3, 4, 6, 7, 8-heptabromodibenzofuran (1, 2, 3, 4, 6, 7, 8-HpBDF), and octabromodibenzofuran (OBDF) were positive, with detection rates of 72.5%, 100%, and 67.5%, respectively.
Conclusion This method has exhibited rapidness, accuracy, efficiency, and reliability for the determination of PBDD/Fs in human milk samples. It provides methodological support for PBDD/Fs exposure risk assessment and toxicological research.
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