Butryn Deena M, Gross Michael S, Chi Lai-Har, Schecter Arnold, Olson James R, Aga Diana S
Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, NY 14260, USA.
Department of Pharmacology and Toxicology, University at Buffalo, The State University of New York, Buffalo, NY 14214, USA; Department of Epidemiology and Environmental Health, University at Buffalo, The State University of New York, Buffalo, NY 14214, USA.
Anal Chim Acta. 2015 Sep 10;892:140-7. doi: 10.1016/j.aca.2015.08.026. Epub 2015 Aug 25.
The presence of polybrominated diphenyl ethers (PBDEs) and their hydroxylated (OH-BDE) and methoxylated (MeO-BDE) analogs in humans is an area of high interest to scientists and the public due to their neurotoxic and endocrine disrupting effects. Consequently, there is a rise in the investigation of the occurrence of these three classes of compounds together in environmental matrices and in humans in order to understand their bioaccumulation patterns. Analysis of PBDEs, OH-BDEs, and MeO-BDEs using liquid chromatography-mass spectrometry (LC-MS) can be accomplished simultaneously, but detection limits for PBDEs and MeO-BDEs in LC-MS is insufficient for trace level quantification. Therefore, fractionation steps of the phenolic (OH-BDEs) and neutral (PBDEs and MeO-BDEs) compounds during sample preparation are typically performed so that different analytical techniques can be used to achieve the needed sensitivities. However, this approach involves multiple injections, ultimately increasing analysis time. In this study, an analytical method was developed for a "one-shot" analysis of 12 PBDEs, 12 OH-BDEs, and 13 MeO-BDEs using gas chromatography with tandem mass spectrometry (GC-MS/MS). This overall method includes simultaneous extraction of all analytes via pressurized liquid extraction followed by lipid removal steps to reduce matrix interferences. The OH-BDEs were derivatized using N-(t-butyldimethylsilyl)-N-methyltrifluoroacetamide (TBDMS-MTFA), producing OH-TBDMS derivatives that can be analyzed together with PBDEs and MeO-BDEs by GC-MS/MS in "one shot" within a 25-min run time. The overall recoveries were generally higher than 65%, and the limits of detection ranged from 2 to 14 pg in both breast milk and serum matrices. The applicability of the method was successfully validated on four paired human breast milk and serum samples. The mean concentrations of total PBDEs, OH-BDEs, and MeO-BDEs in breast milk were 59, 2.2, and 0.57 ng g(-1) lipid, respectively. In serum, the mean total concentrations were 79, 38, and 0.96 ng g(-1) lipid, respectively, exhibiting different distribution profiles from the levels detected in breast milk. This "one-shot" GC-MS/MS method will prove useful and cost-effective in large-scale studies needed to further understand the partitioning behavior, and ultimately the adverse health effects, of these important classes of brominated flame retardants in humans.
由于多溴二苯醚（PBDEs）及其羟基化（OH-BDEs）和甲氧基化（MeO-BDEs）类似物具有神经毒性和内分泌干扰作用，它们在人体内的存在引起了科学家和公众的高度关注。因此，对环境基质和人体中这三类化合物同时出现情况的调查日益增多，以便了解它们的生物累积模式。使用液相色谱 - 质谱联用（LC-MS）对PBDEs、OH-BDEs和MeO-BDEs进行分析可以同时完成，但LC-MS中PBDEs和MeO-BDEs的检测限不足以进行痕量水平的定量。因此，在样品制备过程中通常会对酚类（OH-BDEs）和中性（PBDEs和MeO-BDEs）化合物进行分离步骤，以便能够使用不同的分析技术来达到所需的灵敏度。然而，这种方法需要多次进样，最终增加了分析时间。在本研究中，开发了一种使用气相色谱 - 串联质谱（GC-MS/MS）对12种PBDEs、12种OH-BDEs和13种MeO-BDEs进行“一次进样”分析的方法。该整体方法包括通过加压液体萃取同时提取所有分析物，随后进行脂质去除步骤以减少基质干扰。OH-BDEs使用N-（叔丁基二甲基甲硅烷基）-N-甲基三氟乙酰胺（TBDMS-MTFA）进行衍生化，生成OH-TBDMS衍生物，可在25分钟的运行时间内通过GC-MS/MS与PBDEs和MeO-BDEs一起进行“一次进样”分析。整体回收率一般高于65%，在母乳和血清基质中的检测限范围为2至14 pg。该方法的适用性在四对人母乳和血清样品上成功得到验证。母乳中总PBDEs、OH-BDEs和MeO-BDEs的平均浓度分别为59、2.2和0.57 ng g(-1)脂质。在血清中，总平均浓度分别为79、38和0.96 ng g(-1)脂质，呈现出与母乳中检测水平不同的分布特征。这种“一次进样”GC-MS/MS方法在进一步了解这些重要类别的溴化阻燃剂在人体中的分配行为以及最终了解其对健康的不利影响所需的大规模研究中将被证明是有用且具有成本效益的。
