title: "One-shot" analysis of polybrominated diphenyl ethers and their hydroxylated and methoxylated analogs in human breast milk and serum using gas chromatography-tandem mass spectrometry.
abstract: 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.
authors.affiliation: Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, NY 14260, USA.
authors.forename: Deena M
authors.initials: DM
authors.lastname: Butryn
authors.affiliation: Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, NY 14260, USA.
authors.forename: Michael S
authors.initials: MS
authors.lastname: Gross
authors.affiliation: 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.
authors.forename: Lai-Har
authors.initials: LH
authors.lastname: Chi
authors.affiliation: Department of Pharmacology and Toxicology, University of Louisville College of Medicine, Louisville, KY 40202, USA.
authors.forename: Arnold
authors.initials: A
authors.lastname: Schecter
authors.affiliation: 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.
authors.forename: James R
authors.initials: JR
authors.lastname: Olson
authors.affiliation: Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, NY 14260, USA. Electronic address: dianaaga@buffalo.edu.
authors.forename: Diana S
authors.initials: DS
authors.lastname: Aga
mesh_terms: D052244:Endocrine Disruptors / Q000032:analysis / Q000097:blood / Q000737:chemistry; D004785:Environmental Pollutants / Q000032:analysis / Q000097:blood / Q000737:chemistry; D005260:Female; D008401:Gas Chromatography-Mass Spectrometry; D055768:Halogenated Diphenyl Ethers / Q000032:analysis / Q000097:blood / Q000737:chemistry*; D006801:Humans; D008895:Milk, Human / Q000737:chemistry*
chemical_list: D052244:Endocrine Disruptors; D004785:Environmental Pollutants; D055768:Halogenated Diphenyl Ethers
keywords: Breast milk; Brominated flame retardants; Hydroxylated polybrominated diphenyl ethers; Methoxylated polybrominated diphenyl ethers; Polybrominated diphenyl ethers; Serum