Concurrent extraction, clean-up, and analysis of polybrominated diphenyl ethers, hexabromocyclododecane isomers, and tetrabromobisphenol A in human milk and serum

A method has been developed and validated for the concurrent extraction, clean-up, and analysis of polybrominated diphenyl ethers (PBDEs), α-, β-, and γ-hexabromocyclododecane (HBCD), and tetrabromobisphenol A (TBBPA) in human milk and serum. Milk and serum samples were extracted using accelerated solvent extraction with acetone/hexane 1:1, v/v and liquid–liquid extraction with methyl-tert-butyl ether/hexane 1:1, v/v, respectively. The removal of co-extracted biogenic materials was achieved by gel permeation chromatography followed by sulfuric acid treatment. The fractionation of the PBDEs and HBCD/TBBPA was performed using a Supelco LC-Si SPE cartridge. The detection of the PBDEs was then performed by GC–MS and that of the HBCDs and the TBBPA was performed using UPLC–MS/MS. The pretreatment procedure was optimized, and the characteristic ions and fragmentation of the analytes were studied by MS or MS/MS. A recovery test was performed using a matrix spiking test at concentrations of 0.05–10 ng/g. The recoveries ranged from 78.6–108.8% with RSDs equal to or lower than 14.04%. The LODs were 1.8–60 pg/g. The usefulness of the developed method was tested by the analysis of real human samples, and several brominated flame retardants in different samples were detected and analyzed.