Simple and fast analysis of tetrabromobisphenol A, hexabromocyclododecane isomers, and polybrominated diphenyl ethers in serum using solid‐phase extraction or QuEChERS extraction followed by tandem mass spectrometry coupled to HPLC and GC

Abstract

Two simplified sample preparation procedures for simultaneous extraction and clean-up of tetrabromobisphenol A, α-, β-, and γ-hexabromocyclododecane and polybrominated diphenyl ethers in human serum were developed and validated. The first procedure was based on solid-phase extraction. Sample extraction, purification, and lipid removal were carried out directly on an Oasis HLB cartridge. The second procedure was a quick, easy, cheap, effective, rugged, and safe-based approach using octadecyl-modified silica particles as a sorbent. After sample extraction and cleanup, tetrabromobisphenol A/hexabromocyclododecane was separated from polybrominated diphenyl ethers by using a Si-based cartridge. Tetrabromobisphenol A and hexabromocyclododecane were then detected by high-performance liquid chromatography coupled to tandem mass spectrometry, while polybrominated diphenyl ethers were detected by gas chromatography coupled to tandem mass spectrometry. The results of the spike recovery test using fetal bovine serum showed that the average recoveries of the analytes ranged from 87.3 to 115.3% with relative standard deviations equal to or lower than 13.4 %. Limits of detection of the analytes were in the range of 0.4-19 pg/mL except for decabromodiphenyl ether. The developed method was successfully applied to routine analysis of human serum samples from occupational workers and the general population. Extremely high serum polybrominated diphenyl ethers levels up to 3.32 × 10 ng/g lipid weight were found in occupational workers.

Application of Dispersive Liquid–Liquid Microextraction Followed by High‐Performance Liquid Chromatography/Tandem Mass Spectrometry Analysis to Determine Tetrabromobisphenol A in Complex Matrices

“…The results we obtained suggest that the sample preparation before the DLLME procedure and the miniaturization of what was proposed by Wang et al (2013) led to satisfactory results for TBBPA quantification even in complex matrices. For solid environmental matrices, most of the methods rely on SPE, with conventional (C 18 cartridges; Deceuninck et al 2014; Regueiro and Wenzl 2015; Chi et al 2017; Li et al 2017) or alternative sorbent materials (Chen et al 2016; Hu et al 2019), requiring a large volume of solvents for cartridge activation and analyte elution.…”

“…To determine the presence of TBBPA in complex matrix samples, extraction and clean‐up methods are still based on nonminiaturized techniques. Analytical methods to determine the presence of tetrachlorobisphenol A, pentabromophenol, bisphenol A, TBBPA, hexabromocyclododecane, polybrominated diphenyl ether, and bromophenols in complex solid and aqueous samples based on the use of a larger volume of organic solvent, SPE cartridges, time‐consuming steps throughout the procedure, and a complex apparatus compared with DLLME procedures have been extensively reported (Deceuninck et al 2014; Chen et al 2016; Zhang et al 2016; Chi et al 2017; Li et al 2017). For complex environmental samples, the DLLME technique may be combined with other extraction and/or clean‐up procedures depending on the nature of the sample.…”

Update of the risk assessment of hexabromocyclododecanes (HBCDDs) in food

“…Clean‐up is usually performed by different column chromatographic techniques to remove co‐extracted interfering matrix constituents and to separate HBCDDs from potentially interfering compounds (Covaci et al., 2007; Xu et al., 2013; Kuc and Grochowalski, 2014). Newer approaches make use of modified QuEChERS (quick, easy cheap, effective rugged and safe) methods (Plassmann et al., 2015; Yuan et al., 2016; Li et al., 2017a).…”

Polybrominated Diphenyl Ethers Quinone Induces NCOA4-Mediated Ferritinophagy through Selectively Autophagic Degradation of Ferritin

“…1 PBDEs have been produced commercially in three main formulations, including penta-and octa-BDEs, which were listed as persistent organic pollutants (POPs) in 2009. 2 PBDEs-treated products may enter into the environment through multiple routes. Once spread in biota, they may enter into humans through dietary intake.…”

“…Polybrominated diphenyl ethers (PBDEs) are one of the most used brominated flame retardants in a diverse set of products, including plastics, textiles, and electronic apparatus . PBDEs have been produced commercially in three main formulations, including penta- and octa-BDEs, which were listed as persistent organic pollutants (POPs) in 2009 . PBDEs-treated products may enter into the environment through multiple routes.…”