Simple and fast method for the measurement of legacy and novel brominated flame retardants in human serum

Abstract

Recent and reliable human biomonitoring data on brominated flame retardants (BFRs), either legacy or new BFRs, are still needed to assess human exposure. The aim of this work was therefore to develop and validate an accurate, fast and user-friendly analytical strategy for the determination of 15 legacy and novel BFRs in human serum namely 8 polybrominated diphenylethers (BDE-28, -47, −99, −100, −153, −154, −183, and −209), 1 hexabromobiphenyl (PBB-153), and 6 novel BFRs (pentabromotoluene, hexabromobenzene, pentabromoethylbenzene, 2-ethylhexy-2,3,4,5-tetrabromobenzoate, 1,2-bis(2,4,6-tribromophenoxy)ethane, and decabromodiphenylethane). This analytical procedure consisted in a simple liquid-liquid extraction followed by elution on a PHREE cartridge avoiding further laborious purification steps. The final determination was performed by gas chromatography coupled to mass spectrometry in electron capture negative ionization mode (GC-ECNI-MS). The 15 m long RTX-1614 allowed the simultaneous measurement of the 15 BFRs including low and high brominated species within a single injection on a single column. Except for 2-ethylhexy-2,3,4,5-tetrabromobenzoate (EHTBB) which showed very high response variations resulting in poor linearity, trueness and precision, and decabromodiphenylethane for which very low sensitivity was achieved, the 13 other BFRs passed the validation process with recoveries varying between 56 and 82%, and limits of quantification (LOQs) ranging from 2.5 to 6.0 pg/ml (34.5 pg/ml for BDE-209). Within the validated range of concentrations, the relative bias from the introduced levels were below 20% while the intra and inter precisions were maintained below 15%. The reliability of the technique was confirmed by successfully analyzing interlaboratory test materials (AMAP ring test for POPs in human serum).