High-resolution mass spectrometry recognized Tetrabromobisphenol A bis (2,3-dibromo-2-methylpropyl ether) (TBBPA-DBMPE) as a contaminant in sediment from a flame retardant manufacturing factory

Abstract

Information on contamination status of tetrabromobisphenol, and triazine-based novel brominated flame retardants (NBFRs) in sediment environment is very rare. Here, by use of high performance liquid chromatography coupled with quadrupole orbitrap mass spectrometry (HPLC-Q-Orbitrap/MS), we developed an analytical method for determination of three tetrabromobisphenol, and two triazine-based FRs in sediment samples. By applying this method for analysis of n = 6 sediment samples from a flame retardant manufacturing factory, we observed that total concentrations of 6 NBFRs (∑₆NBFRs) ranged from 7.46 to 1020 ng/g dry weight (dw), which were comparable to those (3.83-820 ng/g dw) of n = 11 sediment samples from e-waste recycling area. Both of them were statistically significantly (p < 0.001, one-way ANOVA) higher than those in n = 10 sediment samples from Taihu Lake (1.22-8.22 ng/g dw). With an aim to find novel tetrabromobisphenol, and triazine-based compounds, we further investigated the ionization characteristics and the fragmentation patterns in ionization source of six target NBFRs. We observed that debromination, ether bond breakage, and the breakage of inter-benzene ring C-C and C-S bonds were the main in-source fragmentation pathways for TBBPA/S derivatives. On the basis of the observed ionization characteristics and an in-house suspect screening list, we tentatively identified 71 NBFR formulas, of which ten TBBPA/S derivatives and one triazine-based BFRs were found for the first time in sediments. Among these NBFR formulas, tetrabromobisphenol A bis (2,3-dibromo-2-methylpropyl ether) (TBBPA-DBMPE) is high of concern due to its male reproductive toxicity according to a recent study, and fully confirmed by comparing unique LC and HRMS characteristics of sediment sample with authentic standard. The work probably provides an opportunity for the structural identification of unknown TBBPA/S derivatives in environmental samples, and reports the occurrence of TBBPA-DBMPE in real environment.

Keywords: High-resolution mass spectrometry (HRMS); Novel brominated flame retardants (NBFRs); Sediment; Tetrabromobisphenol A/S (TBBPA/S) derivatives.