Determination of tetrabromobisphenol-A/S and their main derivatives in water samples by high performance liquid chromatography coupled with inductively coupled plasma tandem mass spectrometry

- A novel method for the determination of TBBPA/S and their derivatives was developed based on the hyphenation of HPLC and ICP-MS/MS techniques.
- ICP-MS/MS was used for the first time for the quantification of TBBPA/S and their derivatives by determining the bromine.
- The method provided higher sensitivity than the previous reported method.
- The HPLC-ICP-MS/MS method was successfully applied for TBBPA/S and their derivatives analysis in water samples.

As the most widely used brominated flame retardants (BFRs), Tetrabromobisphenol-A (TBBPA) as well as its alternative Tetrabromobisphenol-S (TBBPS) and their derivatives have raised wide concerns due to their adverse effects on human health and hence the sensitive detection of those BFRs was urgently needed. Herein, a novel analytical method based on high-performance liquid chromatography (HPLC) coupled with inductively coupled plasma tandem mass spectrometry (ICP-MS/MS) has been developed for the determination of TBBPA/S and their derivatives, including TBBPA-bis(2-hydroxyethyl ether) (TBBPA-BHEE), TBBPA-bis(allylether) (TBBPA-BAE), TBBPA-bis(glycidyl ether) (TBBPA-BGE), TBBPA-bis(2,3-dibromopropyl ether) (TBBPA-BDBPE) and TBBPS-bis(2,3-dibromopropyl ether) (TBBPS-BDBPE) in water samples. After optimization, the TBBPA/S and their derivatives, especially the TBBPA-BAE and TBBPA-BDBPE were simultaneously and sensitively quantified by determination of bromine (m/z = 79) by using the ICP-MS. The instrument limits of detection (LODs) for the TBBPA, TBBPA-BHEE, TBBPA-BGE, TBBPA-BAE, TBBPA-BDBPE, TBBPS and TBBPS-BDBPE were determined to be 0.12, 0.14, 0.19, 0.14, 0.12, 0.17 and 0.13 μg L−1, respectively, which was close to or much better than the reported methods. The relative standard deviations (RSDs, n = 5) of peak area and retention time were better than 2.2% and 0.2% for intra-day analysis, indicating good repeatability and high precision. The proposed method had been successfully applied for the analysis of TBBPA/S and their derivatives in water samples with satisfactory recoveries (67.7%-113%).