RESUMEN

Tetrabromobisphenol A mono(2-hydroxyethyl ether) (TBBPA-MHEE) and TBBPA mono(glycidyl ether) (TBBPA-MGE), two impurities of TBBPA derivatives, were hypothesized to be novel brominated contaminants with potential toxicity. However, due to lacking of analytical method and pure standards, their environmental behavior and toxicity have not been studied. Herein we developed a sensitive method based on ultra-high performance liquid chromatography-Orbitrap Fusion Tribrid mass spectrometer (UHPLC-Orbitrap Fusion TMS) for simultaneous detection of TBBPA-MHEE and TBBPA-MGE in water samples. The sample pretreatment method and the experimental conditions of UHPLC and Orbitrap Fusion TMS, were optimized in detail. The instrument detection limits (IDLs) for TBBPA-MHEE and TBBPA-MGE were 0.5pg and 0.6pg, respectively. The method detection limits (MDLs) for TBBPA-MHEE and TBBPA-MGE in river water samples were 0.9 and 0.8ng/L. With the proposed method, we were able to detect TBBPA-MHEE and TBBPA-MGE for the first time in water samples and technical products of TBBPA derivatives. Therefore, UHPLC-Orbitrap Fusion TMS is a simple and effective tool for identification and quantification of novel contaminants in the environment.

Asunto(s)

RESUMEN

Sensitive detection of tetrabromobisphenol A (TBBPA) and its derivatives, a group of emerging toxic contaminants, is highly necessitated in environmental investigation. Herein a novel analytical strategy based on reactive extractive electrospray ionization (EESI) tandem mass spectrometry for detection of tetrabromobisphenol A bis(2-hydroxyethyl ether) (TBBPA-BHEE), tetrabromobisphenol A bis(glycidyl ether) (TBBPA-BGE), tetrabromobisphenol A bis(allylether) (TBBPA-BAE), and tetrabromobisphenol S bis(allylether) (TBBPS-BAE) in industrial waste water samples was developed. Active silver cations (Ag(+)), generated by electrospraying a silver nitrate methanol solution (10 mg L(-1)), collides the neutral TBBPA derivatives molecules in the EESI source to form [M+Ag](+) complexes of the analytes under the ambient conditions. Upon collision-induced dissociation (CID), characteristic fragments of the [M+Ag](+) complexes were identified for confident and sensitive detection of the four TBBPA derivatives. Under the optimized experimental conditions, the instrumental limits of detection (LODs) of TBBPA-BHEE, TBBPA-BGE, TBBPA-BAE and TBBPS-BAE were 0.37, 0.050, 0.76, and 4.6 µg L(-1), respectively. The linear ranges extended to 1000 µg L(-1) (R(2)≥0.9919), and the relative standard deviations (RSDs), inter-day variation and intra-day variation were less than 7.8% (n=9), 10.0% (n=5), and 14.8% (n=1 per day for 5 days) for all derivatives. TBBPA derivative manufacturing industrial waste water, river water and tap water samples were fast analyzed with the proposed method. The contents of TBBPA derivatives were various in the collected samples, with the highest 19.9±0.3 µg L(-1) of TBBPA-BAE in the waste water samples.