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The wide spread use of tetrabromobisphenol A(TBBPA),tetrabromobisphenol S(TBBPS)and their derivatives have resulted in the presence of novel brominated contaminants in the environment.Tetrabromobisphenol A mono(2-hydroxyethyl ether)(TBBPA-MHEE),TBBPA mono(glycidyl ether)(TBBPA-MGE),TBBPS mono(allyl ether)(TBBPSMAE),TBBPS mono(2-bromoallyl ether)(TBBPS-MBAE)and TBBPS mono(2,3-dibromopropyl ether)(TBBPS-MDBPE),impurities of TBBPA and TBBPS derivatives,were hypothesized to be novel brominated contaminants with potential toxicity.However,the lacking of analytical method and pure standards has blocked the studies of their environmental behavior and toxicity.Herein a sensitive method based on ultra-high performance liquid chromatography-Orbitrap Fusion Tribrid mass spectrometer(UHPLC-Orbitrap Fusion TMS)was developed for the identification of TBBPA-MHEE,TBBPA-MGE,TBBPS-MAE,TBBPS-MBAE and TBBPS-MDBPE in environmental 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,TBBPA-MGE,TBBPS-MAE,TBBPS-MBAE and TBBPS-MDBPE were 0.5 pg,0.6 pg,0.06 pg,0.1 pg and 0.1 pg,respectively.The method detection limits(MDLs)for TBBPA-MHEE and TBBPAMGE in river water samples were 0.9 and 0.8 ng/L.The MDLs for TBBPS-MAE,TBBPS-MBAE and TBBPS-MDBPE in mollusks samples were 0.04 ng/g dry weight(dw),0.08 ng/g dw and 0.06 ng/g dw,respectively.TBBPA-MHEE,TBBPAMGE,TBBPS-MAE,TBBPS-MBAE and TBBPS-MDBPE were detected for the first time in environmental samples and technical products of TBBPA and TBBPS derivatives.UHPLC-Orbitrap Fusion TMS applied for the identification of byproducts of the technical products provides a simple and effective approach for the study of novel contaminants in the environment.