Silver ion post-column derivatization electrospray ionization mass spectrometry for determination of tetrabromobisphenol A derivatives in water samples

Abstract

A rapid and sensitive method was developed for the identification and quantitation of tetrabromobisphenol A (TBBPA) derivatives in water samples. Six major TBBPA derivatives, including tetrabromobisphenol A bis(2-hydroxyethyl) ether (TBBPA-BHEE), tetrabromobisphenol A bis(glycidyl) ether (TBBPA-BGE), tetrabromobisphenol A bis(allyl) ether (TBBPA-BAE), tetrabromobisphenol A mono(2-hydroxyethyl) ether (TBBPA-MHEE), tetrabromobisphenol A mono(glycidyl) ether (TBBPA-MGE) and tetrabromobisphenol A mono(allyl) ether (TBBPA-MAE), were selected as the target compounds. By applying the silver cation (Ag⁺) as the post-column derivatization reagent, the TBBPA derivatives formed complexes ([M + Ag]NO₃) online, which could be effectively electrosprayed to generate ionic clusters ([M + Ag]⁺) for sensitive mass analysis. Under the optimized conditions, the 6 TBBPA derivatives were separated and detected within 10 min. The limits of detection (LODs) were between 0.16 and 1.96 μg L⁻¹, and the linear ranges extended to 200 μg L⁻¹ (R² ≥ 0.9957). The relative standard deviations (RSDs) were less than 7.7% for 10 μg L⁻¹ of the TBBPA derivatives (n = 7). The proposed method was successfully applied in analysis of environmental water samples. The spiked recoveries ranged from 81.3% to 114.9%, suggesting the accuracy and feasibility of the method.