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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., (Copyright © 2014 Elsevier B.V. All rights reserved.)

A novel method for simultaneous determination of five estrogens and four androgens by online solid-phase extraction (SPE) coupled with high-performance liquid chromatography-tandem mass spectrometry (HPLC-ESI-MS/MS) in water samples was developed. An aliquot of 50 mL water sample after filtration was injected directly into autosampler and the analytes were preconcentrated on a NG1 online SPE column. After cleanup step the analytes were eluted in back flush mode and then separated on a liquid chromatography column. The experimental parameters, such as sample loading flow rate, cleanup condition and elution time, were optimized in detail. Estrogens and androgens were detected in negative and positive mode, respectively. High ionization efficiency of all the analytes was achieved by adding of 1‰ ammonia in the mobile phase. The recoveries ranged from 31.8% to 119.0% and the inter-day RSDs ranged from 2.7% to 19.6%. The limits of detections (LODs) were between 0.1 and 2.5 ng/L. The proposed method was successfully applied to the analysis of three types of water samples, including river water, influent and effluent water from a wastewater treatment plant (WWTP). The recoveries of androgens were not that good and a further study is being planned to improve the sensitivity for them. The proposed method is simple, sensitive and suitable for simultaneous analysis and monitoring of estrogens and androgens in water samples., (Copyright © 2013 Elsevier B.V. All rights reserved.)