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反应性萃取电喷雾串联质谱法用于灵敏检测四溴双酚 A 衍生物。

Reactive extractive electrospray ionization tandem mass spectrometry for sensitive detection of tetrabromobisphenol A derivatives.

机构信息

State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China.

Jiangxi Key Laboratory for Mass Spectrometry and Instrumentation, College of Chemistry, Biology and Material Sciences, East China Institute of Technology, Nanchang, 330013, China.

出版信息

Anal Chim Acta. 2014 Mar 3;814:49-54. doi: 10.1016/j.aca.2014.01.035. Epub 2014 Jan 19.

DOI:10.1016/j.aca.2014.01.035
PMID:24528843
Abstract

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.

摘要

痕量检测四溴双酚 A(TBBPA)及其衍生物,作为一组新兴的有毒污染物,在环境调查中非常必要。在此,提出了一种基于反应性萃取电喷雾电离(EESI)串联质谱法检测四溴双酚 A 双(2-羟乙基醚)(TBBPA-BHEE)、四溴双酚 A 双(缩水甘油醚)(TBBPA-BGE)、四溴双酚 A 双(烯丙基醚)(TBBPA-BAE)和四溴双酚 S 双(烯丙基醚)(TBBPS-BAE)的新分析策略。在 EESI 源中,通过电喷雾硝酸银甲醇溶液(10 mg L(-1))产生的活性银离子(Ag(+)),与中性 TBBPA 衍生物分子发生碰撞,在环境条件下形成分析物的M+Ag配合物。在碰撞诱导解离(CID)过程中,鉴定出M+Ag配合物的特征碎片,从而实现对四种 TBBPA 衍生物的可靠和灵敏检测。在优化的实验条件下,TBBPA-BHEE、TBBPA-BGE、TBBPA-BAE 和 TBBPS-BAE 的仪器检出限(LOD)分别为 0.37、0.050、0.76 和 4.6 μg L(-1)。线性范围扩展到 1000 μg L(-1)(R(2)≥0.9919),所有衍生物的相对标准偏差(RSD)、日内变化和日间变化均小于 7.8%(n=9)、10.0%(n=5)和 14.8%(n=1 每天测 5 天)。采用该方法快速分析了 TBBPA 衍生物制造工业废水、河水和自来水样品。在所采集的样品中,TBBPA 衍生物的含量各不相同,废水中 TBBPA-BAE 的含量最高,为 19.9±0.3 μg L(-1)。

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