色谱

色谱 ›› 2014, Vol. 32 ›› Issue (6): 623-628.DOI: 10.3724/SP.J.1123.2014.02012

• 研究论文 • 上一篇    下一篇

分散液液微萃取-衍生化高效液相色谱-荧光检测法测定环境水样中4种酚类内分泌干扰物

王晓燕1, 亓伟梅2, 赵先恩1, 吕涛1, 王西亚1, 郑龙芳1, 闫业浩1, 尤进茂1,3   

  1. 1. 山东省生命有机分析重点实验室, 曲阜师范大学化学与化工学院, 山东 曲阜 273165;
    2. 莱芜职业技术学院化工教研室, 山东 莱芜 271100;
    3. 中国科学院西北高原生物研究所, 青海 西宁 810001
  • 收稿日期:2014-02-17 修回日期:2014-04-10 出版日期:2014-06-08 发布日期:2014-05-22
  • 通讯作者: 赵先恩，尤进茂
  • 基金资助:

    国家自然科学基金项目（81303179）；曲阜师范大学科研启动基金项目（BSQD2012019）.

Determination of four phenolic endocrine disruptors in environmental water samples by high performance liquid chromatography-fluorescence detection using dispersive liquid-liquid microextraction coupled with derivatization

WANG Xiaoyan1, QI Weimei2, ZHAO Xian'en1, LÜ Tao1, WANG Xiya1, ZHENG Longfang1, YAN Yehao1, YOU Jinmao1,3   

  1. 1. Shandong Provincial Key Laboratory of Life-Organic Analysis, College of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, China;
    2. Department of Chemical Engineering, Laiwu Vocational and Technical College, Laiwu 271100, China;
    3. Northwest Institute of Plateau Biology, Chinese Academy of Sciences, Xining 810001, China
  • Received:2014-02-17 Revised:2014-04-10 Online:2014-06-08 Published:2014-05-22

PDF

406

被引次数

19

摘要：

为实现小体积环境水样中酚类化合物的准确、快速、高灵敏测定，通过分散液液微萃取（DLLME）和荧光衍生化的结合，建立了高效液相色谱-荧光检测（HPLC-FLD）双酚A、壬基酚、辛基酚和对特辛基酚的分析方法。考察并优化了DLLME和衍生化条件，结果表明，最优的DLLME条件为萃取剂氯仿用量70 μL，分散剂乙腈用量400 μL，漩涡振荡3 min，高速离心2 min。以2-[2-（7H-二苯并[a，g]咔唑-乙氧基）]-乙基氯甲酸酯（DBCEC-Cl）为柱前衍生试剂，在pH 10.5的Na2CO3-NaHCO3缓冲液/乙腈溶液、50 ℃下衍生反应3 min得到稳定的衍生产物，于10 min内实现了4种酚衍生物的分离。方法的检出限为0.9~1.6 ng/L，定量限为3.8~7.1 ng/L，具有良好的线性、精密度和回收率，与以往报道的方法相比具有一定的优势和实用性，可用于造纸厂废水、湖水、生活废水、自来水中4种酚类内分泌干扰物的测定。

关键词: 分散液液微萃取, 酚类化合物, 高效液相色谱, 环境水样, 内分泌干扰物, 衍生化, 荧光检测

Abstract:

To achieve accurate, fast and sensitive detection of phenolic endocrine disruptors in small volume of environmental water samples, a method of dispersive liquid-liquid microextraction (DLLME) coupled with fluorescent derivatization was developed for the determination of bisphenol A, nonylphenol, octylphenol and 4-tert-octylphenol in environmental water samples by high performance liquid chromatography-fluorescence detection (HPLC-FLD). The DLLME and derivatization conditions were investigated, and the optimized DLLME conditions for small volume of environmental water samples (pH 4.0) at room temperature were as follows: 70 μL chloroform as extraction solvent, 400 μL acetonitrile as dispersing solvent, vortex mixing for 3 min, and then high-speed centrifugation for 2 min. Using 2-[2-(7H-dibenzo[a,g]carbazol-7-yl)-ethoxy] ethyl chloroformate (DBCEC-Cl) as precolumn derivatization reagent, the stable derivatives of the four phenolic endocrine disruptors were obtained in pH 10.5 Na2CO3-NaHCO3 buffer/acetonitrile at 50 ℃ for 3 min, and then separated within 10 min by HPLC-FLD. The limits of detection (LODs) were in the range of 0.9-1.6 ng/L, and the limits of quantification (LOQs) were in the range of 3.8-7.1 ng/L. This method had perfect linearity, precision and recovery results, and showed obvious advantages and practicality comparing to the previously reported methods. It is a convenient and validated method for the routine analysis of phenolic endocrine disruptors in waste water of paper mill, lake water, domestic wastewater, tap water, etc.

Key words: derivatization, dispersive liquid-liquid microextraction (DLLME), endocrine disruptors, environmental water samples, fluorescence detection (FLD), high performance liquid chromatography (HPLC), phenols

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