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  

Determination of four phenolic endocrine disruptors in environmental water samples byhighperformance liquid chromatography-fluorescence detection usingdispersive liquid-liquid microextraction coupled with derivatization

作　　者：王晓燕[1] 亓伟梅[2] 赵先恩[1] 吕涛[1] 王西亚[1] 郑龙芳 闫业浩 尤进茂[1,3] 

机构地区：[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

出　　处：《色谱》2014年第6期623-628,共6页Chinese Journal of Chromatography

基　　金：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)

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70μL，分散剂乙腈用量400μL，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 Na2 CO3-NaHCO 3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。To achieve accurate,fast and sensitive detection of phenolic endocrine disruptors in small volume of environmental water samples,a method of dispersive liquid-liquid microextrac-tion（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＆amp;nbsp;derivatives of the four phenolic endocrine disruptors were obtained in pH 10. 5 Na 2 CO 3-NaHCO 3 buffer / acetonitrile at 50 ℃ for 3 min,and then separated within 10 min by HPLC-FLD. The lim-its 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.

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

分 类 号：O658[理学—分析化学]