在线固相萃取-超高效液相色谱-串联质谱法测定乳制品中双酚A等4种内分泌干扰物  

Determination of 4 Environmental Endocrine Disruptors Involving Bisphenol A in Dairy Products by On-line Solid Phase Extraction Coupled with Liquid Chromatography-Tandem Mass Spectrometry

作　　者：张品[1,2] 张晶[1,2] 陈洁君[3] 段鹤君 邵兵[1,2] 

机构地区：[1]首都医科大学公共卫生学院,北京100058 [2]北京市预防医学研究中心,食物中毒诊断溯源技术北京重点实验室,北京100013 [3]中国生物技术发展中心,北京100039

出　　处：《分析化学》2014年第12期1811-1817,共7页Chinese Journal of Analytical Chemistry

基　　金：质检总局公益性行业科研专项(No.2012104003-03);国家自然科学基金(No.21177014)资助项目~~

摘　　要：建立了乳制品中三氯生、三氯卡班、双酚A和壬基酚4种内分泌干扰物的在线固相萃取超高压液相色谱-串联质谱(On-line SPE LC-MS/MS)检测方法。液态乳制品或奶粉样品中加入乙酸缓冲液,目标物经β-葡糖醛酸苷肽酶/芳基磺酸酯酶酶解后,用乙腈提取,冷冻离心10 min后,取上清液,用水稀释,在线固相萃取串联质谱法测定。样品溶液经Xbridge C8柱富集,BEH C18色谱柱分离,甲醇和水梯度洗脱,三重四极杆质谱电喷雾负离子模式下采集数据,同位素内标法定量。4种目标化合物的线性范围为0.005~5.0μg/L,相关系数R2>0.99;方法的定量限为0.03~1.0μg/kg,3个添加水平的平均加标回收率为80.2%~106.7%,RSD<15%。本方法快速、简单、灵敏度高,适用于乳制品中4种内分泌干扰物的同时检测。应用本方法对原料乳和北京市售液奶样品进行了分析,结果表明,壬基酚的检出率最高。A simple analytical method by means of on-line solid phase extraction followed liquid chromatography-tandem mass spectrometry （SPE-LC-MS/MS） was developed for the simultaneous quantitation of 4 endocrine disruptors （triclosan, triclocarban, bisphenol A and nonylphenol ） in dairy products. Infant formula and milk samples were dissolved in acetic acid buffer and hydrolyzed by fl-glucuronidase/ arylsulfatase. Acetonitrile was used as the extract. Then, the mixture was freeze-centrifuged for 10 min and the supernatant was diluted with water, and analyzed via on-line SPE-LC-MS/MS. The sample extracts were concentrated by an Xbridge C8 cartridge and separated on a BEH Cls column with a gradient mobile phase of methanol and water; then analyzed by triple quadrupole mass spectrometry. Mass acquisition was conducted under negative electrospray ionization mode. Quantification was performed by isotopic internal standard calibration. Acceptable linearity （R2 〉0.99） was achieved over the range of 0. 005-5.0 p^g/L, with limits of quantification of 0.03-1.0 p,g/kg. Average recoveries of four target compounds （spiked at three concentration levels） ranged from 80.2%-106.7% ,with relative standard deviation less than 15%. Due to its rapidity, simplicity, and high sensitivity, the method is suitable for the analysis of endocrine disruptors in dairy products. It has been applied in the analysis of raw milk and milk products collected in Beijing. As a result, nonylphenol was found with a high detectable frequency.

关 键 词：乳制品 三氯生 壬基酚 在线固相萃取 液相色谱-串联质谱 

分 类 号：O657.63[理学—分析化学] TS252.7[理学—化学]