电喷雾萃取电离质谱法直接检测环境水样中的r邻苯二甲酸二(2-乙基己基)酯

摘要

采用电喷雾萃取电离质谱技术(Extractive electrospray ionization mass spectrometry,EESI-MS)分析水样中的有机污染物邻苯二甲酸二(2-乙基己基)酯(Di-2-ethylhexy phthalate,DEHP),系统考察了电喷雾电压、离子传输管温度、样品溶液流速及萃取剂组成对待测物信号强度的影响,优化了检测DEHP的实验条件,建立了水样中DEHP的快速质谱分析方法,并对垃圾渗滤液、城市生活污水及湖水等实际水样进行检测.结果表明,在正离子检测模式下,水样中的DEHP能够在EESI源中有效电离,生成准分子离子[M+H]+(m/z 391.28),进行碰撞诱导解离得到二级特征碎片离子m/z 279.26,167.12,149.11.在5～1000μg/L范围内,DEHP浓度与m/z 149.11质谱峰信号强度的线性关系良好,相关系数R2=0.9991,检出限LOD=0.21μg/L(S/N=3);水样的3个加标水平(8,80和400μg/L)的DEHP回收率为96.2％ ～111.2％,RSD为5.6％ ～11.8％.EESI-MS法检测垃圾渗滤液、城市生活污水和晏湖水中DEHP的含量分别为556.5、275.3和37.8μg/L.本方法具有无需样品预处理、分析速度快(单个样品分析时间约3 min)、操作简便、灵敏度高等优点,为邻苯二甲酸酯类物质的检测提供了一种快速质谱分析新方法.%The environmental organic pollutant of di-2-ethylhexy phthalate ( DEHP ) was analyzed by extractive electrospray ionization mass spectrometry ( EESI-MS ). Effect of some important experimental conditions were investigated systematically, including the electrospray voltage, temperature of ion-transport tube, sample injection rate and extractant composition. Under the optimal conditions, a method for rapid detection of DEHP in water sample was established. DEHP levels in different samples with complex matrixes were measured, including landfill leachate, urban sewage and lake water. The results showed that DEHP in water samples could be ionized by EESI source and obtained the molecule ion (m/ z 391. 28) at the positive detection mode, and then CID experiment were performed to obtain the secondary fragment ions m/ z 279. 26, 167. 12 and 149. 11. The intensity of characteristic peak m/ z 149. 11 possessed a good linearity with the concentration of DEHP in the range of 5-1000 μg / L with the correlation coefficient of R2 = 0. 9991, and the detection limit (LOD) of 0. 21 μg / L. The recoveries of DEHP at three spiked levels (8, 80, 400 μg / L) were 96. 2％ - 111. 2％ , with RSDs of 5. 6％ - 11. 8％ . With the developed EESI-MS method, the concentrations of DEHP in landfill leachate, urban sewage and Yan lake water were 556. 5, 275. 3 and 37. 8 μg / L, respectively. The EESI-MS method possessed many advantages such as no requirement of sample pretreatment, fast analysis speed ( about 3 min per sample), simple operation and high sensitivity, thus providing a new mass spectrometric method for rapid detection of phthalate esters.