UPLC-MS/MS法测定水中135种农药及代谢产物

Ultra High Performance Liquid Chromatography Tandem Mass Spectrometry for Determination of 135 Pesticides and Metabolites in Water

建立了直接进样-超高效液相色谱串联质谱法快速筛查和检测水体中135种农药及代谢产物的方法。样品经0.22μm亲水性聚四氟乙烯滤膜过滤后直接进样,以乙腈和0.05%甲酸水溶液为流动相进行梯度洗脱,经HSS T3色谱柱进行分离,采用电喷雾离子源正离子及负离子模式分析检测,外标法定量。实验结果表明:135种农药及代谢产物在各自范围内线性关系良好,线性相关系数r2>0.995,方法检出限(LOD,S/N=3)为0.015~1.5μg/L,定量限(LOQ,S/N=10)为0.05~5μg/L。将目标化合物在0.5、5、50μg/L浓度水平下加标,水源水和饮用水水样的加标回收率分别在62.9%~123.7%、59.3%~122.3%,相对标准偏差(RSD,n=6)分别在0.3%~17.4%、0.3%~17.6%。该方法解决了多种类农药直接进样时滤膜吸附目标化合物的问题,样品前处理简单,上机后检测完成135种农药及代谢产物仅耗时15 min,具有分析快速、灵敏度高、重现性好的优点,适用于水源水和饮用水中痕量农药类污染物的分析测定,为快速筛查水体中农药污染水平提供了可靠的技术支撑。

This paper established a method of direct injection coupled with ultra high performance liquid chromatography tandem mass spectrometry for rapid screening and detection of 135 pesticides and metabolites in water.The samples were filtered through hydrophilic polytetrafluoroethylene(PTFE)filter membrane with aperture of 0.22μm,directly injected into the chromatographic column in which acetonitrile and 0.05%formic acid aqueous solution were used as mobile phase for gradient elution,and separated by HSS T_3 column.The samples were detected by electrospray ionization in positive and negative ion modes,and quantified by external standard method.The 135 pesticides and metabolites had good linear relationship in their respective ranges.The linear correlation coefficient r~2 was greater than0.995.The limits of detection(LOD,S/N ratio of 3)were between 0.015 and 1.5μg/L,and the limits of quantification(LOQ,S/N ratio of 10)were from 0.05 to 5μg/L.The target compounds were spiked at concentrations of 0.5μg/L,5μg/L,and 50μg/L,respectively.The recoveries of water samples from source water and drinking water were in the ranges of 62.9%-123.7%and 59.3%-122.3%,respectively,and the relative standard deviations(RSD,n=6)were in the ranges of 0.3%-17.4%and 0.3%-17.6%,respectively.This method solved the problem of target compounds adsorbed by filter membrane when many kinds of pesticides were directly injected.The sample pretreatment is simple,and the detection of135 kinds of pesticides and metabolites takes only 15 min.Therefore,the method has the advantages of fast analysis,high sensitivity and good reproducibility,and is suitable for the analysis and determination of trace pesticide pollutants in source water and drinking water,which provides reliable technical support for rapid determination of pesticide pollution in water bodies.