HPLC-MS/MS法测定婴幼儿果蔬米粉中17种新烟碱类杀虫剂及代谢物

Determination of 17 Neonicotinoid Pesticides and Their Metabolites in Baby Fruit and Vegetable Rice Flour by High Performance Liquid Chromatography-Tandem Mass Spectrometry

建立了婴幼儿果蔬米粉中17种新烟碱类杀虫剂及代谢物的高效液相色谱-串联质谱(HPLC-MS/MS)分析方法。样品经含1%(体积分数)甲酸的乙腈提取,QuEChERS净化,氮气吹干后,用含0.1%甲酸的乙腈水溶液(1∶4,体积比)定容。采用Acquity BEH C_(18)色谱柱(2.1 mm×100 mm,1.7μm)分离,0.1%甲酸水溶液和乙腈作为流动相梯度洗脱,高效液相色谱-串联质谱检测。结果表明,17种目标物在对应的质量浓度范围内线性良好,相关系数(r)均大于0.995 4;方法检出限(LOD)为0.02~0.15μg/kg,定量下限(LOQ)为0.06~0.50μg/kg;在LOQ、2.0μg/kg、10.0μg/kg 3个加标水平下,17种目标物在水果米粉中的平均回收率为62.5%~103%,相对标准偏差(RSD)为3.5%~17%;蔬菜米粉中的平均回收率为66.4%~108%,RSD为4.3%~13%。该方法灵敏、准确,简便、可靠,适用于婴幼儿果蔬米粉中17种新烟碱类杀虫剂及代谢物的同时检测。

A high performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS)was developed for the simultaneous determination of 17 neonicotinoid pesticides and their metabolites in baby fruit and vegetable rice flour.After moistened with water,the samples were added anhydrous magnesium sulfate(MgSO_(4)), then extracted with acetonitrile solution containing 1%(volume fraction)formic acid,followed by QuEChERS purification.The final extracts were dried under nitrogen,and the residues were dissolved in water-acetonitrile containing 0.1%formic acid(4∶1,volume ratio),then separated on an Acquity BEH C_(18)(2.1 mm × 100 mm,1.7 μm)column by gradient elution with water containing 0.1%formic acid and acetonitrile as mobile phases.The analytes were finally detected by HPLC-MS/MS in positive electrospray ionization(ESI+)mode under multiple reaction monitoring(MRM)mode,and quantified by the external standard calibration curve method.Under the optimal conditions,17 analytes were well separated within 10 min.The calibration curves for 17 analytes were linear in the respective mass concentration ranges with their correlation coefficients(r)larger than 0.995 4.The limits of detection(LODs)and limits of quantitation(LOQs)were in the range of 0.02-0.15 μg/kg and 0.06-0.50 μg/kg,respectively.The average recoveries for 17 analytes in baby fruit rice flour samples at three spiked levels of LOQ level,2.0 μg/kg and10.0 μg/kg ranged from 62.5%to 103%,with relative standard deviations(RSDs)of 3.5%-17%,while the average recoveries for vegetable rice flour samples at three spiked levels ranged from 66.4%to 108%,with RSDs of 4.3%-13%.The established method was applied to the detection of 17 neonicotinoid pesticides and their metabolites in baby fruit and vegetable rice flour samples by random sampling principle,and acetamiprid was detected in one of the vegetable rice flour samples with content of 7.4 μg/kg.The method was sensitive,accurate,convenient and reliable,and it could meet the requirements for simultaneous detection of 17 neonicotinoid pesticides and their metabolites in baby fruit and vegetable rice flour.