超高效液相色谱-三重四级杆质谱同时快速测定苹果中91种农药残留

Ultra-high-performance liquid chromatography coupled to triple quadruple mass spectrometry for rapid simultaneous determination of 91 pesticide residuals in apple

目的建立可同时快速检测水果中91种农药残留超高效液相色谱-三重四级杆质谱法(UHPLC-MS/MS)。方法采用QuEChERS技术进行样品前处理,加入6 g无水MgSO_(4)作为脱水剂,100 mg C18+100 mg PSA作为净化包提取浓缩,收集上清液浓缩后,用乙腈定容上机。使用Shim-pack XR-ODS Ⅲ(1.6μm)色谱柱分离,以2 mmol/L乙酸铵+0.02%(V/V)甲酸水溶液-乙腈为流动相,梯度洗脱。选择电喷雾电离源在多重反应监测模式下进行质谱分析检测,采用外标法定量。结果91种农药残留在5~100μg/L质量浓度范围内线性关系良好,相关系数(r)均>0.9900,91种农药残留的检出限(S/N=3)为0.003~1.41μg/L,定量限(S/N=10)为0.01~4.23μg/L,相对标准偏差(n=6)为1.37%~11.38%,在高、中、低3个水平下平均加标回收率为77.70%~145.5%(n=3)。结论建立的方法高效快捷,灵敏度高,适合大批量水果样品中91种农药残留的快速检测。

Objective To establish ultra-high-performance liquid chromatography coupled to triple quadruple mass spectrometry(UHPLC-MS/MS)for rapid simultaneous determination of 91 pesticide residuals in fruits.Methods Sample pretreatment was performed using the QuEChERS sample preparation kits.Then,6 g anhydrous MgSO_(4) was added as a dehydrating agent,while 100 mg C18+100 mg PSA served as a clean-up kit for extraction and concentration.The supernatant was collected for concentration,and acetonitrile was used for constant volume.The Shim-pack XR-ODS III column(1.6μm)was used for separation,and 2 mmol/L ammonium acetate+0.02%(V/V)formic acid aqueous solution-acetonitrile served as mobile phase for gradient elution.An electrospray ionization source was applied and operated in multiple reactions monitoring(MRM)mode for mass spectrometry,and quantitative analysis was performed using the external standard method.Results The residuals of 91 pesticides showed a good linear relationship at mass concentrations of 5 to 100μg/L(r>0.9900),with detection limits(S/N=3)of 0.003 to 1.41μg/L,quantitation limits(S/N=10)of 0.01 to 4.23μg/L,and relative standard deviations(n=6)of 1.37%to 11.38%.The mean spiked recovery rates were 77.70% to 145.5%(n=3)for high-,moderate-and low-concentrations of pesticides.Conclusion The established UHPLC-MS/MS is highly efficiently,rapid and highly sensitive for rapid determination of residuals of 91 pesticides in fruit samples.