高效液相色谱-串联质谱法测定蜂蜜中9种农药残留

Determination of nine pesticide residues in honey using high performance liquid chromatography-tandem mass spectrometry

建立了同时测定蜂蜜中9种苯并咪唑类和新烟碱类农药的全自动固相萃取-高效液相色谱-串联质谱检测方法。蜂蜜样品用磷酸盐缓冲液(pH=7. 8)溶解,超声提取,经亲水亲脂平衡(hydrophilic-lipophilic balance,HLB)固相萃取小柱净化,氮吹浓缩,定容,过滤膜后进行高效液相色谱-串联质谱分析,采用多反应监测(MRM)模式测定,以内标法定量。结果表明,在0. 002～0. 05 mg/L范围内9种农药呈现出较好的线性关系(相关系数r2≥0. 99),检出限和定量限分别为0. 1～1. 0μg/kg和0. 3～2. 0μg/kg。对阴性蜂蜜,在5. 0、10. 0、20. 0μg/kg 3个水平下分别进行加标回收试验,测出9种农药的平均回收率在78. 2%～101. 2%之间,相对标准偏差为1. 3%～14. 3%(n=6)。该方法可适用于大批量蜂蜜样品的快速准确测定。

A method is proposed for the simultaneous determination of nine benzimidazole and neonicotinoid pesticides present in honey by employing automatic solid-phase extraction with high performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS).A honey sample was dissolved in a phosphate buffer(pH=7.8)followed by ultrasonic extraction.The extracts were then purified through solid-phase extraction(SPE)with hydrophilic-lipophilic balance(HLB)cartridges.Finally,nitrogen was blown on the obtained mixture,and the mixture was subsequently filtered for conducting HPLC-MS/MS analysis.Nine compounds were detected under the multiple reaction monitoring(MRM)mode,and the corresponding quantification was performed by employing the method of internal standards.The nine detected pesticides demonstrated good linearity in the range of 0.002-0.05 mg/L,with the correlation coefficient values(r^2)being higher than 0.99.The limits of detection(LODs)(S/N=3)and limits of quantification(LOQs)(S/N=10)were found to be in the ranges of 0.1-1.0μg/kg and 0.3-2.0μg/kg,respectively.Furthermore,the results indicated that the recoveries of the nine detected pesticides range from 78.2%-101.2%at three spiked levels of 5.0,10.0,and 20.0μg/kg with a relative standard deviation(RSD)range of 1.3%-14.3%(n=6).Hence,the proposed method is rapid and can be employed for accurate determination of pesticide residues in large quantities of honey samples.