超高效液相色谱-同位素稀释高分辨质谱法测定红葡萄酒中的18种农药残留

建立了采用超高效液相色谱-同位素稀释高分辨质谱法同时快速测定红葡萄酒中18种农药残留的方法。样品采用乙腈提取，以N-丙基乙二胺（PSA）和C₁₈作为吸附剂的分散固相萃取法（d-SPE）进行净化，以BEH C₁₈色谱柱进行色谱分离，分别通过高分辨质谱的全扫描/实时二级质谱扫描（full scan/ddms²）和目标选择离子监测（targeted SIM，tSIM）模式进行定性筛查和定量检测。以多菌灵-D₄、毒死蜱-D₁₀、吡虫啉-D₄、甲氧虫酰肼-D₉、嘧霉胺-D₅和戊唑醇-D₆为内标进行内标法定量，有效地降低了样品基质的影响。待测物在0.5~50 μg/L范围内呈良好的线性关系，相关系数（r）大于0.999。18种农药残留的检出限（LOD）为0.5 μg/kg，定量限（LOQ）为1.0 μg/kg。空白红葡萄酒样品在1~40 μg/kg范围内的4个加标水平的平均回收率为85.4%~117.9%，相对标准偏差为0.5%~6.1%。应用该方法对市售的红葡萄酒样品进行检测，共检出多菌灵、吡虫啉、嘧霉胺、戊唑醇和三唑醇5种农药残留，含量分别为2.6~143.0 μg/kg、0.6~0.9 μg/kg、2.1~3.1 μg/kg、0.6~3.0 μg/kg和0.6 μg/kg。该方法适用于红葡萄酒中农药残留的快速筛查和定量检测。

Determination of 18 pesticide residues in red wine by ultra high performance liquid chromatography-high resolution mass spectrometry with isotope dilution technique

A method for the simultaneous determination of 18 pesticide residues in red wine was developed using ultra high performance liquid chromatography-high resolution mass spectrometry (UPLC-HRMS) with isotope dilution technique. The red wine samples were extracted with acetonitrile, and the extracts were cleaned up with dispersive solid phase extraction (d-SPE) using the mixture of N-propyl ethylene diamine (PSA) and C18 powder as sorbent. The extracted components were separated on a BEH C₁₈ column by gradient elution. The qualitative and quantitative analyses were operated under full scan/data dependent MS/MS (ddms²) and targeted selective ion monitoring (tSIM) by high resolution mass spectrometry, respectively. Carbendazim-D₄, chlorpyrifos-D₁₀, imidacloprid-D₄, methoxyfenozide-D₉, pyrimethanil-D₅ and tebuconazole-D₆ were used as the internal standards to reduce the matrix effects. The response of each pesticide showed a good linearity in the range of 0.5-50 μg/kg with the correlation coefficient more than 0.999. The limits of detection and quantification for the 18 pesticides in the spiked blank red wine were 0.5 μg/kg and 1.0 μg/kg, respectively. The recovery results with spiked blank red wine samples at the levels of 1 to 40 μg/kg were satisfactory with average recoveries of 85.4%-117.9% and the RSDs of 0.5%-6.1%. The method was applied for the determination of the red wine real samples from the market. Carbendazim, imidacloprid, pyrimethanil, tebuconazole and triadimenol were detected in the samples. The results show that the method is suitable for the rapid screening and quantitative analysis of pesticide residues in red wine.