Department of Analytical Chemistry, Nutrition and Food Sciences. Research Institute On Chemical and Biological Analysis (IAQBUS), Universidade de Santiago de Compostela, Santiago de Compostela, 15782, Spain.
Anal Bioanal Chem. 2022 Jan;414(3):1445-1455. doi: 10.1007/s00216-021-03775-w. Epub 2021 Nov 25.
The performance of two different analytical methodologies to investigate the presence of glyphosate (GLY) and aminomethylphosphonic acid (AMPA) residues in wine samples was evaluated. Transformation of compounds in their fluorene-9-methyloxycarbonyl derivatives permitted their separation under reversed-phase liquid chromatography with tandem mass spectrometry (LC-MS/MS) determination. Although the wine matrix severely impaired the efficiency of GLY derivatization, this drawback was solved using a molecularly imprinted sorbent for the previous, selective extraction of GLY and AMPA from wine. Alternatively, the use of a strong anionic exchange, polyvinyl alcohol-based LC column, turned to be the most effective alternative for direct determination of both compounds in diluted wine samples. The chromatographic behavior of this column and the magnitude of matrix effects observed during analysis of diluted wine samples were significantly affected by the composition of the mobile phase. Under final working conditions, this column permitted the separation of AMPA and the fungicide fosetyl (which shows common transitions in tandem MS/MS methods), it improved significantly the sample throughput versus extraction-derivatization-purification method, and it allowed the use of solvent-based calibration standards. Both analytical procedures provided similar limits of quantification (LOQs) for GLY (0.5-1.0 ng mL), while the multistep method was 8 times more sensitive to AMPA than the direct procedure. GLY residues stayed above method LOQs in 70% of the processed wines; however, concentrations measured in 95% of positive samples remained 100 times below the maximum residue limit (MRL) set for GLY in vinification grapes.
两种不同分析方法检测葡萄酒样品中草甘膦（GLY）和氨甲基膦酸（AMPA）残留的性能进行了评估。将化合物转化为芴-9-甲氧基羰基衍生物，允许在反相液相色谱-串联质谱（LC-MS/MS）测定下进行分离。尽管葡萄酒基质严重影响了 GLY 衍生化的效率，但通过使用分子印迹吸附剂对 GLY 和 AMPA 进行选择性提取，解决了这一缺点。或者，使用强阴离子交换、聚乙烯醇基 LC 柱作为直接测定稀释葡萄酒样品中两种化合物的最有效替代方法。该柱的色谱行为以及在分析稀释葡萄酒样品时观察到的基质效应的大小，显著受到流动相组成的影响。在最终工作条件下，该柱允许 AMPA 和杀菌剂乙膦（在串联 MS/MS 方法中显示共同的转换）的分离，与提取-衍生化-净化方法相比，显著提高了样品通量，并允许使用基于溶剂的校准标准。两种分析方法对 GLY（0.5-1.0ng mL）的定量限（LOQs）相似，而多步方法对 AMPA 的灵敏度比直接方法高 8 倍。在处理过的葡萄酒中，70%的 GLY 残留量高于方法的 LOQs；然而，在 95%的阳性样品中测量的浓度仍低于酿造葡萄中 GLY 的最大残留限量（MRL）的 100 倍。
