RESUMO
Hydrophilic interaction liquid chromatography is an alternative liquid chromatography mode for separation of polar compounds. In the recent years, this liquid chromatography mode has been recognized as an important solution for the analysis of compounds not amenable to reverse phase chromatography. In this work, we evaluated three different hydrophilic liquid chromatography stationary phases for the determination of 14 highly polar anionic molecules including pesticides such as glyphosate, glufosinate, ethephon and fosetyl, their main metabolites, and bromide, chlorate, and perchlorate. Several mobile phase compositions were evaluated combined with different gradients for the chromatographic run. The two columns that presented the best results were used to assess the performance for the determination of the 14 compounds in challenging highly complex feed materials. Very different matrix effects were observed for most of the compounds in each column, suggesting that different interactions can occur. Using isotopically labeled internal standards, acceptable quantitative performance and identification could be achieved down to 0.02 mg kg-1 (the lowest level tested) for most compounds. While one column was found to be favorable in terms of scope (suited for all 14 compounds), the other one was more suited for quantification and identification at lower levels, however, not for all analytes tested.
RESUMO
In this work, an easy and fast procedure for the selective multiresidue determination of 14 highly polar pesticides (including glyphosate, glufosinate, ethephon and fosetyl) and metabolites in beverages is presented. After an initial sample dilution (1:1, v/v), the extract is shaken and centrifuged, further diluted and then injected directly into the LC-MS/MS system, using hydrophilic interaction liquid chromatography (HILIC) and tandem mass spectrometry. No clean-up procedure was needed. The method was validated according to the current European guidelines for pesticide residue analysis in food and feed and linearity, limits of detection and quantification, matrix effects, trueness and precision were assessed. For plant-based milk, wine and beer samples, 10, 11 and 12 analytes, respectively, out of 14 were fully validated at 10 µg kg-1, the lowest spike level tested. The matrix effect was negative in most of the cases, showing for some compounds, such as HEPA, up to 80% suppression when compared to the response from standards in solvent. The use of isotopically labelled internal standards is required for the optimal quantification, as it compensates for high and varying matrix effects and also for recovery losses during extraction.
