Development, validation, and application of a multi-method for the determination of mycotoxins, plant growth regulators, tropane alkaloids, and pesticides in cereals by two-dimensional liquid chromatography tandem mass spectrometry

Abstract

Mycotoxins and pesticides regularly co-occur in agricultural products worldwide. Thus, humans can be exposed to both toxic contaminants and pesticides simultaneously, and multi-methods assessing the occurrence of various food contaminants and residues in a single method are necessary. A two-dimensional high performance liquid chromatography tandem mass spectrometry method for the analysis of 40 (modified) mycotoxins, two plant growth regulators, two tropane alkaloids, and 334 pesticides in cereals was developed. After an acetonitrile/water/formic acid (79:20:1, v/v/v) multi-analyte extraction procedure, extracts were injected into the two-dimensional setup, and an online clean-up was performed. The method was validated according to Commission Decision (EC) no. 657/2002 and document N° SANTE/12682/2019. Good linearity (R2 > 0.96), recovery data between 70-120%, repeatability and reproducibility values < 20%, and expanded measurement uncertainties < 50% were obtained for a wide range of analytes, including very polar substances like deoxynivalenol-3-glucoside and methamidophos. However, results for fumonisins, zearalenone-14,16-disulfate, acid-labile pesticides, and carbamates were unsatisfying. Limits of quantification meeting maximum (residue) limits were achieved for most analytes. Matrix effects varied highly (−85 to +1574%) and were mainly observed for analytes eluting in the first dimension and early-eluting analytes in the second dimension. The application of the method demonstrated the co-occurrence of different types of cereals with 28 toxins and pesticides. Overall, 86% of the samples showed positive findings with at least one mycotoxin, plant growth regulator, or pesticide. Graphical abstract

Occurrence and Chemistry of Tropane Alkaloids in Foods, with a Focus on Sample Analysis Methods: A Review on Recent Trends and Technological Advances

“…Regarding detectors, MS detectors predominate, considering that the lack of a strong chromophore in TAs molecules requires detections at low wavelengths, making it difficult to identify these compounds with UV detectors. For this reason, different analyzers based on MS are used to determine TAs, usually triple quadrupole (QqQ) [13,14,[17][18][19][21][22][23]25,[28][29][30]33,41,42] but also quadrupole-ion trap (QTRAP) [27,38]. High-resolution mass spectrometry analyzers (HRMS) such as the Orbitrap analyzer [5,16,18,26,32,39,40] or its variant quadrupoleorbitrap (Q-Orbitrap) [5] have also been used.…”

“…As can be seen in Table 4, there are many studies that use this technique to extract TAs from different foods [13,17,23,25,27,33,[38][39][40][41][42]. Table S2 (see Supplementary Materials) shows useful information about instrumental analysis and details about the validation parameters of these methods.…”

Overview of Recent Liquid Chromatography Mass Spectrometry-Based Methods for Natural Toxins Detection in Food Products

“…Finally, another 2D-LC-MS/MS multiclass method was developed and validated for the determination of mycotoxins and TAs together with plant growth regulators and pesticides in cereals [ 185 ]. A rapid acetonitrile/water/formic acid extraction procedure was optimized before LC-MS/MS analysis.…”

Strategic Priorities of the Scientific Plan of the European Research Infrastructure METROFOOD-RI for Promoting Metrology in Food and Nutrition

“…In the field of instrumental methods, the chromatographic ones coupled to different MS detectors (e.g., LC-MS/MS, LC-QTOF-MS, GC-MS) is still the most suitable means to detect contaminants in foods. There is a trend in employing both targeted and non-targeted high-resolution-MS methods (HRMS), which detect a wider array of compounds (multiclass), such as the one developed by Steiner et al [ 56 ] for the detection of more than 1200 biotoxins, pesticides and veterinary drugs in a complex feed and that of Rausch et al which detects 40 mycotoxins, 2 plant growth regulators, 2 tropane alkaloids, and 334 pesticides in cereals [ 57 ]. TOF accurate mass techniques can be applied for the non-targeted identification of pesticides, their metabolites, or degradation products and other unknown compounds present in the samples [ 58 ].…”