Regulated and Non-Regulated Mycotoxin Detection in Cereal Matrices Using an Ultra-High-Performance Liquid Chromatography High-Resolution Mass Spectrometry (UHPLC-HRMS) Method

Abstract

Cereals represent a widely consumed food commodity that might be contaminated by mycotoxins, resulting not only in potential consumer health risks upon dietary exposure but also significant financial losses due to contaminated batch disposal. Thus, continuous improvement of the performance characteristics of methods to enable an effective monitoring of such contaminants in food supply is highly needed. In this study, an ultra-high-performance liquid chromatography coupled to a hybrid quadrupole orbitrap mass analyzer (UHPLC-q-Orbitrap MS) method was optimized and validated in wheat, maize and rye flour matrices. Nineteen analytes were monitored, including both regulated mycotoxins, e.g., ochratoxin A (OTA) or deoxynivalenol (DON), and non-regulated mycotoxins, such as ergot alkaloids (EAs), which are analytes that are expected to be regulated soon in the EU. Low limits of quantification (LOQ) at the part per trillion level were achieved as well as wide linear ranges (four orders of magnitude) and recovery rates within the 68–104% range. Overall, the developed method attained fit-for-purpose results and it highlights the applicability of high-resolution mass spectrometry (HRMS) detection in mycotoxin food analysis.

Developments in mycotoxin analysis: an update for 2021-22

“…In the period since the last review, a few methods for the analysis of mycotoxins with targeted HRMS have been published, which apply well-known QuEChERS-based extraction procedures in combination with clean-up protocols (Mateus et al, 2021, Tsagkaris et al, 2021. For pistachios, a product frequently found in the European Rapid Alert System for Food and Feed due to exceedance of regulatory limits for mycotoxins such as aflatoxins or OTA, Mateus et al (2021) developed a ultra-high pressure liquid chromatography (UHPLC)-HRMS multi-analyte method.…”

Interpol Review of Drug Analysis 2019-2022

“…2019 analysis of EAs in wheat and rye products in Italy [ 602 ]; LC-FLD method for the analysis of EAs in Rye Products using Lysergic Acid Diethylamide as an Internal Standard [ 603 ]; 2D LC-MS/MS method for the simultaneous determination of 350 pesticides, 16 mycotoxins, the six most important EAs (e.g. ergotamine/ergotaminine) and two modified mycotoxins (deoxynivalenol-3-glucoside and zearalenone-sulfate) [ 604 ]; 2020 a rapid NIRS method to detect and quantify alkaloids [ 605 ]; determination of the covariation of ergot severity and the content of 12 EAs using HPLC and ELISA [ 606 ]; NMR study for the complete assignment of the H-1, C-13, and N-15 NMR signals of two alkaloids [ 607 ]; LC-MS/MS method for determination of EAs and tropane alkaloids (TAs) [ 608 ]; 2021 review [ 609 ]; UHPLC-MS/MS analysis of EAs [ 610 ]; analytical workflow including mass spectral library, generic sample preparation, chromatographic separation, and analysis by HRMS was developed and applied to 156 compounds including 90 plant toxins (pyrrolizidine alkaloids (Pas), TAs, glycoalkaloids, isoquinoline alkaloids and aristolochic acids), 54 mycotoxins (including EAs and Alternaria toxins) and 12 phytoestrogens (including isoflavones, lignans and coumestan) [ 611 ]; UHPLC-MS/MS method for determination of major EAs (ergometrine, ergosine, ergotamine, ergocornine, ergokryptine, ergocristine) and their epimers (ergometrinine, ergosinine, ergotaminine, ergocorninine, ergokryptinine, and ergocristinine) [ 612 ]; review of analytical methods for EAs [ 613 ]; serotonin receptor activity profiles for nine commercialized EAs and corresponding risks of causing hallucinations [ 614 ]; UHPLC-MS/MS method for the quantification of six EAs (Ergocornine, ergocristine, ergometrine, ergosine, ergotamine, alpha-ergocryptine) and their corresponding epimers [ 615 ]; LC-MS/MS method for monitoring 12 EAs [ 616 ]; simultaneous determination of 11 EAs by UHPLC-MS/MS [ 617 ]; development and validation of an LC-MS/MS method to determine fifteen toxic alkaloids (EAs, PAs and TAs) [ 618 ]; UHPLC-MS/MS method to detect ten EAs [ 619 ]; UHPLC-q-Orbitrap MS method to monitor both mycotoxins, e.g., ochratoxin A (OTA) or deoxynivalenol (DON), and EAs [ 620 ]; detection of EAs and indole diterpenoids in ergot sclerotia using LC-HRMS/MS diagnostic fragment filtration [ 621 ];…”

Development of High-Throughput Sample Preparation Procedures for the Quantitative Determination of Aflatoxins in Biological Matrices of Chickens and Cattle Using UHPLC-MS/MS

“…However, HPLC-UV/FLD methods generally need tedious sample preparation and pre- or post-column derivatization steps, whereas ELISA methods may show potential cross-reactivity with metabolites of the analytes of interest or matrix components [ 7 , 11 , 25 ]. In recent decades, (ultra)high-pressure liquid chromatography ((U)HPLC) coupled with mass spectrometry (MS) has become the standard method for the analysis of mycotoxins in food, feed, and other matrices due to its superior specificity and sensitivity [ 5 , 6 , 8 , 27 , 28 , 29 , 30 ]. Either triple quadrupole MS instruments enabling tandem mass spectrometry (MS/MS), which provide high sensitivity and specificity [ 1 , 28 ], or high-resolution mass spectrometry [ 31 , 32 ] are used.…”