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Multi-mycotoxin stable isotope dilution LC-MS/MS method for Fusarium toxins in cereals

Analytical and Bioanalytical Chemistry volume 408, pages 307–317 (2016)Cite this article

Abstract

A multi-mycotoxin stable isotope dilution LC-MS/MS method was developed for 14 Fusarium toxins including modified mycotoxins in cereals (deoxynivalenol, 3-acetyldeoxynivalenol, 15-acetyldeoxynivalenol, HT2-toxin, T2-toxin, enniatin B, enniatin B1, enniatin A1, enniatin A, beauvericin, fusarenone X, nivalenol, deoxynivalenol-3-glucoside, and zearalenone). The chromatographic separation of the toxins with particular focus on deoxynivalenol and deoxynivalenol-3-glucoside was achieved using a C18-hydrosphere column. An expedient sample preparation method was developed that uses solid-phase extraction for the purification of trichothecenes combined with zearalenone, enniatins, and beauvericin and provides excellent validation data. Linearity, intra-day precision, inter-day precision, and recoveries were ≥0.9982, 1–6 %, 5–12 %, and 79–117 %, respectively. Method accuracy was verified by analyzing certified reference materials for deoxynivalenol, HT2-toxin, and T2-toxin with deviations below 7 %. The results of this method found barley malt samples from 2012, 2013, and 2014 frequently contaminated with high concentrations of enniatin B, deoxynivalenol, and its modified mycotoxin deoxynivalenol-3-glucoside. Samples from 2012 were especially contaminated. Fusarenone X was not detected in any of the analyzed samples.

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Abbreviations

15-ADON:

15-Acetyldeoxynivalenol

3-ADON:

3-Acetyldeoxynivalenol

BEA:

Beauvericin

D3G:

Deoxynivalenol-3-glucoside

DON:

Deoxynivalenol

ENN:

Enniatin

ESI:

Electrospray ionization

FUSX:

Fusarenone X

HT2:

HT2-toxin

NIV:

Nivalenol

SPE:

Solid-phase extraction

T2:

T2-toxin

ZEA:

Zearalenone

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Acknowledgments

We thank Cajetan Geißinger, Chair of Brewing and Beverage Technology, TU München, and Katharina Hofer, Chair of Phytopathology, TU München, for providing wheat, barley, and malt samples. This project was supported by the Forschungskreis der Ernährungsindustrie e.V. (FEI, Bonn), the AiF, the German Federal Ministry of Economic Affairs and Energy (AiF-Project No.: 17221 N), and the Wissenschaftsförderung der Deutschen Brauwirtschaft e.V. Moreover, the authors gratefully acknowledge the support by the Faculty Graduate Center Weihenstephan of TUM Graduate School at Technische Universität München, Germany.

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  1. Chair of Analytical Food Chemistry, Technische Universität München, Alte Akademie 10, 85354, Freising, Germany

    Katharina Habler & Michael Rychlik

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  1. Katharina Habler
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  2. Michael Rychlik
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Correspondence to Michael Rychlik.

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Habler, K., Rychlik, M. Multi-mycotoxin stable isotope dilution LC-MS/MS method for Fusarium toxins in cereals. Anal Bioanal Chem 408, 307–317 (2016). https://doi.org/10.1007/s00216-015-9110-7

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  • DOI: https://doi.org/10.1007/s00216-015-9110-7

Keywords

  • Trichothecenes
  • Enniatins
  • Stable isotope dilution assay
  • LC-MS/MS
  • Solid-phase extraction
  • Barley