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A liquid chromatography/tandem mass spectrometric multi-mycotoxin method for the quantification of 87 analytes and its application to semi-quantitative screening of moldy food samples

Abstract

This paper describes the extension of a previously published method based on liquid chromatography/electrospray ionization tandem mass spectrometry (HPLC/ESI-MS/MS) from 39 to currently 87 analytes. Besides the mycotoxins for which regulated concentrations exist, the method now comprises not only almost all mycotoxins for which standards are commercially available, but also a number of other important metabolites produced by fungi involved in food spoilage. The method is based on a single extraction step using an acidified acetonitrile/water mixture followed by analysis of the diluted crude extract. Method performance characteristics were determined after spiking breadcrumbs as model matrix at multiple concentration levels. With very few exceptions, coefficients of variation of the whole procedure of <5% and repeatabilities at the highest spiking level of <7% were obtained. Limits of detection ranged between 0.02 and 225 μg kg−1. The quantitative determination of ergopeptides was disturbed by epimerization due to the acidic conditions. From the remaining 77 analytes, the apparent recoveries of nine substances deviated significantly from the CEN target range of 70–110% due to incomplete extraction and/or matrix effects. In principle, the latter can be compensated for by the application of matrix-matched calibration. The developed method was applied to 18 moldy samples (including bread, fruits, vegetables, jam, cheese, chestnuts and red wine) from private households. This study revealed the great value of the described method: 37 different fungal metabolites were identified at concentrations of up to 33 mg kg−1, and some of these have never been reported before in the context of moldy food products.

ESI (+) MS/MS chromatogram (total ion current of all MRMs) of a sample of moldy dark bread

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Acknowledgements

The authors thank the government of Lower Austria and the Christian Doppler Society for the financial support and Kristian Fog Nielsen, Marika Jestoi, Herbert Oberacher and Hans Brückner for providing mycotoxin standards. Claus Zeppelzauer and the Ecoplus business agency of Lower Austria are also greatly acknowledged.

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Correspondence to Rudolf Krska.

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Sulyok, M., Krska, R. & Schuhmacher, R. A liquid chromatography/tandem mass spectrometric multi-mycotoxin method for the quantification of 87 analytes and its application to semi-quantitative screening of moldy food samples. Anal Bioanal Chem 389, 1505–1523 (2007). https://doi.org/10.1007/s00216-007-1542-2

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  • DOI: https://doi.org/10.1007/s00216-007-1542-2

Keywords

  • Liquid chromatography
  • Tandem mass spectrometry
  • Mycotoxins
  • Multi-target analysis
  • Food analysis
  • Molds