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 microg 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.

Determination of the serine palmitoyl transferase inhibitor myriocin by electrospray and Q‐trap mass spectrometry

“…The authors do not report analytically useful information that may facilitate measurement of Myriocin also in other matrices (Shimshoni et al, 2013). Furthermore, Myriocin was never mentioned in earlier articles that describe multi-residue analyses of several tens of fungal metabolites that possibly contaminate grains and wheat (Sulyok et al, 2006;Sulyok et al, 2007aSulyok et al, , 2007b.…”

Scientific Opinion on the risk for public and animal health related to the presence of sterigmatocystin in food and feed

“…Liquid chromatography-tandem mass spectrometry (LC-MS/MS) multi-mycotoxin methods that include STC are frequently based on a single extraction step for all investigated mycotoxins (e.g., acetonitrile/water mixture) followed by the direct analysis of the diluted crude extract (Sulyok et al, 2007;Spanjer et al, 2008). This so-called dilute-and-shoot approach requires very sensitive analytical instruments and often suffers from considerable matrix effects.…”

Aflatoxins: Contamination, Analysis and Control

“…The ionization sources employed based on atmospheric pressure ionization techniques such as electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI) has resulted in a range of new methods (Beltrán et al, 2011;Cavaliere et al, 2007;Kokkonen & Jestoi, 2009;Sulyok et al, 2007). The advantages of LC-MS techniques lie in the improved detection limits, the confirmation provided by mass spectral fragmentation and the ability to filter out by mass any impurities that interfere in spectrophotometric detectors.…”