Determination of Mycotoxins in Dried Fruits Using LC-MS/MS—A Sample Homogeneity, Troubleshooting and Confirmation of Identity Study

Abstract

To monitor co-exposure to toxic mycotoxins in dried fruits, it is advantageous to simultaneously determine multiple mycotoxins using a single extraction and liquid chromatography with tandem mass spectrometry (LC-MS/MS) analysis. In this study, we applied a stable isotope dilution and LC-MS/MS method to multi-mycotoxin analysis in dried fruits, selecting raisins, plums, figs, and cranberries for matrix extension. Samples were prepared using cryogenic grinding, followed by the fortification of carbon-13 (13C) uniformly labeled internal standards for twelve mycotoxins, and extraction using 50% acetonitrile. Homogeneity of prepared samples, defined as particle size Dv90 < 850 µm for the tested matrices, was characterized using a laser diffraction particle size analyzer, and reached using cryogenic grinding procedures. The majority of recoveries in the four matrices for aflatoxins and ochratoxin A spiked at 1–100 ng/g; fumonisins, T-2 toxin, HT-2 toxin, and zearalenone spiked at 10–1000 ng/g, ranged from 80 to 120% with relative standard deviations (RSDs) of <20%. Deoxynivalenol was not detected at 10 and 100 ng/g in plums, and additional troubleshooting procedures using liquid-liquid extraction (LLE), solid phase extraction (SPE), and elution gradient were evaluated to improve the detectability of the mycotoxin. Furthermore, we confirmed the identity of detected mycotoxins, ochratoxin A and deoxynivalenol, in incurred samples using enhanced product ion scans and spectral library matching.