Profiling of compounds and degradation products from the postharvest treatment of pears and apples by ultra-high pressure liquid chromatography quadrupole-time-of-flight mass spectrometry.

This study deals with a simple strategy to pinpoint potential unknown compounds in full scan mass spectrometry (MS) experiments. Forty samples of apples and pears intended for human consumption were analyzed by ultra-high performance liquid chromatography quadrupole-time-of-flight (UPLC-QqTOF-MS), after extraction of the possible contaminants by rinsing the peel of the fruit with ethyl acetate. The peaks were visually recognized in the total ion chromatogram (TIC). Two major types of postharvest treatments were detected in this set of samples: imazalil (IMZ)/ethoxyquin (EQ) and thiabendazole (TBZ)/diphenylamine (DPA). The present work also describes the metabolites formed by degradation of EQ (to our knowledge not previously reported) and DPA (there was mass spectral evidence of some of them but full identification was not pursued). Hydroxy-DPA, n-phenyl-4-quinoneimine, methoxy-DPA, demethyl-EQ, demethyldehydro-EQ, EQ-dimer, methyl-EQ, EQ-N-oxyl and 2',2,4,-trimethyl-6-quinolone were unequivocally identified and confirmed. Some relationships between the applied postharvest treatment and the metabolites formed were established. Remarkably, they may constitute a useful fingerprint in further investigations of postharvest treatments. Among other significant results, the study also reveals for the first time the presence of some EQ metabolites in fruits, which are different from those previously reported in animal tissues. There is not information on the occurrence of EQ metabolites in fruits and the DPA ones have not been studied extensively in pears and apples. The levels of the metabolites found exceeded several times those of the parent compounds.