Electrolyzed water combined with ozone treatment for efficient removal of mancozeb residues from grapes

Existing cleaning methods mainly focus on removing free-state pesticides. However, mancozeb can bind to the wax layer of grapes, forming bound-state residues that are difficult to remove. This study aims to develop an effective cleaning strategy to eliminate both free and bound mancozeb residues from grapes. Compared with the untreated mancozeb aqueous solution, the concentration of free mancozeb significantly decreased (p < 0.05) after treatment with ozonated water (OW), electrolyzed water (EW), and their combination (OW+EW) for 60 min. The combined treatment synergistically promoted mancozeb degradation, thus reducing its half-life to 38% and 75% of that observed when OW and EW were used alone, respectively. To investigate the effect of the waxy layer on mancozeb removal, oleanolic acid (OLA) was selected as a representative component. The binding effect of OLA limited the degradation of mancozeb in OW and EW, extending its half-life by 1.27 and 1.20 times, respectively. Density functional theory elucidated the mechanism by which the binding of OLA affects the degradation of mancozeb. Interestingly, the decomposition of mancozeb in OW + EW was almost unaffected by the introduction of OLA, indicating that the combined treatment could effectively remove bound-state mancozeb. The combined treatment was then successfully applied to remove mancozeb from grapes. After exposure to OW + EW for 10 min, the removal efficiency of mancozeb reached up to 80.61% with minimal risks of ethylene thiourea formation. There was no obvious change in the surface color of grapes after treatment. The findings provide valuable guidance for removing mancozeb from fresh fruits rich in waxy coatings.