Simultaneous determination and method validation of difenoconazole, propiconazole and pyraclostrobin in pepper and soil by LC-MS/MS in field trial samples from three provinces, China

A liquid chromatography-electrospray ionization tandem mass spectrometry method was developed for simple and accurate detection of the fungicides difenoconazole, propiconazole and pyraclostrobin in peppers and soil. Three fungicides residues were extracted from samples by acetonitrile and cleaned up by dispersive solid-phase extraction before instrumental analysis. The accuracy and precision of the method were evaluated by conducting an intra- and inter-day recovery experiment. The limits of quantification and detection of difenoconazole, propiconazole and pyraclostrobin in pepper and soil were 0.005 and 0.0015 mg/kg, respectively. The recoveries were investigated by spiking pepper and soil at three levels, and were found to be in the ranges 79.62-103.15% for difenoconazole, 85.94-103.35% for propiconazole and 80.14-97.69% for pyraclostrobin, with relative standard deviations <6.5%. Field experiments were conducted in three locations in China. The half-lives of difenoconazole, propiconazole and pyraclostrobin were 5.3-11.5 days in peppers and 6.1-32.5 days in soil. At harvest, pepper samples were found to contain difenoconazole, propiconazole and pyraclostrobin well below the maximum residue limits of European Union at the interval of 21 days after last application following the recommended dosage.