Determination of carbosulfan and its metabolites in oranges by liquid chromatography ion-trap triple-stage mass spectrometry

Liquid chromatography ion-trap mass spectrometry LC–MSn has been successfully applied to identify and confirm carbosulfan and seven of its metabolites in oranges after pressurized liquid extraction (PLE) with dichloromethane. Mass spectra of carbosulfan and its metabolites were investigated using multiple stages of mass spectrometry. Although interpretation of the fragmentation pathways, based on mass spectra, enables structural elucidation and identification of these compounds, the proposed fragmentation pathways and ion structures need verification by exact mass measurements. The analytical method—PLE and LC–MS3—was validated: limits of quantification (LOQ) ranged from 0.01 to 0.07 mg kg−1; at this level, recoveries were 55–90% with RSDs (five replicate analyses) from 8 to 19%. The degradation of carbosulfan was determined in a laboratory study carried out in mature oranges (Valencia Late) and tangerines (Clementine of Nules) already harvested. Main degradation products of carbosulfan were carbofuran, 3-hydroxycarbofuran, 3-ketocarbofuran and dibutylamine.