Co-Authors:
Muszkat, L., Pestic. Chem. Resid. Res. Lab., Agric. Res. Organ., Volcani Cent. Bet Dagan, Israel
Aharonson, N., Pestic. Chem. Resid. Res. Lab., Agric. Res. Organ., Volcani Cent. Bet Dagan, Israel
Abstract:
A direct GC/MS determination of aldicarb [2-methyl-2-(methylthio)propionaldehyde o-(methyl carbamoyl) oxime], of its structural isomer butocarboxime [2-methylthio-o-(N-methyl carbamoyl) butanone-3-oxime], and of their toxic sulfoxide and sulfone metabolites is developed. Mild GC conditions using a 2% OV-17 (phenyl-methyl silicone polymer) liquid phase column provide the lowest extent of degradation. The CI/MS of the directly introduced molecules is compared to their GC/CI/MS. Butocarboxime is analyzed intact whereas its metabolites, as well as aldicarb and its sulfone derivative, undergo an on-column dehydration. The intact carbon skeleton is maintained in this process, as evidenced by the [M-18]+ fragment observed in the isobutane-CI mass spectra. Aldicarb sulfoxide, the more labile molecule in these series, degrades on-column to the corresponding nitrile. Typical fragmentation patterns are observed in the GC/MS analysis which allow distinction between the two series of isomers.A direct GC/MS determination of aldicarb left bracket 2-methyl-2-(methylthio)propionaldehyde o-(methyl carbamoyl) oxime right bracket , of its structural isomer butocarboxime left bracket 2-methylthio-o-(N-methyl carbamoyl) butanone-3-oxime right bracket , and of their toxic sulfoxide and sulfone metabolites is developed. Mild GC conditions using a 2% OV-17 (phenyl-methyl silicone polymer) liquid phase column provide the lowest extent of degradation. The CI/MS of the directly introduced molecules is compared to their GC/CI/MS. Butocarboxime is analyzed intact whereas its metabolites, as well as aldicarb and its sulfone derivative, undergo an on-column dehydration. The intact carbon skeleton is maintained in this process, as evidenced by the left bracket M-18 right bracket ** plus fragment observed in the isobutane-Cl mass spectra.