Quantification and Confirmation of Fifteen Carbamate Pesticide Residues by Multiple Reaction Monitoring and Enhanced Product Ion Scan Modes via LC-MS/MS QTRAP System

Abstract

In this research, fifteen carbamate pesticide residues were systematically analyzed by ultra-high performance liquid chromatography–quadrupole-linear ion trap mass spectrometry on a QTRAP 5500 system in both multiple reaction monitoring (MRM) and enhanced product ion (EPI) scan modes. The carbamate pesticide residues were extracted from a variety of samples by QuEChERS method and separated by a popular reverse phase column (Waters BEH C18). Except for the current conformation criteria including selected ion pairs, retention time and relative intensities from MRM scan mode, the presence of carbamate pesticide residues in diverse samples, especially some doubtful cases, could also be confirmed by the matching of carbamate pesticide spectra via EPI scan mode. Moreover, the fragmentation routes of fifteen carbamates were firstly explained based on the mass spectra obtained by a QTRAP system; the characteristic fragment ion from a neutral loss of CH3NCO (−57 Da) could be observed. The limits of detection and quantification for fifteen carbamates were 0.2–2.0 μg kg−1 and 0.5–5.0 μg kg−1, respectively. For the intra- (n = 3) and inter-day (n = 15) precisions, the recoveries of fifteen carbamates from spiked samples ranged from 88.1% to 118.4%, and the coefficients of variation (CVs) were all below 10%. The method was applied to pesticide residues detection in fruit, vegetable and green tea samples taken from local markets, in which carbamates were extensively detected but all below the standard of maximum residue limit.

Keywords

• carbamates
• multiple reaction monitoring (MRM)
• enhanced product ion (EPI)
• mass fragmentation
• confirmatory method
• pesticide residues