Ultrahigh-Performance Liquid Chromatography Electrospray Ionization Q-Orbitrap Mass Spectrometry for the Analysis of 451 Pesticide Residues in Fruits and Vegetables: Method Development and Validation

Abstract

This paper presents an application of ultrahigh-performance liquid chromatography electrospray ionization quadrupole Orbitrap high-resolution mass spectrometry (UHPLC/ESI Q-Orbitrap MS) for the determination of 451 pesticide residues in fruits and vegetables. Pesticides were extracted from samples using the QuEChERS (quick, easy, cheap, effective, rugged, and safe) procedure. UHPLC/ESI Q-Orbitrap MS in full MS scan mode acquired full MS data for quantification, and UHPLC/ESI Q-Orbitrap Full MS/dd-MS(2) (i.e., data-dependent scan mode) obtained product ion spectra for identification. UHPLC/ESI Q-Orbitrap MS quantification was achieved using matrix-matched standard calibration curves along with the use of isotopically labeled standards or a chemical analogue as internal standards to achieve optimal method accuracy. The method performance characteristics include overall recovery, intermediate precision, and measurement uncertainty evaluated according to a nested experimental design. For the 10 matrices studied, 94.5% of the pesticides in fruits and 90.7% in vegetables had recoveries between 81 and 110%; 99.3% of the pesticides in fruits and 99.1% of the pesticides in vegetables had an intermediate precision of ≤20%; and 97.8% of the pesticides in fruits and 96.4% of the pesticides in vegetables showed measurement uncertainty of ≤50%. Overall, the UHPLC/ESI Q-Orbitrap MS demonstrated acceptable performance for the quantification of pesticide residues in fruits and vegetables. The UHPLC/ESI Q-Orbitrap Full MS/dd-MS(2) along with library matching showed great potential for identification and is being investigated further for routine practice.

Multi-mycotoxin Analysis of Finished Grain and Nut Products Using Ultrahigh-Performance Liquid Chromatography and Positive Electrospray Ionization–Quadrupole Orbital Ion Trap High-Resolution Mass Spectrometry

“…At R FWHM = 70 000 and 140 000, the average δ M and SD improved to ±1.0 ppm and <1 ppm, respectively. These results are consistent with other studies using single-stage or hybrid (quadrupole and ion trap) orbital trap MS analyzers at various R FWHM settings, ranging 10 000−100 000 for analyzing drugs in dried blood spots 21 and pesticides in fresh produce 22 as well as mycotoxins and other chemical contaminants in food commodities 23 and baby food. 24 The δ M values from the solvent and wheat matrix at 1.0 ng/mL decrease, with increasing R FWHM , but no significant trend was observed with the peanut matrix.…”

Evaluation of gas chromatography – electron ionization – full scan high resolution Orbitrap mass spectrometry for pesticide residue analysis

“…Numerous applications can be found in the literature, often combining quantitative determination with an additional qualitative screening in one analysis [e.g. [11][12][13][14][15][16][17][18][19][20].…”

A high‐resolution accurate mass (HR/AM) approach to identification, profiling and characterization of in vitro nefazodone metabolites using a hybrid quadrupole Orbitrap (Q‐Exactive)

“…Q‐Exactive) to integrate a combined quantitative and qualitative approach for early‐phase metabolism assays. The following description of the workflow will expand on its qualitative capabilities; detailed interrogation of the quantitative performance of HR/AM versus more traditional QQQ instruments can be found in the literature …”