Applications of nDATA for screening, quantitation, and identification of pesticide residues in fruits and vegetables using UHPLC/ESI Q‐Orbitrap all ion fragmentation and data independent acquisition

Abstract

High sample throughput and effective multiresidue methods for screening, quantitation, and identification are desired for the analysis of a large number of pesticides in routine monitoring programs for food safety. This study was designed to explore the use of an UHPLC/ESI Q‐Orbitrap nontarget data acquisition for target analysis (nDATA) workflow for screening 655 pesticides and quantifying a small group of 46 most likely incurred pesticide residues in fruits and vegetables in a single analysis. High‐resolution mass spectrometers such as the Q‐Orbitrap offer unique applications for pesticide analysis using full MS scan with data independent acquisition (DIA) or all ion fragmentation (AIF) scan. The experiments were designed to achieve a balance between selectivity and cycle time by considering parameter settings such as mass resolution and the number of mass isolation windows or isolation window widths. Coupled with ultra‐high performance liquid chromatography (UHPLC), both full MS/DIA and full MS/AIF nDATA workflows were evaluated for screening, quantification, and identification in a single analysis. In general, UHPLC/ESI full MS/vDIA detected more fragment ions per pesticide than AIF when one to four fragments were compared. UHPLC/ESI full MS/vDIA and AIF generated comparable quantitative results, but the latter provided slightly better repeatability likely due to its shorter cycle time and more scans across a chromatographic peak. UHPLC/ESI full MS/vDIA may be preferable for screening, quantitation and identification when the testing scope covers a few hundreds of pesticides in a single analysis.

Current Role of Mass Spectrometry in the Determination of Pesticide Residues in Food

“…However, as discussed in Section 2, analytical methods are evolving to cover a larger number of compounds. In this framework, HRMSbased methods have significantly expanded the testing scope of pesticides, monitoring almost 1000 analytes in less than 15 min [118]. Despite the fact that targeted analysis of pesticides can also be addressed by HRMS [22,154], HRMS-based workflows are primarily intended for non-targeted analysis of pesticides, including suspect screening approaches.…”

“…ESI has been shown to be more universal than APCI for the ionization of many pesticides, whereas photoionization of pesticides has rarely been reported [90]. A large number of multiresidue methods and mega-methods have been proposed for the determination of pesticide residues by LC-ESI-MS in a wide variety of feed [73] and food products, such as vegetables and fruits [118] or honey [119].…”

Traceable and Integrated Pesticide Screening (TIPS), a Systematic and Retrospective Strategy for Screening 900 Pesticides and Unknown Metabolites in Tea

“…14,15 In addition, the retention time tolerance criterion was 0.5 min for screening purposes recommended by the Canadian Food Inspection Agency (CFIA) and the US Food and Drug Administration (USFDA). 16 The traditional analysis of pesticides is carried out with multiple reaction monitoring (MRM) mode in triple-quadrupole tandem mass spectrometry (QqQ). This method is considered the gold standard for pesticide residue analysis because of its good selectivity and sensitivity.…”

“…This method is considered the gold standard for pesticide residue analysis because of its good selectivity and sensitivity. 16 This approach is based on the concept of "known knowns" in Rumsfeld quadrants that the targeted compounds are expected and found. 17 The commercial availability of standards and the instrument cycle time are the limits of this targeted technique.…”

“…Orbitrap and time-of-flight (TOF) are frequently utilized as mass analyzers in HRMS in pesticide analysis. In a positive identification, a precursor and at least one fragment are required, and the mass accuracy of these ions required in the legislation is better than 5 ppm to prevent false positives. , In addition, the retention time tolerance criterion was 0.5 min for screening purposes recommended by the Canadian Food Inspection Agency (CFIA) and the US Food and Drug Administration (USFDA) …”