General Screening and Multiple Dissociation Methods for Complementary LC-MS Analysis of Pesticides in Beverages: Potential and Pitfalls.

A commercial QqTOF platform (ZenoTOF 7600 system) was modified to enable three fragmentation modes: collision-induced dissociation (CID), electron-activated dissociation (EAD), and ultraviolet photodissociation (UVPD) at 266 nm. 168 pesticides, which showed fragmentation in CID, also provide EAD spectra. In the case of UVPD, 158 compounds fragmented under 266 nm photon irradiation. The performance of the novel platform was evaluated using data-independent SWATH CID acquisition for the general screening, and multiple product ion acquisitions were scheduled with CID/EAD/UVPD for confirmatory analysis of pesticides in juice and white and red wine samples. A column-switching liquid chromatography (LC) method with online dilution was developed to inject large volumes (80 μL) into the system. The approach enabled the detection and concentration estimation of approximately 30 pesticides in juices and wines, including insecticides, neonicotinoids, and fungicides. Pesticide limits of detection (LODs) were found to be in the picogram per milliliter to nanogram per milliliter range for MS1 and MS2 acquisitions.