Retention time-independent strategy for screening pesticide residues in herbs based on a fingerprint database and all ion fragmentation acquisition with LC-QTOF MS

Abstract

A retention time (RT)-independent strategy for nontargeted screening of pesticide residues in herbs was exploited using liquid chromatography-quadrupole time-of-flight mass spectrometry (LC-QTOF MS). The core of this strategy is a fingerprint database coupled with a data-independent acquisition (DIA) scan mode of all ion fragmentation (AIF). In the fingerprint database, a total of 150 pesticides with quasimolecular ions and fragment ions at five-level collision energies were collected as qualified ions for screening. During the data acquisition, the AIF scan was performed via real unbiased full-spectrum MS/MS acquisition. Six herb matrices spiked with 30 banned pesticides were used to evaluate the applicability of the strategy in real samples. The use of the narrow ion mass extraction window (10 mDa) and the narrow RT window (0.1 min) enabled the effective extraction of spectra from noisy backgrounds and the discovery of suspected pesticides via similarity matching of filtered qualified ions. On average, more than 11/30 of pesticides at 1 ng mL⁻¹ and more than 23/30 of pesticides at 10 ng mL⁻¹ or lower could be screened out in each matrix using at least two qualified ions. In addition, the AIF mode exhibited superior anti-interference capability compared to data-dependent acquisition (DDA) and sequential window acquisition of all theoretical mass spectra (SWATH), as determined by comparing the limits of screening (LOSs) of 30 banned pesticides spiked into Isatidis Folium. Finally, the developed strategy was applied to screen pesticide residues in extracts of Ganoderma and Foeniculi Fructus. Phorate-sulfone and phorate-sulfoxide were found in Ganoderma, as well as terbufos-sulfone and terbufos-sulfoxide were found in Foeniculi Fructus. In conclusion, the developed RT-independent strategy based on a fingerprint database and AIF acquisition with LC-QTOF MS seems to be one of the most efficient tools for the analysis of nontargeted pesticide residues in complicated matrices.