Validation of a qualitative screening method for pesticides in fruits and vegetables by gas chromatography quadrupole-time of flight mass spectrometry with atmospheric pressure chemical ionization

• Applicability of GC-(APCI)QTOF MS as new tool for wide-scope screening of pesticides in fruits and vegetables demonstrated.
• Validation of screening method according to SANCO/12571/2013.
• Detection of the pesticides based on the presence of M+·/MH+ in most cases.
• Screening detection limit 0.01 mg kg−1 for 77% of the pesticides investigated.
• Successful identification at 0.01 mg kg−1 for 70% of the pesticides/matrix combinations.

A wide-scope screening method was developed for the detection of pesticides in fruit and vegetables. The method was based on gas chromatography coupled to a hybrid quadrupole time-of-flight mass spectrometer with an atmospheric pressure chemical ionization source (GC-(APCI)QTOF MS). A non-target acquisition was performed through two alternating scan events: one at low collision energy and another at a higher collision energy ramp (MSE). In this way, both protonated molecule and/or molecular ion together with fragment ions were obtained in a single run. Validation was performed according to SANCO/12571/2013 by analysing 20 samples (10 different commodities in duplicate), fortified with a test set of 132 pesticides at 0.01, 0.05 and 0.20 mg kg−1. For screening, the detection was based on one diagnostic ion (in most cases the protonated molecule). Overall, at the 0.01 mg kg−1 level, 89% of the 2620 fortifications made were detected. The screening detection limit for individual pesticides was 0.01 mg kg−1 for 77% of the pesticides investigated. The possibilities for identification according to the SANCO criteria, requiring two ions with a mass accuracy ≤±5 ppm and an ion-ratio deviation ≤±30%, were investigated. At the 0.01 mg kg−1 level, identification was possible for 70% of the pesticides detected during screening. This increased to 87% and 93% at the 0.05 and 0.20 mg kg−1 level, respectively. Insufficient sensitivity for the second ion was the main reason for the inability to identify detected pesticides, followed by deviations in mass accuracy and ion ratios.

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