Analysis of carbamate and phenylurea pesticide residues in fruit juices by solid-phase microextraction and liquid chromatography–mass spectrometry

Abstract

A new analysis method to detect carbamates and phenylurea pesticide residues in fruit juices was developed using solid-phase microextraction (SPME) coupled with liquid chromatography–single quadrupole mass spectrometry (LC/MS) and liquid chromatography–quadrupole ion trap mass spectrometry (LC/QIT-MS). The pesticide residues present in watery matrices as fruit juices were extracted using three types of fibers: 50-μm Carbowax/templated resin (CW/TPR), 60-μm poly(dimethylsiloxane)/divinylbenzene (PDMS/DVB) and 85-μm polyacrylate. The different extraction conditions were evaluated choosing as the best parameters 90 min (time), 20 °C (temperature) and 1 ml (volume). After extraction, the desorption (in a static mode) was performed in the specific interface chamber SPME/HPLC, previously filled with 70% methanol and 30% water. The best recoveries, evaluated at two fortification levels (0.2 and 0.5 mg kg −1) in fruit juices, were obtained using PDMS/DVB and CW/TPR fibers, and ranged from 25 to 82% (monolinuron, diuron and diethofencarb), with relative standard deviations (RSDs) from 1 to 17%. All the limits of quantification (LOQs) were in the range of 0.005–0.05 μg ml −1 and, in any case, equal to, or lower than, maximum residue limits (MRLs) established by Italian and Spanish legislations. The mass spectrometry analyses were carried out using an electrospray ionization (ESI) source operating in the positive mode both for single quadrupole and for QIT mass analysers, operating in selected ion monitoring (SIM) and in multiple reaction monitoring (MRM) modes, respectively. The proposed new method can be applied to the determination of selected pesticides in real samples of fruit juices.