Comparison of Simple and Rapid Extraction Procedures for the Determination of Pesticide Residues in Fruit Juices by Fast Gas Chromatography–Mass Spectrometry

Abstract

Three sample treatment methods, based on QuEChERS, solid-phase extraction (SPE) and solid-phase microextraction (SPME), were compared and evaluated in order to obtain the best conditions to determine pesticide residues in fruit juice by fast gas chromatography-mass spectrometry (single quadrupole GC-MS). Analysis were performed under selected ion monitoring, acquiring the three most abundant and/or specific ions for each analyte and using their relative intensity ratios as a confirmatory parameter. The 3 methodologies (QuEChERS, SPE and SPME) were validated taking 15 selected pesticides as model compounds, using commercial apple juice. QuEChERS procedure was based on the AOAC Official Method 2007.01, using acetonitrile (containing 1 % acetic acid) as extraction solvent and primary-secondary amine during the dispersive solid-phase extraction. Oasis hydrophilic-lipophilic balance cartridges were used for SPE, and polyacrylate fibers were used for direct immersion SPME procedure. Three isotopically labeled standards were added to the samples before extraction and used as surrogate standards. Validation parameters as recoveries, limits of detection, and limits of quantification (LOQ), as well as matrix effects and sample throughput, were obtained and compared for the three extraction procedures. QuEChERS was considered faster and led to the best quantitative results.In this way, validation was extended to up to 56 pesticides by applying QuEChERS in multi-fruit juice samples, obtaining LOQs ranging from 2 to 20 µg/L for most 2 compounds. Accuracy and precision were evaluated by means of recovery experiments at two concentration levels (10 and 100 µg/L), obtaining recoveries between 70 and 120 % in most cases and relative standard deviations below 15 %.Finally, the QuEChERS method was applied to the analysis of commercial juices, including mango-apple, pineapple, grapefruit and orange.

In Situ Real-Time Tracing of Organophosphorus Pesticides in Apples by Solid-Phase Microextraction with Developed Sampling-Rate Calibration

“…The SPME parameters here were selected mainly to meet the needs of practical application of in vivo SPME for apples where salt cannot be added, temperature cannot be changed, and a long extraction time is not preferred. Nevertheless, the parameters were still close to those reported in some references for these commercial fibers [33,37]. The results shown in Figure 3 indicated that the overcoated fiber was infinitely superior to the other fibers.…”

“…Up to now, DI-SPME for pesticide residual investigation in apples has been rarely reported. Cherta et al performed DI-SPME in commercial apple juice after dilution with a commercial polyacrylate (PA) fiber [33]. No significant differences or signal enhancements were observed between spiked water and spiked juice samples after 4-fold dilution with deionized water, indicating that commercial apple juice is much less complex than fresh natural apple pulp.…”

Application of gas and liquid chromatography coupled to time‐of‐flight mass spectrometry in pesticides: Multiresidue analysis

“…Gas chromatography coupled with mass spectrometry is the most commonly applied and established technique for determination of volatile and semi‐volatile analytes of low medium polarity in water and foods. Different types of MS analyzers have been applied for this goal, such as single‐quadrupole, TOF, ion trap and triple quadrupole; however, the two latter can work under tandem MS mode (Cherta, Beltran, Pitarch, & Hernández, ; Hayward, Wong, & Park, ; Lambropoulou, ; Notardonato, Avino, Cinelli, & Russo, ; Ziarrusta, Olivares, Delgado, Zuloaga, & Etxebarria, ).…”

Binary–solvent–based ionic–liquid–assisted surfactant‐enhanced emulsification microextraction for the determination of four fungicides in apple juice and apple vinegar

“…Pesticide residues can penetrate into plant tissues and remain in agricultural commodity after they are applied to crops, even after being washed, processed and prepared, and may result in adverse consequences to the human health . As fungicides are widely used in preharvest and postharvest treatments to control fungal diseases of fruits, the residues may appear in processed products such as fruit juices, which are widely consumed . Previous studies reported that fungicides such as azoxystrobin and pyrimethanil could remain in grape products after physicochemical and biological processes and become a significant route of human exposure .…”

“…Pesticide residues can penetrate into plant tissues and remain in agricultural commodity after they are applied to crops, even after being washed, processed and prepared, and may result in adverse consequences to the human health [1]. As fungicides are widely used in preharvest and postharvest treatments to control fungal diseases of fruits, the residues may appear in processed products such as fruit juices, which are widely consumed [2,3]. Previous studies reported that fungicides such as azoxystrobin and pyrimethanil could remain in grape products after physicochemical and biological processes and become Abbreviations: BS-ILASEME, binary-solvent-based ionic-liquid-assisted surfactant-enhanced emulsification microextraction; DLLME, dispersive liquid-liquid microextraction; EF, enrichment factor; [HMIM]PF 6 , 1-hexyl-3-methylimidazolium hexafluorophosphate; LDS-LPME, low-density-solvent-based liquid-phase microextraction; UASEME, ultrasound-assisted emulsification microextraction; VASEME, vortex-assisted emulsification microextraction Conflict of interest: The authors declare no potential conflict of interests.…”