Comparison of four extraction methods for the determination of fungicide residues in grapes through gas chromatography-mass spectrometry.

Four different methods for simultaneous extraction of vinclozolin, dichlofluanid, penconazole, captan, quinoxyfen, fluquinconazol, boscalid and pyraclostrobin from grapes were optimized and further tested. Microwave assisted extraction (MAE), matrix solid-phase dispersion (MSPD), solid-liquid extraction (SLE) and QuEChERS were compared in terms of their limits of detection and quantification and recoveries. For MAE, MSPD and ethyl acetate extraction, the optimal conditions were optimized by using experimental designs. The analysis was performed using gas chromatography-mass spectrometry in the selected ion monitoring mode (GC-MS, SIM). The proposed methods showed good sensitivity, limits of quantification were lower than MRLs and precision (expressed as relative standard deviation) ranged from 2.9 to 11.1%. The recoveries obtained from MAE, MSPD, SLE and QuEChERS were in the range 78-100%, 66-102%, 58-88% and 68-96%, respectively. In addition, the four methods were compared in two ways: by means of calibration curves obtained with 10 fortified samples in the studied range of concentrations and by the application of statistical tests such as Levene's test (to study variance homogeneity), ANOVA and Tukey's test (in case of Levene's test was satisfactory) for the assessment of the information obtained in the analysis of real samples. Both ways of comparison led to the same results: no differences between the four methods for the extraction of vinclozolin, dichofluanid, quinoxyfen, fluquinconazol and pyraclostrobin were found. However, there were differences for the analysis of captan, boscalid and penconazole.

Response surface optimization for determination of pesticide residues in grapes using MSPD and GC-MS: assessment of global uncertainty.

In this work, a simple and low-cost method based on matrix solid-phase dispersion (MSPD) and gas chromatography to determine eight multi-class pesticides such as vinclozolin, dichlofluanid, penconazol, captan, quinoxyfen, fluquinconazol, boscalid, and pyraclostrobin in grapes is described. Fungicide residues were identified and quantified using gas chromatography-mass spectrometry in selected ion monitoring mode (GC-MS, SIM). The experimental variables that affect the MSPD method, such as the amount of solid phase, solvent nature and elution volume were optimized using an experimental design. The best results were obtained using 0.5 g of grapes, 1.0 g of silica as clean-up sorbent, 1.50 g of C(18) as bonded phase and 10 mL of dichloromethane/ethyl acetate (1:1, v/v) as eluting solvent. Significant matrix effects observed for most of the pesticides tested were eliminated using matrix-matched standards. The pesticide recoveries in grapes samples were better than 80% except for captan. Intra-laboratory precision in terms of Horwitz ratio of the pesticides evaluated was below 0.5, suggesting ruggedness of the method. The quantification limits of the pesticides were in the range of 3.4-8.7 microg kg(-1), which were lower than the maximum residue limits (MRLs) of the pesticides in grapes samples established by the European legislation. Decision limits (CCalpha) and detection capability (CCbeta) have been calculated. The expanded uncertainties at two levels of concentration were <20% for all analytes.

Fate and distribution of pyrimethanil, metalaxyl, dichlofluanid and penconazol fungicides from treated grapes intended for winemaking.

Tempranillo grapes were immersed in solutions of pyrimethanil, metalaxyl, dichlofluanid and penconazol fungicides at different concentrations for several different times. Determinations of the fungicide residues was carried out by GC-NPD, with an additional confirmation by GC-MS. The percentage absorption was determined as well as the distribution between surface, skin and pulp of the grapes. The percentage absorption ranged from 7.2 to 85.5%. These values depended on the time the grapes were in contact with the fungicide solutions. Residues were mainly found in skins, with percentages in skins ranging from 66.3 to 90.3% of total residues. In pulp, these values ranged from 3.5 to 31.0%. The overall methodology was applied to the determination of pyrimethanil in Tempranillo grapes treated with the recommended doses, respecting the safety period. Pyrimethanil residues found in treated grapes were higher in the skin. In grapes collected within the safety period (21 days), the levels found for fungicide residues were below maximum residues levels.

Simultaneous determination of organotin compounds by hydride generation-gas phase molecular absorption spectrometry.

This study describes the determination of ternary mixtures of dimethyltin chloride (DMT), trimethyltin chloride (TMT) and monobutyltin chloride (BT) by hydride generation-gas phase molecular absorption spectrometry and the application of different chemometric methods: principal components regression (PCR) and partial least squares (PLS). The two methods are applied to the absorption spectra of mixtures of DMT, TMT and BT. Two different experimental designs are tested for the mixtures, a triangular design and a central composite design. The models obtained from the triangular design offer the best prediction results. The effects of the number of working wavelengths and the number of factors included in the calibration model is studied and a different behaviour is seen for each compound and calibration model. The methods are applied to the analysis of artificial aqueous samples containing different concentrations of DMT, TMT and BT species. No significant differences are observed between the calibration models investigated.