Residues of spiroxamine in grapes following field application and their fate from vine to wine.

Dissipation of the fungicide spiroxamine in grapes of two vine varieties, Roditis and Cabernet Sauvignon, exposed to field treatments was evaluated. Vines of a grape vineyard located in central Greece were sprayed once or twice with a commercial formulation of the fungicide at 30 g a.i./hL. Residues in grapes, must, and wine were determined by gas chromatography/IT-MS after extraction with cyclohexane-dichloromethane (9:1), with a limit of quantitation 0.02 mg/kg in grapes and 0.012 mg/kg in wine. Under field conditions, spiroxamine dissipation on grapes was faster during the first 2 weeks and then slower to the sixth week. About 7 days after application, half of the initial spiroxamine concentration remained on the grapes; the respective proportion at 42 days was about 10%. At 14 and 35 days, residues were lower than 0.44 and 0.22 mg/kg, respectively, values below the maximum residue levels set by the European Union (1 mg/kg). Spiroxamine residues transferred from grapes into the must and through the vinification process into the wine were also studied. Mean transfer factors of 0.26 and 0.55 were found from grapes into wine for the wines obtained without maceration and with maceration, respectively. Residues in wine, prepared from grapes with a spiroxamine content of 0.11-0.20 mg/kg, varied from <0.026 to 0.09 mg/kg. Spiroxamine diastereomer B was found to dissipate slower than diastereomer A in the field as well as during the vinification process.

Determination of spiroxamine residues in grapes, must, and wine by gas chromatography/ion trap-mass spectrometry.

Analytical methodology was developed and validated for the determination of spiroxamine residues in grapes, must, and wine by gas chromatography/ion trap-mass spectrometry (GC/IT-MS). Two extraction procedures were used: the first involved grapes, must, and wine extraction with alkaline cyclohexane-dichloromethane (9 + 1, v/v) solution, and the second grape extraction with acetone, dichloromethane, and petroleum ether. In both procedures, the extract was centrifuged, evaporated to dryness, and reconstituted in cyclohexane or 2,2,4-trimethylpentane-toluene (9 + 1, v/v), respectively. Spiroxamine diastereomers A and B were determined by GC/IT-MS, and a matrix effect was observed in the case of grapes but not in must and wine. Recovery of spiroxamine from fortified samples at 0.02 to 5.0 mg/kg ranged from 78-102% for grapes and must, with relative standard deviation (RSD) <13%; for red and white wines, recoveries ranged from 90 to 101% with RSD <9%. The limit of quantification was 0.02 mg/kg for grapes, must, and wine or 0.10 mg/kg for grapes, depending on the extraction procedure used.

A gas chromatographic determination of residues of eleven insecticides and two metabolites on olive tree leaves.

A gas chromatographic (GC) method was developed and statistically validated for the simultaneous determination of residues of pyrethroid, endosulfan, and organophosphorus insecticides and some of their metabolites on olive tree leaves. Pesticide residues were extracted by static extraction with acetone-dichloromethane. After evaporation of the extract to dryness and redissolution in acetone, the organophosphorus insecticides were determined by GC with nitrogen-phosphorus detection. Another portion of the extract, after solvent change to acetonitrile, was cleaned up on an Alumina-N cartridge and analyzed for insecticides sensitive to electron-capture detection (ECD), i.e., pyrethroids and endosulfan and its metabolite. Recoveries of the organophosphorus insecticides ranged from 80.7 to 93.3% with relative standard deviations (RSDs) of < or = 7.2%; recoveries of the ECD-sensitive insecticides ranged from 71.6 to 89.5% with RSDs of < or = 11.6%. The method was used to analyze 26 samples of olive tree leaves from organic olive groves all over Greece, and the results confirmed the viability of the method for routine analysis. Residues of fenthion and fenthion sulfoxide were found in one and 3 samples, respectively, and their identities were confirmed by GC with mass spectrometry.