Field persistence studies on pendimethalin residues in onions and soil after herbicide postemergence application in onion cultivation

Field studies were undertaken to evaluate the fate of pendimethalin residues in spring and dry onions, after postemergence application of the herbicide in a clay soil onion planting in central Greece, at rates of 1.32 and 2.0 kg of active ingredient (ai)/ha. Residues were determined with capillary GC-ECD after onion extraction with 2-propanol/toluene and extract cleanup in a AgNO3-coated alumina column; the recovery of pendimethalin from spiked onions was found to be 82-99% and the limit of determination 0.007 mg/kg. Pendimethalin residues were found to decline rapidly, and it was estimated that 7 days after the treatment only half of the initial concentrations remained for both the low recommended dose (LRD) and the high recommended dose (HRD) experiments. In all cases the residues in dry bulb onion were well below the lowest maximum residue limit (MRL) set by European countries, which is 0.05 mg/kg. Residues in spring onions at harvest time were also below this level when treated at the LRD and were only slightly above in case of the HRD. The pendimethalin concentration in planting soil for the investigated period declined with half-lives of 37 and 39 days for the LRD and the HRD experiments, respectively

Rapid gas chromatographic method for the determination of famoxadone, trifloxystrobin and fenhexamid residues in tomato, grapeand wine samples

Trifloxystrobin, fenhexamid and famoxadone belong to the generation of fungicides acting against a broad spectrum of fungi and widely used in Integrated Pest Management strategies in different agricultural crops but mainly in viticulture. In the present work, a gas chromatographic (GC) method for their determination was developed and validated on tomato, grape and wine matrices. The method was based on a simple one step liquid-liquid microextraction with cyclohexane/dichloromethane (9 + 1, v/v) and determination of fungicides by gas chromatography with nitrogen phosphorous (NP-) and electron capture (EC-) detection, and ion trap mass spectrometry (ITMS) for confirmation. The method was validated by recovery experiments, assessment of matrix effect and calculation of the associated uncertainty. Recoveries for GC-NPD and GC-ECD were found in the range of 81-102% with RSD <12%, while matrix-matched calibration solutions were imposed for quantification. LOQs ranged from 0.005 to 0.05 mg/kg and 0.01 to 0. 10 mg/kg for the GC-ECD and GC-NPD, respectively, depending on the sensitivity of each compound with trifloxystrobin being the most sensitive. The expanded uncertainty, calculated for a sample concentration of 0. 10 mg/kg, ranged from 4.8 to 13% for the GC-ECD and from 5.4 to 29% for the GC-NPD. The concentration levels for famoxadone residues found in tomato and grape samples from field experiments were clearly below the EU established MRL values, thus causing no problems in terms of food safety. (C) 2006 Elsevier B.V. All rights reserved

Evaluation of teflubenzuron residue levels in grapes exposed to field treatments and in the must and wine produced from them

Dissipation of benzoylurea insecticide teflubenzuron in grapes exposed to field treatments was evaluated. Vines of a white grape vineyard located in central Greece were sprayed twice, at a 28-day interval, with a commercial formulation of the insecticide at 12 g of active ingredient/100 L. Residues were determined by HPLC diode array detection, after ethyl acetate extraction and cleanup on silica phase cartridges, with a detection limit of 0.095 mg/kg. Under field conditions teflubenzuron residues in grapes were found to be very stable with no significant reduction for the whole experimental period of 49 days. However, residues were slightly lower than the maximum residue limits set by individual countries. The fate of teflubenzuron during the vinification process was also studied. Residues were found to be transferred completely into the must but, due to their high affinity for the suspended matter, were removed by similar to 98%; thus, very low concentrations were detected in the produced wine. Among various clarifying agents studied, charcoal was the only one found to be effective for removing teflubenzuron residues from wine

High-performance liquid chromatographic determination of benzoylurea insecticides residues in grapes and wine using liquid and solid-phase extraction

A method for the determination of the benzoylurea insecticides diflubenzuron, triflumuron, teflubenzuron, lufenuron and flufenoxuron in grapes and wine by HPLC has been developed and validated. Grape samples (50 g) were homogenized and extracted with ethyl acetate-sodium sulfate and further cleaned-up by solid-phase extraction on silica sorbent. Wine samples (10 ml) diluted with water (1:3) were solid-phase extracted on an octadecyl sorbent using methanol as the eluent. The pesticides were separated on a reversed-phase octadecyl narrow-bore column by gradient elution and the residues were determined with a UV diode array detector. The calibration plots were linear over the range 0.05-5 mu g/ml. Recoveries of benzoylurea pesticides from spiked grapes (0.02-2.0 mg/kg) and wine (0.01-0.2 mg/l) were 85.8-101.6% and 69.1-104.8%, respectively, and the limits of quantification for these insecticides were <0.01 mg/kg for grapes and <0.01 mg/l for wine. The method was applied to the determination of flufenoxuron and teflubenzuron residues in grapes from treated fields and in produced wine. (C) 1999 Elsevier Science B.V. All rights reserved

Determination of benzoylurea insecticides in apples and pears by solid-phase extraction cleanup and liquid chromatography with UV detection

A liquid chromatographic (LC) method was developed and statistically validated for simultaneous determination of 5 benzoylurea insecticides (diflubenzuron, triflumuron, teflubenzuron, flufenoxuron, and lufenuron) in apples and pears. It involves preliminary extraction with ethyl acetate-sodium sulfate and cleanup on silica solid-phase extraction cartridges using dichloromethane-2-propanol (9 + 1) as eluant. The eluate is dried under nitrogen and redissolved in methanol. Benzoylurea insecticides are determined by reversed-phase LC with gradient elution at 42 degrees C and UV diode array detection. Recoveries from samples fortified with the 5 insecticides at 0.02-0.5 mg/kg ranged from 83 to 102% for apples and from 75 to 99% for pears. Relative standard deviations were 0-12%. Limits of detection were 0.01 mg/kg for apples and 0.02 mg/kg for pears

Dissipation of teflubenzuron and triflumuron residues in field-sprayed and cold-stored pears

Dissipation of residues of benzoylurea insecticides teflubenzuron (TFB) and triflumuron (TFM) under field conditions was evaluated on a pear orchard in Greece. Residues were determined by UV-HPLC analysis, with a detection limit of 0.030 mg/kg for both pesticides. TFB residues in pears were found to persist for 2 weeks and decline thereafter with 48% of the initial deposit remaining 42 days after the last application. TFM residues were found to decline following first-order kinetics and with a half-life of 39(+/-7) days. Residues of both pesticides found in pears collected at harvest maturity were lower than the maximum residue limits (MRLs) set by individual countries. Dissipation of TFB and TFM in cold-stored pears was also evaluated. TFB residues were very persistent for the whole storage period, whereas TFM residues did not dissipate for 6 weeks and then showed a constant decline; 7% of the initial concentration remained at the end of the storage period of 29 weeks

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

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