Search

The dissipation behaviors and exposure risks of individual and joint application of procymidone and carbendazim in greenhouse strawberries were studied. The initial concentrations were similar after individual or joint applications, while the dissipation half-lives and finial concentrations were significantly different. After joint application, the dissipation half-lives of procymidone and carbendazim were 12.9 and 16.0 days, respectively, which were about 1.8 times higher than those after individual application. Furthermore, the final residues under joint application condition were 1.8–3.5 times higher than those under individual application condition. The joint application decreased the dissipation rates of procymidone or carbendazim in strawberries, and increased the final residue concentrations. The dietary intake risks of procymidone and carbendazim (whether applied individually or jointly) were no higher than 0.12, which were acceptable for human health. This work would shed a light for the guidance of the joint application and risk assessment of the typical fungicides in strawberry.

The effects of alkaline and acidic electrolyzed water (AlEW, AcEW) treatment on the removal of pesticides (phorate, chlorpyrifos, lambda-cyhalothrin, cyfluthrin, procymidone, and chlorothalonil) and texture quality of fresh-cut cabbage, broccoli, and color pepper were investigated. AlEW efficiently removed pesticides from color pepper, whereas AcEW was the optimal treatment for pesticide removal from cabbage and broccoli. AcEW resulted in greater losses of pyrethroid and organophosphates than fungicides, while AlEW was superior for removing fungicides. The best pesticide removal from cabbage (72.28%–91.04%) was achieved by continuous oscillation treatment, while intermittent oscillation for 20 min achieved optimal results for broccoli and color pepper (72.28%–90.11% and 72.24%–88.12%, respectively). No significant deterioration in texture was detected in samples treated with electrolyzed water for 5–25 min. The results suggest that electrolyzed water treatment is effective for removing organophosphate, pyrethroid, and fungicide residues from fresh-cut vegetables while not negatively affecting their texture quality.

With the aim to develop a new gas chromatography-mass spectrometry method to analyze 24 pesticide residues in baby foods at the level imposed by established regulation two simple, rapid and environmental-friendly sample preparation techniques based on QuEChERS (quick, easy, cheap, effective, robust and safe) were compared - QuEChERS with dispersive liquid-liquid microextraction (DLLME) and QuEChERS with dispersive solid-phase extraction (d-SPE). Both sample preparation techniques achieved suitable performance criteria, including selectivity, linearity, acceptable recovery (70-120%) and precision (⩽20%). A higher enrichment factor was observed for DLLME and consequently better limits of detection and quantification were obtained. Nevertheless, d-SPE provided a more effective removal of matrix co-extractives from extracts than DLLME, which contributed to lower matrix effects. Twenty-two commercial fruit-based baby food samples were analyzed by the developed method, being procymidone detected in one sample at a level above the legal limit established by EU.

The dissipation kinetics of a combined use of procymidone and thiamethoxam, and their impact on the biodiversity and pathogen on surface of tomatoes were studied. The half-lives of procymidone and thiamethoxam, used either on their own or in combination with each other, were 2.94 or 3.26 days and 2.41 or 2.67 days, respectively. The residues dropped below the maximum residue limit (MRL) after 7 or 10 days (MRL 2 mg·kg−1 for procymidone), and 10 or 14 days (MRL 0.2 mg·kg−1 for thiamethoxam), respectively. The phylum Bacteroidetes, Cyanobacteria, and Proteobacteria, were dominantly present in all studied samples. The genus Escherichia-Shigella was found and exposed to the dissipation of procymidone (r = −0.9209 for procymidone on its own, and r = −0.8611 for procymidone in combination with thiamethoxam). These results will contribute to establish adequate monitoring of pesticides residues and their incorporation in surface ecology and pathogen management strategies in tomatoes.

An up-and-down-shaker-assisted dispersive liquid–liquid microextraction (UDSA–DLLME) method coupled with gas chromatography–mass spectrometry was developed for the determination of fungicides (cyprodinil, procymidone, fludioxonil, flusilazole, benalaxyl, and tebuconazole) in wine. The developed method requires 11 μL of 1-octanol without the need for dispersive solvents. The total extraction time was approximately 3 min. Under optimum conditions, the linear range of the method was 0.05–100 μg L−1 for all fungicides and the limit of detection was 0.007–0.025 μg L−1. The absolute and relative recoveries were 31–83% and 83–107% for white wine, respectively, and 32–85% and 83–108% for red wine, respectively. The intra-day and inter-day precision were 0.5–7.5% and 0.7–6.1%, respectively. Our developed method had good sensitivity and high extraction efficiency. UDSA–DLLME is a desirable method in terms of performance and speed.

Thermal processing can concentrate residues or convert residues to more toxic metabolites in food. Chinese traditional cooking pays more attention to thermal processing and more vegetables were eaten after thermal processing. In this study, the effect of Chinese traditional cooking (washing, blanching, stir-frying, frying and combined operations) on eight pesticides residues (pyridaben, procymidone, chlorothalonil, difenoconazole, α-cypermethrin, bifenthrin, S-fenvalerate and λ-cyhalothrin) in cowpea which was one of the most important legume crops in China was examined. Result showed washing and blanching could reduce residues with low Kow while stir-frying and frying were more effective to residues with high Kow; stir-frying and frying could concentrate residues with low Kow; the residue levels in oil increased following increasing frying time and frequency especially the residues with high Kow; one metabolite studied in this paper was not detected. Blanching (5 min) followed by stir-frying (3 min) was the most effective combined operation.

A rapid method based on matrix solid-phase dispersion (MSPD) was developed for the determination of pentachloronitrobenzene, pentachloroaniline, methylpentachloro-phenylsulphide and procymidone in ginseng extract using gas chromatography. The optimal conditions selected for MSPD extraction were as follows: after blending 5 mL of aqueous ginseng extract (10%, w/v) with Florisil (10 g), the mixture was passed into a small chromatographic column and extracted twice with 10 mL ethyl acetate–hexane solvent mixture (70:30, v/v) for 15 min in an ultrasonic bath at room temperature. The analytical performance of this method showed MSPD to be efficient, fast, simple and had little or no matrix effect. The method detection limits varied from 0.1 to 0.4 μg/L. Mean recoveries were found in the range of 83.5–97.4% and had a good linear relationship ( r 2 ⩾ 0.9987) with relative standard deviations less than 10%. The proposed method has proved to be a feasible one for the analysis of fungicide residues in ginseng extract.

Pesticides applied to grape vines before harvest may concentrate in the grape seed due to their high oil solubility. Twenty-four samples of grape marc, representing a range of red and white wine grape varieties, were collected and analysed for selected fungicides and insecticides. Fifteen of the 24 samples were matched with insecticide and fungicide application diaries. Residue concentrations of the fungicides, procymidone, iprodione, cyprodinil, fenhexamid, fludioxinil, pyrimethanil and trifloxystrobin, and the insecticides, indoxacarb and tebufenozide, were higher in grape seed oil and grape seed meal than in the fruit and the marc. The relative concentrations were approximately proportional to the octanol to water partition coefficients, log Kow. A range of other fungicides and insecticides were detected but were not significantly concentrated in the oil and seed meal relative to fruit and marc. The presence of pesticide residues in grape seed oil and grape seed meal will impact on the possibility of producing these wine by-products.

Solid-phase microextraction (SPME) in combination with sample stacking micellar electrokinetic chromatography (MEKC) was studied for the simultaneous determination of 11 multi-class pesticides residues (pirimicarb, metalaxyl, pyrimethanil, procymidone, nuarimol, azoxystrobin, tebufenozide, fenarimol, benalaxyl, penconazole and tetradifon) in red wines samples. Pesticide residues present in the samples were preconcentrated by SPME using poly(dimethylsiloxane)/divinylbenzene (PDMS/DVB) fibers and the injection of large sample volumes into the capillary by reversed-electrode polarity stacking mode (REPSM). Validation of the method was carried out. The combination of both preconcentration procedures (SPME and REPSM) allowed the determination of 10 of these pesticides in red wines at concentrations between 0.049 and 1.69 mg/L ( i.e ., levels well below the maximum residue limits (MRLs) allowed for these compounds in wine grapes, except for pirimicarb). Repeatability and accuracy of the SPME-MEKC-DAD method was verified by five consecutive extractions of spiked red wine samples at three levels of concentration. Apparent recovery values were in the range 90–107%. The potential of the method was demonstrated by analyzing multiple homemade red wine samples from the Canary Islands and two commercial samples. Only pyrimethanil, procymidone and azoxystrobin were found in the homemade samples; among them, the pesticide most frequently detected was procymidone.

The aim of this work was to report on a total of 23 fungicides and insecticides residues in 75 green and leafy vegetables (Swiss chards, Spinaches and Lettuces) collected from Ourense (NW Spain) by Spring 2007. The pesticides in the study samples were extracted with acetonitrile; the extracts were then cleaned-up by solid-phase extraction and concentrated before determination by PTV (Programmable Temperature Vaporization Injector) – GC-ITMS. Use of analyte protectants mixtures provided the best results in terms of effective compensation for matrix-induced enhancement effect. Pesticide residues were determined above the maxima residue limits (MRL) in 15 of the 75 analyzed samples, with a total of 18 violations of the MRL (three of the samples did not fulfil with two different pesticide MRL). The highest concentrations of fungicides were found in lettuce (procymidone, 12 mg/kg) and the highest concentrations of insecticides were found in Swiss chard (cypermethrin, 6 mg/kg). More positives for fungicides were detected and at larger concentrations than insecticides, especially for lettuces. Accumulation of pesticides in lettuces is higher than for the other leafy vegetables. The findings of this study pointed to the following recommendation: the need for a monitoring program for residues of iprodione and procymidone, together with cypermethrin, in food crops at the national level.

In this study, controlled applications of captan and procymidone were carried out on tomatoes grown in two different greenhouses at different times. The first group of samples were collected immediately after the application and the second group were collected 14 days later. Additionally, control samples were collected before application. The effects of washing, peeling and predetermined storage period, at 4 °C for 7 and 14 days, on the reduction of residue levels in the plant tissues were investigated in the two groups. A gas chromatographic method using acetone, dichloromethane and petroleum ether as extraction solvents, was used to analyse residual captan and procymidone in tomatoes, with obtained recoveries higher than 83%. Captan and procymidone were determined by gas chromatography-electron capture detection (GC-ECD), using a 5% phenylmethylpolysiloxane-coated fused-silica capillary column. Results showed that waiting for the recommended pre-harvest intervals, indicated on the prospectuses of both pesticides, lowered the residue levels to within acceptable limits. Culinary applications, such as washing and peeling and refrigeration storage, were also effective in reducing the residue levels.

A gas chromatographic method for the determination of endocrine disruptor pesticides (Chlorpyrifos, Penconazole, Procymidone, Iprodione, Bromopropylate and Lambda-Cyhalothrin) in wine samples is described. A general DFG-S19 method for residual pesticide determination in all kind of food stuff was investigated to simplify and adopt for wine samples in this work. Alternative sample preparation routes were elucidated and compared according to their recovery values. Four different separation techniques were tested and the method employing florosil column after a LLE procedure was applied for wine samples with satisfactory recovery ratios (72–97%). The pesticides were extracted from the sample by cyclohexane–ethyl acetate mixture (1:1 v/v) and cleaned up by florosil column. The regression coefficients were at least 0.99 and relative standard deviations were no higher than 16%. Detection limits were in the range of 0.6–2.9 ng/mL and the relative expanded measurement uncertainties were calculated in the 7–22% range.

A method based on ultrasonic extraction and purification by solid phase extraction followed by LC-MS/MS and GC-MS analysis was developed for the determination of genistein, genistin, iprodione, vinclozolin and procymidone in infant powdered formulas. The method was tested for different formulations: milk, soy and hypoallergenic, and was applied to European pooled samples. Spike recoveries ranged from 53.1% to 91.5% and the relative standard deviation values for repeatability ranged from 9.6% to 17.7%, except for iprodione in milk formula (22.3%). None of the fungicides were found in the European pooled formulae, while genistein was found at 9.7μg/g in soy formula and the concentration of genistin, its β-glycosylated form, was respectively 31.4ng/g and 476ng/g in milk and soy formula.