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The localization of procymidone fungicide residue in cucumbers was investigated by mass spectrometry imaging (MSI). Cucumbers were grown, harvested, and then divided into two groups that were either sprayed or not sprayed with procymidone. The content of procymidone in the cucumbers was quantitatively determined by chromatographic techniques. Subsequently, the spatial distribution of procymidone was imaged by MSI. Procymidone reached the central part of the cucumbers following spraying compared with the control.

A metabolite of procymidone, hydroxylated-PCM, causes rat-specific developmental toxicity due to higher exposure to it in rats than in rabbits or monkeys. When procymidone was administered to chimeric mice with rat or human hepatocytes, the plasma level of hydroxylated-PCM was higher than that of procymidone in rat chimeric mice, and the metabolic profile of procymidone in intact rats was well reproduced in rat chimeric mice. In human chimeric mice, the plasma level of hydroxylated-PCM was less, resulting in a much lower exposure. The main excretion route of hydroxylated-PCM-glucuronide was bile (the point that hydroxylated-PCM enters the enterohepatic circulation) in rat chimeric mice, and urine in human chimeric mice. These data suggest that humans, in contrast to rats, extensively form the glucuronide and excrete it in urine, as do rabbits and monkeys. Overall, procymidone’s potential for causing teratogenicity in humans must be low compared to that in rats.

A sample preparation method, dispersive liquid-liquid microextraction assisted by an emulsion with low concentration of a surfactant in water and dispersed solvent coupled with gas chromatography-mass spectrometry, was developed for the analysis of the fungicides cyprodinil, procymidone, fludioxonil, flusilazole, benalaxyl, and tebuconazole in wine. A microsyringe was used to withdraw and discharge a mixture of extraction solvent and 240 μL of an aqueous solution of Triton X-100 (the dispersed agent) four times within 10 s to form a cloudy emulsion in the syringe. This emulsion was then injected into a 5 mL wine sample spiked with all of the above fungicides. The total extraction time was approximately 0.5 min. Under optimum conditions using 1-octanol (12 μL) as extraction solvent, the linear range of the method in analysis of all six fungicides was 0.05-100 μg L(-1), and the limit of detection ranged from 0.013 to 0.155 μg L(-1). The absolute recoveries (n = 3) and relative recoveries (n = 3) were 30-83 and 81-108% for white wine at 0.5, 5, and 5 μg L(-1), and 30-92 and 81-110% for red wine, respectively. The intraday (n = 7) and interday (n = 6) relative standard deviations ranged from 4.4 to 8.8% and from 4.3 to 11.2% at 0.5 μg L(-1), respectively. The method achieved high enrichment factors. It is an alternative sample preparation technique with good performance.

The dissipation of six pesticides (carbendazim, thiabendazole, procymidone, bifenthrin, λ-cyhalothrin, and β-cyfluthrin) in shiitakes from cultivation to postharvest drying process was investigated, and the dietary exposure risk was estimated thereafter. The field trial study indicates that the half-lives of carbendazim, thiabendazole, and procymidone were much shorter than those of bifenthrin, λ-cyhalothrin, and β-cyfluthrin. Furthermore, the effects of two drying processes on the residues and processing factors (PFs) were investigated. The results showed that hot-air drying resulted in higher residues than sunlight exposure drying. Both drying processes led to pesticide residue concentration (with PF1), except for thiabendazole upon sunlight exposure treatment. The estimated daily intakes (EDIs) ranged from 0.06% of the acceptable daily intake (ADI) for thiabendazole to 42.43% of the ADI for procymidone. The results show that the six pesticide residues in dried shiitakes are still within acceptable levels for human consumption on the basis of a dietary risk assessment.

The effect of red wine malolactic fermentation on the fate of seven fungicides (carbendazim, chlorothalonil, fenarimol, metalaxyl, oxadixyl, procymidone, and triadimenol) and three insecticides (carbaryl, chlorpyrifos, and dicofol) was investigated. After malolactic fermentation using Oenococcus oeni, which simulated common Australian enological conditions, the concentrations of the active compounds chlorpyrifos and dicofol were the most significantly reduced, whereas the concentrations of chlorothalonil and procymidone diminished only slightly. The effect of these pesticides on the activity of the bacteria was also studied. Dicofol had a major inhibitory effect on the catabolism of malic acid, whereas chlorothalonil, chlorpyrifos, and fenarimol had only a minor effect.

In this review the results obtained in the 1990s from research on the behavior of pesticide residues on grapes, from treatment to harvest, and their fate in drying, wine-making, and alcoholic beverage processing are reported. The fungicide residues on grapes (cyproconazole, hexaconazole, kresoxim-methyl, myclobutanil, penconazole, tetraconazole, and triadimenol), the application rates of which were of a few tens of grams per hectare, were very low after treatment and were not detectable at harvest. Pyrimethanil residues were constant up to harvest, whereas fluazinam, cyprodinil, mepanipyrim, azoxystrobin, and fludioxonil showed different disappearance rates (t(1/2) = 4.3, 12, 12.8, 15.2, and 24 days, respectively). The decay rate of the organophosphorus insecticides was very fast with t(1/2) ranging between 0.97 and 3.84 days. The drying process determined a fruit concentration of 4 times. Despite this, the residue levels of benalaxyl, phosalone, metalaxyl, and procymidone on sun-dried grapes equalled those on the fresh grape, whereas they were higher for iprodione (1.6 times) and lower for vinclozolin and dimethoate (one-third and one-fifth, respectively). In the oven-drying process, benalaxyl, metalaxyl, and vinclozolin showed the same residue value in the fresh and dried fruit, whereas iprodione and procymidone resides were lower in raisins than in the fresh fruit. The wine-making process begins with the pressing of grapes. From this moment onward, because the pesticide on the grape surface comes into contact with the must, it is in a biphasic system, made up of a liquid phase (the must) and a solid phase (cake and lees), and will be apportioned between the two phases. The new fungicides have shown no effect on alcoholic or malolactic fermentation. In some cases the presence of pesticides has also stimulated the yeasts, especially Kloeckera apiculata, to produce more alcohol. After fermentation, pesticide residues in wine were always smaller than those on the grapes and in the must, except for those pesticides that did not have a preferential partition between liquid and solid phase (azoxystrobin, dimethoate, and pyrimethanil) and were present in wine at the same concentration as on the grapes. In some cases (mepanipyrim, fluazinam, and chlorpyrifos) no detectable residues were found in the wines at the end of fermentation. From a comparison of residues in wine obtained by vinification with and without skins, it can be seen that their values were generally not different. Among the clarifying substances commonly used in wine (bentonite, charcoal, gelatin, polyvinylpolypyrrolidone, potassium caseinate, and colloidal silicon dioxide), charcoal allowed the complete elimination of most pesticides, especially at low levels, whereas the other clarifying substances were ineffective. Wine and its byproducts (cake and lees) are used in the industry to produce alcohol and alcoholic beverages. Fenthion, quinalphos, and vinclozolin pass into the distillate from the lees only if present at very high concentrations, but with a very low transfer percantage (2, 1, and 0.1%, respectively). No residue passed from the cake into the distillate, whereas fenthion and vinclozolin pass from the wine, but only at low transfer percentages (13 and 5%, respectively).

Recent legislation in the European Union requires regulators of member states to carry out risk assessments using data for actual or potential operator exposure, or estimates of exposure from models. However, the existing models have few datasets from studies carried out on greenhouse or indoor crops, particularly in southern Europe. In this study potential dermal and inhalatory exposures were measured in two trials in Italian greenhouses. The total potential dermal operator exposure of the applicator, measured with a whole-body passive dosimetry method, was 15.4 and 37.1 mL/h of the diluted pesticide mixture. The majority of the contamination was on the hands and on the lower part of the coverall. Approximately 0. 003% of the active ingredient (ai) applied to the crop area contaminated the coverall worn by the operator. The potential dermal exposure during the mixing and loading phase accounted for 6-8% of the total potential dermal exposure during the whole process. Inhalation exposure accounted for only 0.05-0.07% of the total potential operator exposure. Model predictions of the potential operator exposure using a modified version of the German model overestimate the mixing-loading exposure while underestimating the application exposure. These data are evidence that the estimation coefficient set for hand-held application to ornamental and horticultural crops may be inadequate for the agronomic conditions of southern Europe.

The fate of three fungicides (dichlofluanid, procymidone, and iprodione) applied under field conditions was studied during strawberry processing to juice, wine, and jam. An untreated control was compared to raw material treated with fungicides according to recommended doses and to a sample with 6-fold higher application rates. The highest residue values were found in the pomace after pressing. Residue values in readily produced juices and fruit wines were very low and did not exceed legally required maximum residue levels. Generally, processing steps such as pressing and clarification diminished fungicide residues from 50 to 100%. If the whole fruit is processed, as in fruit preparations or jam, the residue levels remain higher due to missing processing steps.

Iprodione, procymidone, and vinclozolin are dicarboximidic fungicides commonly used in preharvest viticulture treatments to prevent gray mold (Botrytis) and other fungal diseases. The aim of this study is to determine the degradation of these fungicides in five vineyard soils of Penedes after three treatments at 100-day intervals with commercial formulations under laboratory conditions. The analyses were conducted over a period beginning the same day of each treatment and lasting for up to 77 days afterward. In these conditions, the degradation rates of all three fungicides increased with the number of applications. Times elapsed to 90% degradation of iprodione, procymidone, and vinclozolin following first, second, and third treatments were about 35, 21, and 7 days, respectively. No residues were found at 77 days. These results showed that the residual levels of these three fungicides in soils decreased with time. Keywords: Iprodione; procymidone; vinclozolin; dicarboximidic fungicides; residues; soils

The fate of eight fungicides (benalaxyl, fenarimol, iprodione, metalaxyl, myclobutanil, procymidone, triadimefon, and vinclozolin) and five insecticides (dimethoate, fenthion, methidathion, parathi...

The absorption of some organochlorine and organophosphorus pesticides on low-density polyethylene (LDPE) films used as agricultural soil covers is studied. Four different types of LDPE films (black, normal, thermic, and extra low density) and a copolymer of ethylene and vinyl acetate (EVA) were selected to do the kinetic study. Temperature ranged from 24 to 50 °C, and contact time between plastic films and a standard solution of pesticides in aqueous phase varied between 3 and 20 days. As pesticides the following were studied: dicloran, malathion, procymidone, folpet, α- and β-endosulfan, chlorothalonil, chlorpyriphos, and methylchlorpyriphos. Kinetic equations of first order were obtained in all cases having kinetic constants from 6.5 × 10-4 to 1 × 10-4 days-1. Most of the pesticides studied were completely absorbed on the plastic films after 15 days of contact time. No degradation of pesticides was observed once they were absorbed on the plastic. Both the absorption process and the capacity of absorpti...

Temperature-gradient capillary gas chromatography-mass spectrometry with selected at m/z 124, 187, and 283 and isocratic reversed-phase high-performance liquid chromatography with ultraviolet (UV) detection at 207 nm were compared for the determination of residual levels of procymidone in wine. Previous extraction was carried out using Sep-Pak C18 cartridges. Calibration plots were linear from 1 to 50 ppm of procymidone. Method detection limits for GC-MS and HPLC-UV were 6 and 10 ppb (w/v), respectively, and percent recoveries were 94.7 +/- 5.7% and 96.9 +/- 4.3%. The methods do not give statistically different values, but GC-MS has the advantage of confirming the identity of procymidone, thus increasing the reliability of the residual analysis.

To explore new potential fungicides, a series of novel compounds, including 11 2-oxocycloalkylsulfonamide (3) and 21 2-hydroxycycloalkylsulfonamide (4) derivatives, were synthesized and their structures were confirmed by (1)H nuclear magnetic resonance (NMR), infrared (IR), and elemental analysis. The results of the bioassay showed that the compounds 3 and 4 possessed excellent fungicidal activity against Botrytis cinerea Pers. both in vitro and in vivo. The fungicidal activity of the compounds with 7- or 8-membered rings is better than those with 5-, 6-, or 12-membered rings. According to the results of the mycelium growth rate test, the EC50 values of the compounds 3C, 4C, 3D, and 4D were 0.80, 0.85, 1.22, and 1.09 μg/mL, respectively, and similar to or better than commercial fungicide procymidone. The bioassay results of spore germination indicated that most of the compounds exhibited obvious inhibitory effects against B. cinerea and the inhibition rates of 2-oxocycloalkylsulfonamides were higher than 2-hydroxycycloalkylsulfonamides, among them. The EC50 values of compounds 3A, 3B17, 3E, and 4A were 4.21, 4.21 3.24, and 5.29 μg/mL, respectively. Those compounds containing 5- or 6-membered rings showed better activity than those containing 7-, 8-, or 12-membered rings. Furthermore, the results of the pot culture test showed that almost all of the compounds had effective control activity in vivo and 2-hydroxycycloalkylsulfonamides were obviously superior to 2-oxocycloalkylsulfonamides. The compounds 3E, 4C and 4D presented higher control efficacy than procymidone and pyrimethanil against gray mold disease on cucumber plants.

PCM-CH 2 OH [N-(3,5-dichlorophenyl)-1-hydroxymethyl-2-methylcyclopropane-1,2-dicarboximide] and PA-CH 2 OH [2-carboxyl-N-(3,5-dichlorophenyl)-1-hydroxymethyl-2-methylcyclopropane-1-carboxamide] are metabolites of the fungicide procymidone [N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide] in rat. The distribution and metabolism of PCM-CH 2 OH and PA-CH 2 OH were here clarified by analyzing plasma and tissues (liver, kidney, heart, lung, spleen and ovary) of female rats after single subcutaneous administration of [phenyl- 14 C]PCM-CH 2 OH and [phenyl- 14 C]PA-CH 2 OH at 62.5 mg/kg, respectively. In both rats dosed with PCM-CH 2 OH and PA-CH 2 OH, the radioactivity was similarly distributed into plasma and tissues, and PA-CH 2 OH was detected as the main metabolite in plasma, whereas PCM-CH 2 OH predominated in tissues except for kidney at 1 h after administration of PA-CH 2 OH. Furthermore, the cyclization ratio [PCM-CH 2 OH/(PCM-CH 2 OH + PA-CH 2 OH)] increased in tissues of PA-CH 2 OH dosed rats with passage of time. Both procymidone and PCM-CH 2 OH have convertible conformations (closed and open ring forms), so influence of pH conditions to their conversion was examined. Both compounds demonstrated closed rings under acidic conditions, and open rings under alkaline conditions. Generally, intracellar pH is kept at approximately neutral, and extracellular pH is kept at 0.6-0.7 units higher in all the animal species, so that our in vitro results supported in vivo findings.

The one-dimensional chromatographic flow model PEARL was used to simulate the movement of the insecticide imidacloprid and the fungicide procymidone through a greenhouse soil. The model was parametrized using measured and literature values of soil hydrological parameters. Soil water movement and soil temperature were reasonably well described by the model. The ability of PEARL to simulate the fate of imidacloprid and procymidone following four applications of each compound was evaluated against greenhouse data. Simulated imidacloprid residues in the 0-10 cm layer were in good agreement with measured data. Below 10 cm, the model overestimated imidacloprid remaining following the spray applications, whereas simulated residues following the chemigation applications were in reasonable agreement with measured data. Simulated residues of procymidone in the 0-10 cm layer were in general agreement with measured values. In the 10-20 cm layer, peaks in simulated concentrations occurred later than observed in the greenhouse. Predictions of procymidone residues below 20 cm were poor and underestimated compared to the measured data. For both pesticides, discrepancies between modeled and measured data in the 10-20 cm layer were attributed to the drip irrigation method used in the greenhouse. The model was unable to satisfactorily predict pesticide movement from the soil surface by irrigation water unless the scenario was modified to reflect the localized pattern of water application. Scenario analysis indicated that air boundary layer thickness is a key parameter for readily volatilized pesticides such as procymidone. This is of particular relevance to the greenhouse environment, where the boundary layer thickness may be greater than that in outdoor conditions.

Prunes are processed in three phases: washing, drying, and rehydration, which is performed immediately before packing. The entire drying process was subdivided into six steps. In this paper each of these steps was studied separately in order to determine which could be accountable for residue changes. The studied pesticides were diazinon, bitertanol, iprodione, phosalone, and procymidone. Although the drying process caused a fruit concentration factor of 3, the pesticide residues on the dried fruits were not higher than on the fresh fruits. Phosalone showed the same residue, while the values for procymidone, iprodione, and bitertanol were respectively 0.6, 2.3, and 3.2 times lower. The changes in residue values caused by the different steps were not the same in the different pesticides. Keywords: Prunes; drying process; pesticides; residues

The disappearance of bitertanol, diazinon, iprodione, phosalone, and procymidone on field-sprayed apricots and their fate during sunlight- and oven-drying processes were studied. After treatments in the field, diazinon disappeared completely after a week, whereas the other pesticides at preharvest time showed residues 50% below MRLs. The pesticides decreased with pseudo-first-order kinetics and half-lives ranging from 9.1 to 24.4 days. The sunlight- and oven-drying processes caused the fruit to concentrate by a factor of ∼6 times. Nevertheless, the pesticide residues present in the dried fruit were lower than in the fresh fruit. The residue decreases were higher in the sunlight process than in the oven process. In the former, on average, the residues on the dried fruits were about half those on the fresh fruits, whereas in the latter they were about equal. Keywords: Apricots; drying processes; pesticides; residues

The fate of the residues of benalaxyl, dimethoate, iprodione, metalaxyl, phosalone, procymidone, and vinclozolin in sunlight and oven raisin processing was studied. The drying process caused a fruit concentration factor of 4, while the decreases in residue with the two drying processes were different for the different pesticides. In sunlight-drying the residue level in the raisins was identical to that in the fresh fruits for benalaxyl, metalaxyl, and phosalone, whereas it was higher for iprodione (1.6) and lower for vinclozolin and dimethoate (one-third and one-fifth, respectively). The oven-drying process was preceded by washing, which caused residue decreases for iprodione and procymidone of 57 and 41%, respectively, whereas no decrease was observed in all of the other pesticides. During oven-drying pesticide residues in raisins with respect to fresh fruits showed an increase of 2.7 for phosalone, the same values for benalaxyl, metalaxyl, and procymidone, and lower values for vinclozolin and dimethoate...

Levels of procymidone and propargite residues were studied in an experiment in greenhouse tomatoes. The pesticides were applied according to recommended application procedures in Greece. Tomatoes received six sprayings with procymidone, at 10-day intervals, at rate of application 62.5 g of ai/100 L and a single spraying with propargite, at rate of 60 g of ai/100 L. In separate experimental plots double doses were applied, according to the same scheme. Residues were determined with a simple gas chromatographic method; the recovery of procymidone from tomatoes was 85-104% and of propargite 94-101%; the limits of determination were 0.005 mg/kg for procymidone and 0.01 mg/kg for propargite

The residual amount of nonionized pesticides incorporated to foliage and stem (foliage) and seed (fruit) of crops via root hairs from the water phase was estimated using the uptake models newly including metabolic parameters by which the amount of intact pesticide remaining in crops was considered with its proportion in a transpiration stream. A new parameter was also introduced for the seed model that accounts for the pesticide loss by adsorption to the inner surface of xylem tissue. Validation of the model was conducted using six pesticides with soybean and spinach plants. The ratio of the predicted concentration of pesticide to the measured one was 0.44−1.49 and 0.57−2.93 with foliage and seed models, respectively, showing that these improved models would be effective as a prediction tool. Keywords: Plant uptake model; pesticide; transpiration stream concentration factor; metabolism

Dicarboximide fungicides iprodione, vinclozolin, and procymidone were examined for their capacity to inhibit mycelial growth, to cause cellular leakage, and to cause lipid peroxidation on Botrytis cinerea isolate BC2. All three fungicides effectively inhibited the mycelial growth of the fungi. The IC(50) values were found to be about 2 µM for all three fungicides, indicating that the fungicidal activity of the individual fungicides was almost the same. The fungicides caused significant cellular leakage and lipid peroxidation on the fungi in a concentration-dependent manner. Fungicidal activity of the three individual fungicides on inhibiting mycelial growth of the fungi correlated positively well with both cellular leakage and lipid peroxidation that were caused by the respective fungicides. Positive correlations were also found between the degree of cellular leakage and lipid peroxidation following treatment with the fungicides. Our results support the view that dicarboximide fungicides exert their fungicidal activity mainly through membrane lipid peroxidation and subsequent cellular leakage from the treated fungi.

Residue levels and degradation rates of procymidone residues were studied in green beans grown in a greenhouse. Experiments were planned to also assess the influence of planting density on the behavior of procymidone residues on this type of crop. The study was carried out in four random blocks considering three sub-blocks of different planting densities into each block. Plants were sprayed with Sumisclex 50 WP (1077.5 g of ai/ha) 52 days after the transplantation, and sampling was carried out daily during two different periods of 6 and 5 consecutive days, respectively, around the two harvest days (days 12 and 28 after the treatment). Residue levels of procymidone were determined by using the Luke extraction method and GC-NPD. The average residue levels of procymidone in the overall planting (mean of 12 determinations) were below 2 mg/kg (European maximum residue limit) for all the sampling days, obtaining values of 1.01 +/- 0.55 and 0.37 +/- 0.10 mg/kg, respectively, at the two harvest days. The decline behavior of procymidone residues in the overall plantation and in each block could be described as a pseudo-first-order reaction, obtaining half-life values (t(1/2)) of 10-11 days in all cases. The calculated residue level at the preharvest time (5 days) in the overall plantation was 1.7 mg/kg, but this value in the blocks depended on the block position along the greenhouse and ranged from 2.3 to 0.9 mg/kg. In this work, additional data on the residual behavior of the fungicide pyrazophos in green beans were also obtained.