286 resultados para organochlorine pesticides
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The promoting activity of the herbicide Diuron was evaluated in a medium-term rat liver carcinogenesis bioassay that uses as endpoint immunohistochemically identified glutathione S-transferase positive (GST-P+) foci. Male Wistar rats were allocated to the following groups: G1 to G6 were initiated for liver carcinogenesis by a single dose of diethylnitrosamine (DEN, 200 mg/kg) while groups G7 and G8 received only 0.9% NaCl (DEN vehicle). From the 2nd week animals were fed a basal diet (G1 and G7) or a diet added with Diuron at 125, 500, 1250, 2500 and 2500 ppm (G2 to G5 and G8, respectively) or 200 ppm Hexaclorobenzene (HCB; G6). The animals were submitted to 70% partial hepatectomy at the 3rd week and sacrificed at the 8th week. The herbicide did not alter ALT or creatinine serum levels. No conspicuous GST-P+ foci development was registered in non-initiated rats fed Diuron at 2500 ppm. While DEN-initiated animals fed Diuron at 1250 or 2500 ppm developed mild centrilobular hypertrophy, DEN-initiated HCB-fed animals showed severe liver centrilobular hypertrophy and significant GST-P+ foci development. These findings indicate that the medium-term assay adopted in this study does not reveal any liver carcinogenesis initiating or promoting potential of Diuron in the rat.
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Oxidative stress generating active oxygen species has been proved to be one of the underlying agents causing tissue injury after the exposure of Eucalyptus (Eucalyptus spp.) plants to a wide variety of stress conditions. The objective of this study was to perform data mining to identify favorable genes and alleles associated with the enzyme systems superoxide dismutase, catalase, peroxidases, and glutathione S-transferase that are related to tolerance for environmental stresses and damage caused by pests, diseases, herbicides, and by weeds themselves. This was undertaken by using the eucalyptus expressed-sequence database (https//forests.esalq.usp.br). The alignment results between amino acid and nucleotide sequences indicated that the studied enzymes were adequately represented in the ESTs database of the FORESTs project.
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A gas chromatography-mass-selective (GC-MS) detection method to determine buprofezin, pyridaben, and tebufenpyrad on the pulp, peel, and whole fruit of clementines is described. The extraction/partition procedure was performed in one step and no cleanup was necessary with the GC-MS in the SIM-mode pesticide determination. Recovery ranged from 75 to 124% with coefficients of variance ranging between 1 and 13%. The limit of determination was 0.01 mg/kg for all pesticides. The field trials showed a similar degradative behavior for all active ingredients (AI), with a great residue decrease during the first week and stability in the second. Just after treatment buprofezin and tebufenpyrad showed lower residues than the maximum residue limit (MRL) fixed in Italy, while pyridaben was below the MRL after a week.
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A competitive enzyme-linked immunosorbent assay (ELISA) method for carbaryl quantitation in crop extracts was validated by liquid chromatography (LC) with diode array detection (DAD). For this purpose, six crops (banana, carrot, green bean, orange, peach and potato) were chosen for recovery and reproducibility studies. The general sample preparation included extraction with methanol followed by liquid-liquid partitioning and clean-up on Celite-charcoal adsorbent column of the vegetable extracts. ELISA samples consisted of a diluted LC extract in assay phosphate buffer (pH 7.5). The potential effect of methanol in these samples was evaluated. It was observed that a maximum content of 10% methanol present in the assay buffer could be tolerated without expressive losses in the ELISA performance. Under these conditions, a IC50 similar to 1.48 mu g l(-1) was obtained. A minimum matrix effect with a 1:50 dilution of the methanolic extracts in assay buffer was noticed, except for green bean samples that inhibited completely the assay. For the vegetable extracts, the ELISA sensitivities varied from 3.9 to 5.7 mu g l(-1), and good recoveries (82-96%) with R.S.D.s ranging from 5.7 to 12.1% were found. An excellent correlation between the LC-DAD and ELISA techniques was obtained. The confirmation of the carbaryl in less concentrated samples was achieved by LC-mass spectrometry interfaced with atmospheric pressure chemical ionisation. The [M + H](+)= 202 and [M + H-57](+)=145 ions, equivalent to the protonated molecular and l-naphthol ions, respectively, were used to carbaryl identification in these samples. (C) 1998 Elsevier B.V. B.V. All rights reserved.
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An analytical method for the determination of aldicarb, and its two major metabolites, aldicarb sulfoxide and aldicarb sulfone in fruits and vegetables is described. Briefly the method consisted of the use of a methanolic extraction, liquid-liquid extraction followed by solid-phase extraction clean-up. Afterwards, the final extract is analyzed by liquid chromatography-atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS). The specific fragment ion corresponding to [M-74](+) and the protonated molecular [M+K](+) ion were used for the unequivocal determination of aldicarb and its two major metabolites. The analytical performance of the proposed method and the results achieved were compared with those obtained using the common analytical method involving LC with post-column fluorescence detection (FL). The limits of detection varied between 0.2 and 1.3 ng but under LC-FL were slightly lower than when using LC-APCI-MS. However both methods permitted one to achieve the desired sensitivity for analyzing aldicarb and its metabolites in vegetables. The method developed in this work was applied to the trace determination of aldicarb and its metabolites in crop and orange extracts. (C) 2000 Elsevier B.V. B.V. All rights reserved.
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Residues of three pesticides (dimethoate, parathion, and pyrazophos) in two artichoke cultivars, Masedu and Spinoso sardo, were investigated. The amount of pesticides in artichokes was greatly affected by the head shape. In the case of the calix-shaped Masedu artichoke, the residues in whole heads at commercial ripening were on average about twice higher than those of the pagoda-shaped Spinoso sardo artichoke. In the heart this ratio was 4 to 42 times greater. Residue decay rates were very fast, mainly owing to the dilution effect due to head growth.
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A simultaneous method for the trace determination of acidic, neutral herbicides and their transformation products in estuarine waters has been developed through an on-line solid-phase extraction method followed by liquid chromatography with diode array and mass spectrometric detection. An atmospheric pressure chemical ionization (APCI) interface was used in the negative ionization mode after optimization of the main APCI parameters. Limits of detection ranged from 0.1 to 0.02 ng/ml for 50 mi of acidified estuarine waters preconcentrated into polymeric precolumns and using time-scheduled selected ion monitoring mode. Two degradation products of the acidic herbicides (4-chloro-2-methylphenol and 2,4-dichlorophenol) did not show good signal response using APCI-MS at the concentration studied due to the higher fragmentor voltage needed for their determination For molinate and the major degradation product of propanil, 3,4-dichloroaniline, positive ion mode was needed for APCI-MS detection. The proposed method was applied to the determination of herbicides in drainage waters from rice fields of the Delta del Ebro (Spain). During the S-month monitoring of the herbicides, 8-hydroxybentazone and 4-chloro-2-methylphenoxyacetic acid were successively found in those samples. (C) 2000 Elsevier B.V. B.V. All rights reserved.
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After treatment lipophilic pesticides tend to diffuse by penetrating the epicuticular wax of fruits. In this way, solar radiation only acts on pesticide molecules after passing through the waxes. The effect of epicuticular waxes of three fruits (orange, nectarine, and olive) on the photodegradation of fenthion was studied. The waxes affected the photodegradation process of fenthion. The decay rate of fenthion increased in the presence of orange and nectarine waxes, while it decreased when olive wax was used. In all waxes, the transformation of fenthion produced mainly fenthion sulfoxide and low amounts of fenthion sulfone. In orange wax, 50% of the initial fenthion was transformed into unknown compounds. In nectarine wax, fenthion was degraded stoichiometrically into fenthion sulfoxide and fenthion sulfone. In olive wax, the photodegradation of fenthion yielded about 80% of fenthion sulfoxide.
Environmental Behaviour of Metolachlor and Diuron in a Tropical Soil in the Central Region of Brazil
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The environmental behaviour of metolachlor and diuron was studied in the Central-western region of Brazil, by means of a field study where six experimental plots were installed. The soil was classified as a Latosol, and the soil horizons were characterized. Sorption of metolachlor and diuron was evaluated in laboratory batch experiments. Metolachlor and diuron were applied to the experimental plots on uncultivated soil in October 2003. From this date to March 2004, the following processes were studied: leaching, runoff and dissipation in top soil. K (oc) of metolachlor varied from 179 to 264 mL g(-1) in the soil horizons. K (oc) of diuron in the Ap horizon was 917 mL g(-1), decreasing significantly in the deeper horizons. Field dissipation half-lives of metolachlor and diuron were 18 and 15 days, respectively. In percolated water, metolachlor was detected in concentrations ranging from 0.02 to 2.84 mu g L-1. In runoff water and sediment, metolachlor was detected in decreasing concentrations throughout the period of study. Losses of 0.02% and 0.54% of the applied amount by leaching and runoff, respectively, were observed confirming the high mobility of this herbicide in the environment. In percolated water, diuron was detected with low frequency but in relatively high concentrations (up to 6.29 mu g L-1). In runoff water and soil, diuron was detected in decreasing concentrations until 70 days after application, totalizing 13.9% during the whole sampling period. These results show the importance of practices to reduce runoff avoiding surface water contamination by these pesticides, particularly diuron.
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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With the advance of agriculture, there was consequent rising in environment degradation. Therefore, It is interesting the use of plants which have in their chemical composition substances capable of helping in the control of weeds to minimize the use of pesticides. Hence, the objective of this paper was to evaluate solutions of leucena extract on weeds that are frequent on soybean crop. The treatments were leucena extracts at 0, 20, 40, 60, 80 and 100% at room temperature water and water heated to 80 degrees C. The extracts were obtained by crushing 200g of leucena leaves and mixing them with one liter of distilled water with the help of a blender. Seeds were kept in B.O.D. at a temperature of 25 degrees C, with a photoperiod of 12 hours of light. Evaluations were done oil a daily basis, from the first to the last day of the experiment, varying according to the species. Results show a negative interference of the extracts, both hot and cold, in the root length of Ipomoea grandifolia, in the percentage of germination and in the root length of Arrowleaf sida and Hair beggarticks. There was no negative interference in the analyzed parameters for soybean seeds. Thus, the results indicate allelopatic potential of Leucaena leuucocephala as an alternative for the management of weeds without interfering on the development of the soybean crop.
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The effects of the herbicides atrazine, 2,4-D, glyphosate (direct and rodeo) and trifluralin were determined on the growth and death of fronds of the aquatic macrophytes Spirodela punctata (G.F.W. Meyer) Thompson and Salvinia minima Baker, through three series of concentrations of each herbicide in climatic chamber (3000 lux, 12/12 hours photoperiod, temperature 23 ± 1°C). After seven days, the concentrations of series 1 (0.025, 0.125, 0.625 and 3.125 mg.L -1) inhibited the growth of Salvinia minima. In Spirodela punctata, only the herbicides rodeo and trifluralin caused growth inhibition. These concentrations did not caused death of fronds in the species. The concentrations of series 2 (40, 60, 80 and 100 mg.L -1) of the herbicides 2,4-D, direct e trifluralin decreased growth of Salvinia minima; death of fronds was caused by 2,4-D and trifluralin to Salvinia minima, and by direct and trifluralin to Spirodela punctata. For the series 3 (200, 400, 600, 800 and 1000 mg.L -1), the herbicide 2,4-D caused growth decrease of both species. The herbicides rodeo and trifluralin showed to be the most lethal for both species. The herbicide atrazine caused death of fronds in Spirodela punctata.
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The determination of 2,4-D (2,4-dichlorophenoxyacetic acid) and Dicamba (2-methoxy-3,6-dichlorobenzoic acid) residues in sugar cane, rice and corn was performed by a supercritical fluid extraction (SFE) method using CO2/acetone as extraction mix and an SFE apparatus developed in our laboratory. The extracts were cleaned up after extraction by both liquid- liquid partition and a Florisil column. Micellar electrokinetic capillary chromatography (MEKC) coupled with ultraviolet on-column detection was used for the analysis of these pesticides. The detection limits were improved by the preparation of a special detection cell with an increased pathlength that gave detection limits of ca. 0.6 pg for 2,4-D and Dicamba. Our results demonstrated that capillary electrophoresis can be a powerful new analytical tool for pesticide residue analysis.