Persistence of insecticide residues in olives and olive oil

The decay rate of six insecticides (azinphos methyl, diazinon, dimethoate, methidathion, parathion methyl, and quinalphos) used to control Dacus oleae was studied. Degradation of pesticides showed pseudo-first-order kinetics with correlation coefficients ranging between -0.936 and -0.998 and half-lives between 4.3 days for dimethoate and 10.5 days for methidathion. Residues in olive oil were greater than on olives, with a maximum concentration factor of 7. Dimethoate was the only pesticide with lower residues in the oil than on the fruits. Olive washing affects pesticide residues ranging from no reduction to a 45% decrease. During 8 months of storage of the olive oil, diazinon, dimethoate, parathion methyl, and quinalphos did not show any remarkable difference, while methidathion and azinphos methyl showed a moderate decrease.

Simplified multiresidue method for the determination of organophosphorus insecticides in olive oil

A simple and rapid method for the determination of 13 organophosphorus insecticides and their metabolites in olive oil by GC is described. The pesticide was extracted from oil with acetonitrile and no cleanup was needed. GC-nitrogen-phosphorus detection response factors of pesticides were affected by solvents and coextractive substances. Pesticides in hexane showed on average higher response factors. Standards were prepared in the residue-free oil extract solubilized in hexane to handle effects of matrix and solvent. The low amount of coextractive substances does not decrease the column efficiency, even after a few hundred analyses. Recovery at three fortification levels (ca. 0.1, 1.0 and 3.0 mg/kg) ranged from 74 to 118%, With coefficients of variation ranging from 1 to 16.

A simplified method for the determination of fenpropathrin residues in fruits

A simple and efficient method is described for the determination of fenpropathrin in oranges, pears, apples and strawberries. The procedure: is based on the extraction of each homogenized fruit sample with hexane:acetone (1:1, v/v) mixture, followed, by a cleanup technique on a column packed with florisil, using a hexane:ethyl ether (7:3, v/v) mixture, and gas chromatographic, analysis with electron capture detection (ECD). The fortification levels (0.5; 1.0; 2.0 mg kg(-1)) were selected according to the maximum residue limits (MRLs) established for fenpropathrin by Brazilian legislation. Mean recoveries from five replicates of fortified fruit samples ranged from 83 % to 98 %, with:coefficients of variation from 1.4 to 13.5 and detection limits varying from 0.1 to 0.2 mg kg(-1).

Multivariate analysis of photo-Fenton degradation of the herbicides tebuthiuron, diuron and 2,4-D

The degradation of herbicides in aqueous solution by photo-Fenton process using ferrioxalate complex (FeOx) as source of Fe2+ was evaluated under blacklight irradiation. The commercial products of the herbicides tebuthiuron, diuron and 2,4-D were used. The multivariate analysis, more precisely, the response surface methodology was applied to evaluate the role of FeOx and hydrogen peroxide concentrations as variables in the degradation process, and in particular, to define the concentration ranges that result in the most efficient degradation of the herbicides. The degradation process was evaluated by the determination of the remaining total organic carbon content (TOC), by monitoring the decrease of the concentrations of the original compounds using HPLC and by the chloride ion release in the case of diuron and 2,4-D. Under optimized conditions, 20min were sufficient to mineralize 93% of TOC from 2,4-D and 90% of diuron, including oxalate. Complete dechlorination of these compounds was achieved after 10 min reaction. It was found that the most recalcitrant herbicide is tebuthiuron, while diuron shows the highest degradability. However, under optimized conditions the initial concentration of tebuthiuron was reduced to less than 15%, while diuron and 2,4-D were reduced to around 2% after only 1 min reaction. Furthermore, it was observed that the ferrioxalate complex plays a more important role than H2O2 in the photodegradation of these herbicides in the ranges of concentrations investigated. (C) 2004 Elsevier Ltd. All rights reserved.

Determination of buprofezin, pyridaben, and tebufenpyrad residues by gas chromatography mass-selective detection in clementine citrus

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.

The characteristics of a test liquid formulation for use in evaluating the performance of handling and metering systems

Injection metering systems are an important option for the development of pesticide application equipment, with advantages relating to minimising the need for disposal of unused pesticide, improving the ease of cleaning and optimising the accuracy of chemical application. For all injection systems, characteristics such as the steady-state accuracy of delivered dose, dose stability and the time response for dose step changes are related to the ability of the system to operate with different chemical formulations. A system designed to inject liquids should be able to accommodate changes in viscosity and density. The aim of this study was to develop a methodology for testing chemical injection systems using liquids with different viscosities. The experimental arrangement simulating applications with injection metering systems used dye and salt solutions as tracers. Tests were conducted to analyse the influence of salt on the characteristics of the water and a viscous solution. Results showed that the salt interfered with the dye stability in the water solution. In tests with a viscous test liquid, the salt was introduced at different steps during the mixing process, providing four different liquids to be analysed in terms of viscosity, density and pH. Some differences in liquid characteristics were found which could influence the performance of the injection systems.

Determination of carbamate residues in crop samples by cholinesterase-based biosensors and chromatographic techniques

An amperometric biosensor based on cholinesterase (ChE) has been used for the determination of selected carbamate insecticides in vegetable samples. The linear range of the biosensor for the N-methylcarbamates (aldicarb, carbaryl, carbofuran, methomyl and propoxur) varied from 5 x 10(-5) to 50 mg kg(-1). Limits of detection were calculated on the basis that the ChE enzymes were 10% inhibited and varied, depending of the combination ChE (as acetyl- or butyrylcholinesterase) vs. inhibitor (pesticide), from 1 x 10(-4) to 3.5 mg kg(-1). The biosensor-based carbamate determination was compared to liquid chromatography/UV methods. Three vegetable samples were spiked with carbofuran and propoxur at 125 mu g kg(-1) followed by conventional procedures. Good correlations were observed for carbofuran in the vegetable extracts (79, 96 and 91% recoveries for potato, carrot and sweet pepper, respectively), whereas for propoxur unsatisfactory results were obtained. Potato and carrot samples were spiked with 10, 50 and 125 mu g kg(-1) carbofuran, followed by direct determination by the amperometric biosensor. The fortified sampler; resulted in very high inhibition values, and recoveries were: 28, 34 and 99% for potato, and 140, 90 and 101% for carrot, respectively, at these three fortification levels. (C) 1998 Elsevier B.V. B.V.

Immobilization of humic acid in nanostructured layer-by-layer films for sensing applications

Humic acids (HAs), naturally occurring biomacromolecules, were incorporated into nanostructured polymeric films using the layer-by-layer (LbL) technique, in which HA layers were alternated with layers of poly(allylamine hydrochloride) (PAH). Atomic force microscopy (AFM) revealed very smooth films, with mean roughness varying from 0.89 to 1.19 nm for films containing 5 and 15 PAH/HA bilayers, respectively. The films displayed electroactivity, with the presence of only one reduction peak at ca. 0.675 V (vs Ag/AgCl). Such a well-defined electroactivity allowed the films to be used as highly sensitive pesticide sensors, with detection of pentachlorophenol (PCP) in solutions at concentrations as low as 10(-9) mol L(-1).

Effect of epicuticular waxes of fruits on the photodegradation of fenthion

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.

EFFECTS OF 2,4-DICHLOROPHENOXYACETIC ACID (2,4-D) ON OPEN-FIELD BEHAVIOR AND NEUROCHEMICAL PARAMETERS OF RATS

The effects of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) on the central nervous system (CNS) were studied in rats. Behavioural and neurochemical studies were performed. Results show that acute and oral administration of dimethylamine 2,4-D was able to decrease locomotion and rearing frequencies and to increase immobility duration of rats observed in an open-field test. Treatment of rats with p-chlorophenylalanine (PCPA) was unable to change rat's open-field behaviour; 5-hydroxytryptophan (5-HTP) administration not only increased locomotion and rearing frequences but also decreased immobility duration. Pretreatment of the rats with PCPA and 5-HTP decreased and increased dimethylamine 2,4-D effects, respectively. The herbicide was not able to change the striatal levels of dopamine and homovanilic acid but decreased the striatal levels of serotonin (5-HT), as observed for the doses of 100 and 200 mg/kg and increased those of 5-hydroxyindoleacetic acid (5-HIAA) as measured after the 200 mg/kg dose treatment. When the levels of serotonin and 5-HIAA were measured at the brain stem level, only those of 5-HIAA were modified, being increased by diethylamine 2,4-D (60; 100 and 200 mg/kg); this increment on 5-HIAA levels was observed even 1 hr after pesticide administration. Further analysis showed that 2,4-D concentrations chromatographycally detected both in serum and brain of the intoxicated animals were dose-dependent, being found as early as 1 hr after the smaller dose of the herbicide used (10 mg/kg). The results suggest that diethylamine 2,4-D modify 5-HT functional activity within the CNS. Thus, the effects of the herbicide on open-field behaviour of rats could be attributed to a direct or indirect pesticide action on serotoninergic systems.

Conventional (MG-BR46 Conquista) and Transgenic (BRS Valiosa RR) Soybeans Have No Mutagenic Effects and May Protect Against Induced-DNA Damage In Vivo

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Effects of prenatal exposure to deltamethrin on forced swimming behavior, motor activity, and striatal dopamine levels in male and female rats

The effects of prenatal exposure of rat pups to 0.08 mg/kg deltamethrin (DTM) on physical, reflex and behavioral developmental parameters, on forced swimming and open-field behaviors, and on striatal monoamine levels at 60 days of age were observed. Maternal and offspring body weight, physical and reflex development were unaffected by the exposure to the pesticide. At 21 days of age, open-field locomotion frequency and immobility duration of male and female offspring were not different between control and exposed animals. However, male rearing frequency was increased in experimental animals. A decreased immobility latency to float and in general activity after the swimming test in male offspring was observed at adult age; no interference was detected in the float duration during the swimming test. In addition, these animals presented higher striatal 3,4-dihydroxyphenylacetic acid (DOPAC) levels without modification in dopamine (DA) levels and an increased DOPAC/DA ratio. These data indicate a higher activity of the dopaminergic system in these animals. Noradrenaline (NA) levels were increased, while MHPG levels were not detectable in the system studied. Serotonin (5-HT) and 5-hydroxyindolacetic acid (5-HIAA) levels, as well as the homovanillic acid (HVA)/DA ratio, were not modified by the exposure to the pesticide. No changes were observed in swimming and open-field behaviors nor were there any changes in striatal monoamines or their metabolites in the female experimental group. In relation to the pesticide formula, the present data showing that prenatal exposure to DTM alters latency to float and the activity of striatal dopaminergic system might reflect a persistent effect of the pesticide on animal motor activity, mainly in males. on the other hand, the decrease in general activity observed in experimental male rats suggests higher levels of emotionality induced by previous exposure to the swimming behavior test in relation to control animals. Data gathered in the present study may be important for the assessment of the safety of pyrethroid insecticides. (C) 2001 Elsevier B.V. All rights reserved.

Effects of a lectin-like protein isolated from Acacia farnesiana seeds on phytopathogenic bacterial strains and root-knot nematode

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Chlorophyll fluorescence as a marker for herbicide mechanisms of action

Photosynthesis is the single most important source of 02 and organic chemical energy necessary to support all non-autotrophic life forms. Plants compartmentalize this elaborate biochemical process within chloroplasts in order to safely harness the power of solar energy and convert it into usable chemical units. Stresses (biotic or abiotic) that challenge the integrity of the plant cell are likely to affect photosynthesis and alter chlorophyll fluorescence. A simple three-step assay was developed to test selected herbicides representative of the known herbicide mechanisms of action and a number of natural phytotoxins to determine their effect on photosynthesis as measured by chlorophyll fluorescence. The most active compounds were those interacting directly with photosynthesis (inhibitors of photosystem I and II), those inhibiting carotenoid synthesis, and those with mechanisms of action generating reactive oxygen species and lipid peroxidation (uncouplers and inhibitors of protoporphyrinogen oxidase). Other active compounds targeted lipids (very-long-chain fatty acid synthase and removal of cuticular waxes). Therefore, induced chlorophyll fluorescence is a good biomarker to help identify certain herbicide modes of action and their dependence on light for bioactivity. Published by Elsevier B.V.

Mutagenic and genotoxic effects of the Atrazine herbicide in Oreochromis niloticus (Perciformes, Cichlidae) detected by the micronuclei test and the comet assay

Atrazine is the triazinic herbicide most found in the rural aquatic environments due to its extensive use and its stability in such places. The mutagenicity and the genotoxicity of different concentrations of the Atrazine herbicide were determinated by the micronucleus test and the comet assay, using Oreochromis niloticus as test-system. The tested concentrations of Atrazine herbicide were 6.25, 12.5 and 25 mu g/L, both for the micronuclei test and for the comet assay. The results showed a significant rate of micronuclei and nuclear abnormalities for all the tested concentrations of Atrazine herbicide. For the comet assay, we also observed results significantly different from the control in 6.25, 12.5 and 25 mu g/L concentrations. Due to these results, we could infer that such herbicide may be dangerous to the lives of those organisms exposed to it. (c) 2007 Elsevier B.V. All rights reserved.