EVALUATION OF THE PERFORMANCE OF A CASTOR-OIL BASED FORMULATION IN LIMITING PESTICIDE RESIDUES IN STRAWBERRY CROPS

A study was made to evaluate the effect of a castor oil-based detergent on strawberry crops treated with different classes of pesticides, namely deltamethrin, folpet, tebuconazole, abamectin and mancozeb, in a controlled environment. Experimental crops of greenhouse strawberries were cultivated in five different ways with control groups using pesticides and castor oil-based detergent. The results showed that the group 2, which was treated with castor oil-based detergent, presented the lowest amount of pesticide residues and the highest quality of fruit produced.

Assessment of the sublethal toxicity of organochlorine pesticide endosulfan in juvenile common carp (Cyprinus carpio)

This study is aimed at evaluating the sublethal effects of endosulfan (EDS) in juvenile common carp (Cyprinus carpio). For this purpose, fish were exposed for 15 days to the technical EDS (95% pure) diluted in dimethyl sulfoxide (DMSO) 0.1% of the total volume in water solution in a semi-static system at sublethal concentration (1 mu g/L). Subsequently, the liver somatic index (LSI) and factor condition (K) were determined. The total cytocrome P450 (CYP), CYP1A isoform, and the ethoxyresorufin-O-deethylase (EROD) activity were determined from the hepatic microsomal fraction as well as the activity of the oxidative stress enzyme system such as superoxide dismutase (SOD), catalase (CAT), glutathione-S-transferase (GST), glutathione peroxidase (GP(X)), glutathione reductase (GR), and glucose-6-phosphate dehydrogenase (G6PDH). Among the parameters assessed, EDS at the sublethal concentration in subchronic exposure caused significant changes in liver somatic indices as well as induction of the phase I biotransformation system and oxidative stress in juvenile common carp (Cyprinus carpio). Thus, it is seen that the use of biochemical biomarkers of environmental contamination in this study proved to be an extremely important tool for detecting the adverse effects of xenobiotics in the aquatic environment, even at low concentration.

Evaluation of the performance of a castor-oil based formulation in limiting pesticide residues in strawberry crops

A study was made to evaluate the effect of a castor oil-based detergent on strawberry crops treated with different classes of pesticides, namely deltamethrin, folpet, tebuconazole, abamectin and mancozeb, in a controlled environment. Experimental crops of greenhouse strawberries were cultivated in five different ways with control groups using pesticides and castor oil-based detergent. The results showed that the group 2, which was treated with castor oil-based detergent, presented the lowest amount of pesticide residues and the highest quality of fruit produced.

Field and laboratory studies to assess the effects of Vertimec (R) 18EC on Daphnia similis

The present study aimed to evaluate the interactions of the pesticide Vertimec (R) 18EC in aquatic ecosystems. In this respect, soil plots were contaminated with Vertimec (R) 18EC at the concentration indicated for strawberry crops (0.125 L of solution m(-2)). After the contamination, torrential rainfall was simulated and the surface runoff was collected and transferred to mesocosm tanks in five treatments, run in triplicate: (1) control-C; (2) runoff from an uncontaminated plot-UR; (3) runoff from the plot contaminated with Vertimec (R) 18EC-CR; (4) direct application of Vertimec (R) 18EC in the water-V and (5) water samples gathered randomly to verify whether there was contamination between the mesocosms-RS. Water samples from these tanks were also submitted to ecotoxicological tests with Daphnia similis and analyses to evaluate the limnological characteristics, in five collection periods over 10 days (240 h). Physical and chemical differences were observed in the water samples, mainly related to increased turbidity, suspended solids and nutrients (nitrogen and phosphate forms). Acute toxicity was observed for the direct application treatment for the entire experimental period, and in some periods for the CR treatment (from 48 h to 168 h). The results obtained suggest that the pesticide did not fully degrade during the study period (10 days) in the direct application treatment, demonstrating that the presence of other substances in the commercial formulation contribute to the maintenance of toxicity. This represents a potential risk for aquatic ecosystems in areas adjacent to where the chemical is applied. (C) 2011 Elsevier Inc. All rights reserved.

Characterization of a Toxoneuron nigriceps (Viereck) (Hymenoptera: Braconidae) - derived chitinase and its potential for pest control

The larval endoparasitoid Toxoneuron nigriceps (Viereck) (Hymenoptera: Braconidae) has a toolbox of biological weapons to secure for host colonization and the successful parasitization of its host Heliothis virescens (F.) (Lepidoptera: Noctuidae). The cDNA of a putative chitinase has been previously isolated and initially characterized from teratocytes of this parasitoid among the plethora of molecules available in the venom and calyx fluids injected by females, oral and/or anal secretions released by the parasitoid larvae and/or produced by the expression of genes of the symbiotic associated polydnavirus. This putative chitinase has been initially associated with the host cuticle digestion to allow for parasitoid egression and with the asepsis of the host environment, acting as an antimicrobial. As chitinases are commonly expressed in plants against plant pathogens, the chitinase derived from the teratocytes of T. nigriceps is a potential tool for the development of insect pest control methods based on the disruption of the perithrophic membrane of herbivores. Therefore, we aimed to characterize the activity of the putative chitinase from teratocytes of T. nigriceps (Tnchi) produced using the Escherichia coli expression system and its potential to control H. virescens larvae when expressed into transgenic tobacco plants. The purified E. coli-produced Tnchi protein showed no chitinolitic activity, but was active in binding with colloidal and crystalline chitins in water and with colloidal chitin in buffered solution (pH = 6.74). Transgenic tobacco plants showed no enhanced chitinolitic activity relative to control plants, but survival of three-day old larvae of H. virescens was severely affected when directly fed on transgenic tobacco leaves expressing the recombinant Tnchi protein. Some properties of the Tnchi protein and the potential use of Tnchi-transgenic plants to control plant pests are discussed. (c) 2012 Elsevier Inc. All rights reserved.

Evaluation of comprehensive two-dimensional gas chromatography coupled to rapid scanning quadrupole mass spectrometry for quantitative analysis

Comprehensive two-dimensional gas chromatography (GC x GC) is a powerful technique that provides excellent separation and identification of analytes in highly complex samples with considerable increase in GC peak capacities. However, since second dimension analyses are very fast, detectors with a rapid acquisition rate are required. Over the last years, quite a number of studies have discussed the potential and limitations of the combination GC x GC with a variety of quadrupole mass spectrometers. The present research focuses on the evaluation of qMS effectiveness at a 10,000-amu/s scan speed and 20-Hz scan frequency for the identification (full scan mode acquisition-TIC) and quantification (extracted ion chromatogram) of target pesticide residues in tomato samples. The following MS parameters have been evaluated: number of data points per peak, mass spectrum quality, peak skewing, and sensitivity. The validated proposed GC x GC/qMS method presented satisfactory results in terms of repeatability (coefficient of variation lower than 15%), accuracy (84-117%), and linearity (ranging from 25 to 500 ng/g), while significant enhancement in sensitivity was observed (a factor of around 10) under scan conditions. (C) 2012 Elsevier B.V. All rights reserved.

Unexpected toxicity decrease during photoelectrochemical degradation of atrazine with NaCl

This report shows an unexpected toxicity decrease during atrazine photoelectrodegradation in the presence of NaCl. Atrazine is a pesticide classified as endocrine disruptor occurring in industrial effluents and agricultural wastewaters. We therefore studied the effects of the degradation method, electrochemical and electrochemical photo-assisted, and of the supporting electrolyte, NaCl and Na2SO4, on the residual toxicity of treated atrazine solutions. We also studied the toxicity of treated atrazine solutions using Results show that at initial concentration of 20 mg L-1, atrazine was completely removed in up to 30 min using 10 mA cm(-2) electrolysis in NaCl medium, regardless of the electrochemical method used. The total organic carbon removal by the photo-assisted method was 82% with NaCl and 95% with Na2SO4. The solution toxicity increased during sole electrochemical treatment in NaCl, as expected. However, the toxicity unexpectedly decreased using the photo-assisted method. This finding is a major discovery because electrochemical treatment with NaCl usually leads to the formation of toxic chlorine-containing organic degradation by-products.

Determination of Tetradifon in Brazilian Green Bell Pepper by Differential Pulse Voltammetry

Tetradifon, a potentially carcinogenic and mutagenic pesticide, can contribute to environmental and human contamination when applied to green bell pepper crops. In this context, in this work, a reliable and sensitive method for determination of tetradifon in Brazilian green bell pepper samples involving a differential pulse voltammetry (DPV) technique on a glassy carbon electrode is proposed. The electrochemical behavior of tetradifon as followed by cyclic voltammetry (CV) suggests that its reduction occurs via an irreversible five-electron transfer vs. Ag vertical bar AgCl, KCl 3 M reference electrode. Very well-resolved diffusion controlled voltammetric peaks have been obtained in a supporting electrolyte solution composed of a mixture of 40% dimethylformamide (DMF), 30% methanol, and 30% NaOH 0.3 mol L-1 at -1.43, -1.57, -1.73, -1.88, and -2.05 V. The proposed DPV method has a good linear response in the 3.00 - 10.0 mu mol L-1 range, with a limit of detection (L.O.D) of 0.756 mu mol L-1 and 0.831 mu mol L-1 in the absence and in the presence of the matrix, respectively. Moreover, improved L.O.D results (0.607 mu mol L-1) have been achieved in the absence of DMF from the supporting electrolyte solution. Recovery has been evaluated in five commercial green bell pepper samples, and recovery percentages ranging from 91.0 to 109 have been obtained for tetradifon determinations. The proposed voltammetric method has also been tested for reproducibility, repeatability, and potential interferents, and the results obtained for these three analytical parameters are satisfactory for electroanalytical purposes. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.024207jes] All rights reserved.

Physiological effects of glyphosate over amino acid profile in conventional and transgenic soybean (Glycine max)

This paper compares the responses of conventional and transgenic soybean to glyphosate application in terms of the contents of 17 detectable soluble amino acids in leaves, analyzed by HPLC and fluorescence detection. Glutamate, histidine, asparagine, arginine + alanine, glycine + threonine and isoleucine increased in conventional soybean leaves when compared to transgenic soybean leaves, whereas for other amino acids, no significant differences were recorded. Univariate analysis allowed us to make an approximate differentiation between conventional and transgenic lines, observing the changes of some variables by glyphosate application. In addition, by means of the multivariate analysis, using principal components analysis (PCA), cluster analysis (CA) and linear discriminant analysis (LDA) it was possible to identify and discriminate different groups based on the soybean genetic origin. (C) 2011 Elsevier Inc. All rights reserved.

Efficiency of neem oil nanoformulations to Bemisia tabaci (GENN.) Biotype B (Hemiptera: Aleyrodidae)

The nanotechnology, through encapsulation of active ingredients, has showed an important way to avoid problems with quickly degradation of the pesticide molecules. Thus, neem (Azadirachta indica) oil nanoformulations containing beta-ciclodextrin and poli-epsilon-caprolactone (PCL) were tested as to their control efficiency against eggs and nymphs of Bemisia tabaci (Genn.) biotype B reared in soybean. The Lethal Concentration (LC50) was estimated using a commercial neem oil (Organic Neem (R)) on first-instar nymphs to establish the adequate volume of the nanoformulations per treatment. After that, they were sprayed on eggs and first-instar nymphs in laboratory and greenhouse and on third-instar nymphs in greenhouse. The commercial neem oil and distilled water were used as controls. Egg viability was not affected by any treatment. Among six nanoformulations, only one was efficient against the first-instar nymphs in laboratory conditions. However, its effective period was not increased as expected. In greenhouse, first-instar nymphs were more affected by two nanoformulations which were significantly different of the commercial neem oil - the most effective one. No mortality differences among the formulations in the third-instar test were observed. The nanoformulations were less efficient to control the B. tabaci biotype B nymphs than the commercial neem oil.

Sensitivity of Eisenia andrei (Annelida, Oligochaeta) to a commercial formulation of abamectin in avoidance tests with artificial substrate and natural soil under tropical conditions

Obtaining ecotoxicological data on pesticides in tropical regions is imperative for performing more realistic risk analysis, and avoidance tests have been proposed as a useful, fast and cost-effective tool. Therefore, the present study aimed to evaluate the avoidance behavior of Eisenia andrei to a formulated product, Vertimec(A (R)) 18 EC (a.i abamectin), in tests performed on a reference tropical artificial soil (TAS), to derive ecotoxicological data on tropical conditions, and a natural soil (NS), simulating crop field conditions. In TAS tests an adaptation of the substrate recommended by OECD and ISO protocols was used, with residues of coconut fiber as a source of organic matter. Concentrations of the pesticide on TAS test ranged from 0 to 7 mg abamectin/kg (dry weight-d.w.). In NS tests, earthworms were exposed to samples of soils sprayed in situ with: 0.9 L of Vertimec(A (R)) 18 EC/ha (RD); twice as much this dosage (2RD); and distilled water (Control), respectively, and to 2RD: control dilutions (12.5, 25, 50, 75%). All tests were performed under 25 +/- A 2A degrees C, to simulate tropical conditions, and a 12hL:12hD photoperiod. The organisms avoided contaminated TAS for an EC50,48h = 3.918 mg/kg soil d.w., LOEC = 1.75 mg/kg soil d.w. and NOEC = 0.85 mg/kg soil d.w. No significant avoidance response occurred for any NS test. Abamectin concentrations in NS were rather lower than EC50, 48h and LOEC determined in TAS tests. The results obtained contribute to overcome a lack of ecotoxicological data on pesticides under tropical conditions, but more tests with different soil invertebrates are needed to improve pesticides risk analysis.

TOWARDS NEW BOTANICAL PESTICIDES: THE TOXIC EFFECT OF Eremanthus goyazensis (Asteraceae) LEAVES ESSENTIAL OIL AGAINST Brevipalpus phoenicis (Acari: Tenuipalpidae)

This work reports the chemical characterization of Eremanthus goyzensis essential oil and its toxic effect over Brevipalpus phoenicis. The essential oil displayed a major composition of sesquiterpenes (61.87%) including trans-caryophillene (26.81%) and germacrene-D (13.31%). The fumigation test indicated a promising bioactivity over adult B. phoenicis individuals at 24 h (2.03 mu L/L of air) and 48 h (1.08 mu L/L of air) of exposition. A brief discussion of essential oils composition and their singular role on the toxic effect over B. phoenicis is provided here. Our results may contribute to a new and profitable use of a species of Brazilian flora on agribusiness.

Susceptibility to deltamethrin in the predatory mites Neoseiulus californicus and Phytoseiulus macropilis (Acari: Phytoseiidae) populations in protected ornamental crops in Brazil

Knowledge of inter and intra-specific variation in the susceptibility of natural enemies to pesticides could help to better design integrated pest management strategies. The objective of this research was to evaluate the susceptibility to deltamethrin in populations of the predatory mites Neoseiulus californicus (McGregor) and Phytoseiulus macropilis (Banks) populations collected from protected ornamental crops in Brazil. The susceptibility to deltamethrin was characterized against immature and adult stages of both species. The impact of this insecticide was also measured by estimating the intrinsic rate of increase (r (i)). The immature and adult stages of N. californicus were approximately 3,600 and 3,000-fold more tolerant to deltamethrin than those of P. macropilis. However, high variability in the susceptibility to this insecticide was detected among P. macropilis populations, with resistance ratios of up to 3,500-fold. The selection of deltamethrin-resistant strains of P. macropilis could be exploited in applied biological control programs.

Electrochemical detection of carbamate pesticides in fruit and vegetables with a biosensor based on acetylcholinesterase immobilised on a composite of polyaniline-carbon nanotubes

A sensitive electrochemical acetylcholinesterase (AChE) biosensor was successfully developed on polyaniline (PANI) and multi-walled carbon nanotubes (MWCNTs) core-shell modified glassy carbon electrode (GC), and used to detect carbamate pesticides in fruit and vegetables (apple, broccoli and cabbage). The pesticide biosensors were applied in the detection of carbaryl and methomyl pesticides in food samples using chronoamperometry (CA). The GC/MWCNT/PANI/AChE biosensor exhibited detection limits of 1.4 and 0.95 mu mol L-1, respectively, for carbaryl and methomyl. These detection limits were below the allowable concentrations set by Brazilian regulation standards for the samples in which these pesticides were analysed. Reproducibility and repeatability values of 2.6% and 3.2%, respectively, were obtained in the conventional procedure. The proposed biosensor was successfully applied in the determination of carbamate pesticides in cabbage, broccoli and apple samples without any spiking procedure. The obtained results were in full agreement with those from the HPLC procedure. (C) 2012 Elsevier Ltd. All rights reserved.

Integrated ecological risk assessment of pesticides in tropical ecosystems: A case study with carbofuran in Brazil

The aim of the present study is to contribute an ecologically relevant assessment of the ecotoxicological effects of pesticide applications in agricultural areas in the tropics, using an integrated approach with information gathered from soil and aquatic compartments. Carbofuran, an insecticide/nematicide used widely on sugarcane crops, was selected as a model substance. To evaluate the toxic effects of pesticide spraying for soil biota, as well as the potential indirect effects on aquatic biota resulting from surface runoff and/or leaching, field and laboratory (using a cost-effective simulator of pesticide applications) trials were performed. Standard ecotoxicological tests were performed with soil (Eisenia andrei, Folsomia candida, and Enchytraeus crypticus) and aquatic (Ceriodaphnia silvestrii) organisms, using serial dilutions of soil, eluate, leachate, and runoff samples. Among soil organisms, sensitivity was found to be E. crypticus < E. andrei < F. candida. Among the aqueous extracts, mortality of C. silvestrii was extreme in runoff samples, whereas eluates were by far the least toxic samples. A generally higher toxicity was found in the bioassays performed with samples from the field trial, indicating the need for improvements in the laboratory simulator. However, the tool developed proved to be valuable in evaluating the toxic effects of pesticide spraying in soils and the potential risks for aquatic compartments. Environ. Toxicol. Chem. 2012;31:437-445. (C) 2011 SETAC