Intraclonal variability in Daphnia acetylcholinesterase activity: The implications for its applicability as a biomarker

The relationship between individual growth and acetylcholinesterase (AChE).activity was evaluated for Daphnia magna. Analysis on the influence of two different culture media on baseline AChE activity was performed with Daphnia similis. The results indicated an inverse relationship between D. magna body length and AChE activity. An increase in total protein, which was not proportional to an increase in the rate of the substrate hydrolysis (Delta absorbance/min), seems to be the reason for this inverse size versus AChE activity relationship. Therefore, toxicants such as phenobarbital, which affect protein and size but not AChE activity directly, have an overall affect on AChE activity. In contrast, the AChE inhibitor parathion altered AChE activity but not protein. Culture medium also had a significant affect on AChE activity in D. similis. Changes in total protein seem to be the main reason for the variations in baseline AChE activity in Daphnia observed in the different evaluations performed in this work. Therefore, AChE activity in Daphnia must be interpreted carefully, and variations related to changes in total protein must be taken into account when applying this enzyme as a biomarker in biological monitoring.

A comparative study on the relationship between acetylcholinesterase activity and acute toxicity in Daphnia magna exposed to anticholinesterase insecticides

Acetylcholinesterase (AChE) activity was measured in Daphnia magna that had been exposed to four organophosphates (OPs; parathion, chlorpyrifos, malathion, and acephate) and one carbamate (propoxur) for 48 h. These results were related to acute toxicity (median effective concentration [EC50] for immobility). For the four OPs, the EC50s were 7.03 pM, 3.17 pM, 10.56 pM, and 309.82 microM, respectively. The EC50 for propoxur was 449.90 pM. Reduction in AChE activity was directly related to an increase in immobility in all chemicals tested. However, the ratio between the EC50 and the AChE median inhibiting concentration ranged from 0.31 to 0.90. A 50% reduction in AChE activity generally was associated with detrimental effects on mobility. However, for acephate, high levels of AChE inhibition (70%) were observed in very low concentrations and were not associated with immobility. In addition, increasing the concentration of acephate further had a slight negative effect on AChE activity but a strong detrimental effect on mobility. Binding sites other than AChE possibly are involved in acephate toxicity to D. magna. Our findings demonstrate different associations between AChE inhibition and toxicity when different chemicals are compared. Therefore, the value of using AChE activity as a biomarker in D. magna will be dependent on the chemical tested.

Matrix effects observed during pesticides residue analysis in fruits by GC

The influence of the sample matrix in the CC-electron-capture detection analysis of the pesticides dimethoate, diazinon, chlorothalonil.. parathion methyl and fenitrothion in fruits samples has been studied. Experiments have been carried out where the pesticide responses in standard solutions prepared in selected solvent were compared with their response when present in apple, mango, papaya, banana, pineapple and melon extracts. The presence of matrix effects (MEs) and their extent were shown to be simultaneously influenced by several factors (matrix concentration, matrix type, pesticide concentration, analytical range). Pronounced MEs were observed particularly for dimethoate and diazinon in all matrices tested; in lower concentrations, all pesticides presented significant ME. The other pesticides presented variable ME. Higher ME enhancement was detected at lower pesticide concentration levels of and/or at higher matrix concentration solutions. The ME detected for fenitrothion, in the analytical range evaluated, were dependent on matrix type. For each pesticide, solvent and matrix-matched calibrations were compared for all fruit samples, and it could be concluded that quantitation based on standard solutions prepared in blank matrix extract (matrix-matched calibration) should be used to compensate the MEs and to obtain more accurate results for the pesticides studied.

Responsiveness of the interrenal tissue of Jundia (Rhamdia quelen) to an in vivo ACTH test following acute exposure to sublethal concentrations of agrichemicals

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Eficácia do paration metílico e do extrato aquoso de folhas secas de nim no controle de anacanthorus penilabiatus (monogenoidea) em pacu (piaractus mesopotamicus)

This work determined the efficacy of the insecticide methyl parathion and the natural pesticide azadirachtin present in the aqueous extract of dry neem leaves (AEDNL) to Anacanthorus penilabiatus (Monogenoidea) control in pacu (Piaractus mesopotamicus). The efficacy of methyl parathion was evaluated in an experiment consisting of six treatments (0.0, 3.0, 4.0, 5.0, 6.0 and 7.0 mg methyl parathion/L water) and five exposure times (2, 4, 8, 16 and 24 h). The efficacy of azadirachtin present in AEDNL was assessed in an experiment consisting of seven treatments (0,0; 25; 50; 75; 100; 125; e 150 mL/L water) and five exposure times (24, 48, 72, 96 and 120 h). The efficacy of methyl parathion increased with increasing concentration and exposure time. The highest control efficacy was obtained with a concentration of 7 mg methyl parathion/L at all exposure times. In this treatment, the highest efficacies were observed at 16 and 24 h of exposure, with a control rate of 96.2 and 97.0%, respectively. For the AEDNL, the highest control efficacy (89.2%) was obtained with a concentration of 2.9 mg/L after 120 h of exposure. The efficacy in the treatments employing 1.47 and 1.18 mg/L was 83.9 and 82.5%, respectively, after 120 h of exposure. Methyl parathion presented a higher efficacy in the control of A. penilabiatus than the AEDNL. The AEDNL was moderately effective in the control of the parasite.

Efeito de inseticidas em insetos predadores em culturas de algodão

Com o objetivo de verificar o efeito de inseticidas em insetos predadores em cultura de algodão (Gossypium hirsutum L.), instalaram-se, em 1993-1994, dois experimentos, um no campo, e outro, em laboratório. No experimento realizado no campo, os tratamentos foram: Fipronil 200 SC (75 g/ha de i.a.); Fipronil 800 WDG (64, 80 e 100 g/ha de i.a.); Endosulfan 350 CE (700 g/ha de i.a.); e testemunha. em laboratório, além das formulações à base de Fipronil foi utilizado o Paration metílico 600 CE (480 g/ha de i.a.). Fipronil foi seletivo para os artrópodes predadores (Scymnus sp., Geocoris ventralis, Cycloneda sanguinea e Doru lineare) no campo, e a Cycloneda sanguinea (L.), em laboratório, e pode ser recomendado em programas de manejo integrado de pragas na cultura do algodoeiro para o controle de Alabama argillacea (Rueb.), e Anthonomus grandis Boh. Endosulfan foi seletivo em relação a Scymnus sp., Geocoris ventralis Thomazini e Doru lineare (Eschs) no campo, com uma redução dos insetos inferior a 30%, e o Paration metílico não foi seletivo para C. sanguinea em laboratório.

Tetanorhynchus leonardosi (Mello-Leitão) (Orthoptera: Proscopiidae), nova praga em eucaliptos

We report for the first time the attack of the walking stick Tetanorhynchus leonardosi (Mello-Leitão) (Orthoptera: Proscopiidae) on young eucalyptus, Eucalyptus urophylla, in Brazil. The upper third of the trees was attacked (apical meristems and new leaves). During the hottest hours of the day the insects were found sheltered between leaves on the median third of the plants, and feeding when temperatures were milder. The attack was heterogeneous in the stand, being more concentrated when it was neighbouring an area of native 'Cerrado' vegetation. Mean defoliation was 5.8%, with an average of 5.2% of plants with apical meristems cut by the walking sticks. An application of Methyl Parathion was not effective against the pest. Apparently plants older than 6 months were less attacked by the insects, that preferred 3-month old trees. The reduction of native vegetation may explain the dispersion of T. leonardosi from its native host plants to the exotic eucalyptus.

Seletividade de agroquímicos ao ácaro predador Iphiseiodes zuluagai Denmark & Muma (Acari: Phytoseiidae)

Testes de efeito adverso de agroquímicos sobre Iphiseiodes zuluagai Denmark & Muma (Acari: Phytoseiidae) foram conduzidos em laboratório, utilizando o método residual de contato com pulverização em superfície de vidro. Foram testados 42 produtos químicos, a maioria utilizada na citricultura brasileira. A mortalidade e o efeito dos produtos na reprodução do ácaro foram avaliados diariamente durante oito dias. Os produtos foram classificados quanto ao efeito total causado ao ácaro (combinação da mortalidade e efeito na reprodução) em quatro classes de toxicidade propostas pela IOBC/WPRS. Os resultados mostraram que cerca de 26% dos produtos testados foram inócuos (captan, clofentezine, fenbutatin oxide, fosetyl, hexythiazox, hidróxido de cobre, naled, oxicloreto de cobre, óxido cuproso e tetradifon), 14% levemente nocivos (abamectin, chlorothalonil, sulfato de cobre, thiophanate-methyl (PM) e ziram), 7% moderadamente nocivos (enxofre, parathion-methyl e thiophanate-methyl (SC)) e 52% nocivos ao ácaro (acrinathrin, amitraz, azinphos-ethyl, azocyclotin, benomyl, bifenthrin, bromopropylate, carbaryl, carbosulfan, chlorfenapyr, cyhexatin, dicofol, fenpropathrin, fenpyroximate, mancozeb, óleo mineral e vegetal, phosmet, propargite, quinomethionate, triazophos, e vamidothion).

Determination of pesticide residues in coconut water by liquid-liquid extraction and gas chromatography with electron-capture plus thermionic specific detection and solid-phase extraction and high-performance liquid chromatography with ultraviolet detection

Two simple methods were developed to determine, 11 pesticides in coconut water, a natural isotonic drink rich in salts, sugars and vitamins consumed by the people and athletes. The first procedure involves solid-phase extraction using Sep-Pak Vac C-18 disposable cartridges with methanol for elution. Isocratic analysis was carried out by means of high-performance liquid chromatography with ultraviolet detection at 254 nm to analyse captan, chlorothalonil, carbendazim, lufenuron and diafenthiuron. The other procedure is based on liquid-liquid extraction with hexane-dichloromethane (1:1, v/v), followed by gas chromatographic analysis with effluent splitting to electron-capture detection for determination of endosulfan, captan, tetradifon and trichlorfon and thermionic specific detection for determination of malathion, parathion-methyl and monocrotophos. The methods were validated with fortified samples at different concentration levels (0.01-12.0 mg/kg). Average recoveries ranged from 75 to 104% with relative standard deviations between 1.4 and 11.5%. Each recovery analysis was repeated at least five times. Limits of detection ranged from 0.002 to 2.0 mg/kg. The analytical procedures were applied to 15 samples and no detectable amounts of the pesticides were found in any samples under the conditions described. (C) 2002 Elsevier B.V. B.V. All rights reserved.

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.

Pesticides in the distilled spirits of wine and its byproducts

The fate of eight fungicides (benalaxyl, fenarimol, iprodione, metalaxyl, myclobutanil, procymidone, triadimefon, and vinclozolin) and five insecticides (dimethoate, fenthion, methidathion, parathion methyl, and quinalphos) in wine and its byproducts (cake and lees) during the production of distilled spirits was studied. Among the pesticides studied, only fenthion, quinalphos, and vinclozolin residues were present in the distilled spirits. During wine distillation, respectively 13% and 5% of the initial residues of fenthion and vinclozolin were transferred to the distilled spirit. Low percentages (2% for fenthion and 0.1% for vinclozolin) of these active ingredients (AI) also passed from the lees to the final-distilled spirit, when samples were fortified at 10.1 and 26.1 ppm for fenthion and vinclozolin, respectively. Quinalphos passed only from the lees to the final-distilled spirit in percentages lower than 1% when samples were fortified at the highest concentration (4.6 ppm).

Pesticide residues in artichokes: Effect of different head shape

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.

Multiresidue analysis of pesticides in water from rice cultures by on-line solid phase extraction followed by LC-DAD

An automated on-line solid phase extraction procedure followed by liquid chromatography with diode array detection was investigated for the determination of different classes of pesticides in water samples containing varied amount of humic substances. The different pesticides used were: carbendazin, carbofuran, atrazine, diuron, propanil, molinate, alachlor, parathion-ethyl, diazinon, trifluralin and the degradation products deisopropylatrazine and deethylatrazine. Humic substances extracted from a Brazilian sediment were used from 5 to 80 mg/l and their influence on recoveries was evaluated in neutral and acidic media. Recoveries higher than 70% were obtained for all the pesticides, from the preconcentration of 75 mi of aqueous sample fortified at 2 ng/ml using precolumns packed with PLRP-S. Good recoveries were obtained at neutral pH for most of the analytes up to 40 mg/l of humic acid. Only at 80 mg/l the recoveries were significantly affected, both at acidic and neutral pH. The method was applied to the determination of pesticides in river water spiked at 0.1 to 1 ng/ml. Detection limits obtained for water containing 10 mg/l of humic acid were between 0.05 and 0.3 ng/ml.

Cortisol response to acute stress in jundiá Rhamdia quelen acutely exposed to sub-lethal concentrations of agrichemicals

Exposure to agrichemicals can have deleterious effects on fish, such as disruption of the hypothalamus-pituitary-inter-renal axis (HPI) that could impair the ability of fish to respond to stressors. In this study, fingerlings of the teleost jundiá (Rhamdia quelen) were used to investigate the effects of the commonly used agrichemicals on the fish response to stress. Five common agrichemicals were tested: the fungicide - tebuconazole, the insecticide - methyl-parathion, and the herbicides - atrazine, atrazine + simazine, and glyphosate. Control fishes were not exposed to agrichemicals and standard stressors. In treatments 2-4, the fishes were exposed to sub-lethal concentrations (16.6%, 33.3%, and 50% of the LC50) of each agrichemical for 96 h, and at the end of this period, were subjected to an acute stress-handling stimulus by chasing them with a pen net. In treatments 5-7 (16.6%, 33.3%, and 50% of the LC50), the fishes were exposed to the same concentrations of the agrichemicals without stress stimulus. Treatment 8 consisted of jundiás not exposed to agrichemicals, but was subjected to an acute stress-handling stimulus. Jundiás exposed to methyl-parathion, atrazine + simazine, and glyphosate presented a decreased capacity in exhibiting an adequate response to cope with stress and in maintaining the homeostasis, with cortisol level lower than that in the control fish (P < 0.01). In conclusion, the results of this study clearly demonstrate that the acute exposure to sub-lethal concentrations of methyl-parathion, atrazine + simazine, and glyphosate exert a deleterious effect on the cortisol response to an additional acute stressor in the jundiá fingerlings. © 2008 Elsevier Inc. All rights reserved.