Improving the Detectability of Sequential Injection Chromatography (SIC): Determination of Triazines by Exploiting Liquid Core Waveguide (LCW) Detection

Coupling a liquid core waveguide cell to a sequential injection chromatograph improved the detection limits for determination of triazine herbicides without compromising peak resolution. Separation of simazine, atrazine, and propazine was achieved in water samples by a 25mm long C18 monolithic column. Detection was made at 238nm using a type II LCW (silica capillary coated with Teflon (R) AF2400) cell with 100cm of optical path length. Detection limits for simazine, atrazine, and propazine were 2.3, 1.9, and 4.5 mu g L-1, respectively. Reduced analysis time and low solvent consumption are other remarkable features of the proposed method.

Poly(epsilon-caprolactone)nanocapsules as carrier systems for herbicides: Physico-chemical characterization and genotoxicity evaluation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Seletividade de herbicidas, aplicados em pós-emergência, às plantas de alfafa

Foram conduzidos doi experimentos na UNESP/Jaboticabal, em casa-de-vegetação, com o objetivo de avaliar-se a toxicidade de diferentes herbicidas, aplicados em pós-emergênica, às plantas de alfafa. No primeiro, utilizou-se de um delineamento experimental com parcelas inteiramente casualizadas para avaliar-se os efeitos fitotóxicos dos seguintes herbicidas: MSMA, clethodim + óleo mineral, lactofen, fluazifop-pbutil, fomesafen + óleo mineral haloxyfop-methyl + óleo mineral, fenoxaprop-ethyl, chlorimuronethyl, halosulfuron + óleo mineral, nicosulfuron, acifluorfen, imazethapyr, bentazon + óleo mineral e cyanazine + simazine, todos em só dose. Foram feitas avaliações da fitotoxicidade por meio de notas, atribuídas visualmente, em função dos sintomas constatados nas plantas. A altura das plantas e o peso da matéria seca da parte área foram avaliadas no período de desenvolvimento inicial e após a primeira rebrota. No segundo experimento foi seguido mesmo esquema de instalação e condução do anterior, após escolherse os herbicidas e doses, sendo eles, o MSMA, chlorimuron-ethyl, imazethapyr, bentazon + óleo mineral, clethodim, clethodim + óleo mineral e bentazon + MSMA. Os herbicidas mais seletivos às plantas de alfafa foram haloxyfop-methyl, fluazifop-p-butil, fenoxaprop-ethyl, MSMA, imazethapyr, bentazon e clethodim isolado e adicionado de óleo mineral).

Efeito de herbicidas residuais, aplicados por vários anos consecutivos, na distribuição do sistema radicular da laranjeira Natal (Citrus sinensis.(L.) osbeck)

O presente trabalho foi desenvolvido com o objetivo de verificar a influência do uso contínuo de vários herbicidas residuais, sobre a distribuição das radicelas de laranjeiras Natal (Citrus sinensis (L.) Osbeck) enxertadas sobre limão Cravo (Cithus limonia Osbeck) e plantadas em janeiro de 1970. O experimento foi instalado no pomar de produção da Faculdade de Ciências Agrárias e Veterinárias do Campus de Jaboticabal (UNESP), em Latossol Roxo distrófico, com 1,6% de matéria orgânica e 51% de argila. O delineamento experimental utilizado foi o de blocos ao acaso, dentro de um esquema fatorial 11x 3x2x2, com três repetições. Os tratamentos utilizados, com as respectivas doses em kg do i.a/ha foram: fluometuron a 4,2; simazíne a 4,8; atrazine a 4,8; bromacil a 3,2;bromacil (40%) + diuron (40%) a 4,8; bromacil (53,3%) + diuron (27,6%) a 4,8; terbacil a 3,2; oxadiazon a 1,5; dichlobenil a 3,0 e 6,0; além de uma testemunha capinada. O estudo das radicel as foi feito pelo método do trado, tendo sido tomadas amostras de solo contendo radicelas, nas distâncias de 80, 160 e 240 cm do tronco, nas camadas de 0 a 15 cm e 15 a 30 cm de profundidade e em duas direções distintas (entrelinhas e entreplantas). Os resultados mostraram que as radicelas localizam-se superficialmente, com 70% delas nos primeiros 15 cm, do total encontrado na camada superficial de 0 a 30 cm de profundidade do solo. Cerca de 75% das radicelas situam-se até a distância de 160 cm do tronco. Na camada mais superficial do solo (0 a 15 cm), a quantidade de radicelas diminuiu de maneira acentuada, à medida que se afastou do tronco. Na camada de 15 a 30 cm de profundidade, ocorreu uma distribuição horizontal mais uniforme, comparada com a da camada de 0 a 15 cm. As radicelas das plantas do cultivar Natal distribuiram-se uniformemente, tanto na direção das plantas da linha vizinha, quanto nas das plantas de uma mesma linha, para o espaçamento de 7,0 m x 7,2 m. Não se detectaram diferenças estatisticamente significativas nas quantidades de radicelas entre as parcelas dos vários tratamentos com herbicidas, excluindo-se desta forma, qualquer efeito negativo de tais produtos químicos sobre o sistema radicular das laranjeiras.

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)

Bioaccumulation of chlorinated pesticides and PCBs in the tropical freshwater fish Hoplias malabaricus: Histopathological, physiological, and immunological findings

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Determination of herbicides residues in soil by small scale extraction

Herbicidas tais como trifluralina, simazina, atrazina, metribuzina e metolaclor são usados na agricultura brasileira. A eficiência de um método em pequena escala para a determinação destes herbicidas e dois produtos de degradação em amostras de solo foi avaliada. Os compostos foram extraídos das amostras de solo (5 g) com 20 ml de acetato de etila em agitador mecânico por 50 min. Após a extração, o sobrenadante foi filtrado em sulfato de sódio anidro, concentrado e analisado por cromatografia a gás de alta resolução com detector termiônico específico. Valores médios de recuperação obtidos de amostras de solo fortificadas em três níveis diferentes variaram de 81 a 115 % com valores de desvio padrão relativo entre 1,2 e 12,7 %. Os limites de detecção do método variaram de 0,01 a 0,06 mg kg-1. A metodologia foi aplicada a amostras de solo de fazendas localizadas próximas à cidade de Araraquara, estado de São Paulo, Brasil.

Determination of herbicides and a metabolite in human urine by liquid chromatography-electrospray ionization mass spectrometry

A method was developed to determine simazine, atrazine and their metabolite, 2-chloro-4,6-diamino-1,3,5-triazine, in urine. The presence of these herbicides in urine may reflect possible exposure to pesticides. Sample preparation involved protein precipitation and solid-phase extraction. The samples were analyzed by high-performance liquid chromatography-mass spectrometry. The detection limits were 0.4 mug/l and the analytes have a linear response in the interval 6-800 mug/l. The precision of the method was reflected in the RSD of <2.4% for the herbicides studied. Based on the detectable herbicide levels from spiked urine samples collected from unexposed volunteers, this method can be used to determine the low levels necessary for establishing reference values of the selected herbicides and the metabolite. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Multiresidue determination of herbicides in environmental waters from Primavera do Leste region (Middle West of Brazil) by SPE-GC-NPD

A study on the presence of herbicides, namely simazine, metribuzin, metolachlor, trifluralin, atrazine and two metabolites, deisopropylatrazine (DIA) and deethylatrazine (DEA), was performed in ground and surface waters from Primavera do Leste region, Mato Grosso state (Middle West of Brazil). The analytical procedure was based on solid-phase extraction (SPE) with Sep-Pak C18 disposable cartridges and ethyl acetate for elution solvent. Residue levels were determined by gas chromatography with nitrogen-phosphorus detection. For most of the pesticides average recoveries at different fortification levels were >with relative standard deviation < The recoveries of DIA and trifluralin in water were 25% and 56%, respectively, which were attributed to the incomplete retention of DIA and strong retention on the sorbing material and high volatility of trifluralin. Detection limits ranged from 0.023 to 0.088 μg L-1. This method was applied for the analysis of 5 superficial water samples and 28 groundwater samples, in places used for human consumption without previous treatment, collected in Primavera do Leste, Mato Grosso, Brazil. Results indicated that the highest level of contamination in a water sample was 1.732 μg L-1 for metolachlor, while metribuzin was the most frequently detected herbicide with maximum concentration of 0.351 μg L-1. ©2006 Sociedade Brasileira de Química.

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.

Resposta cortisolêmica e sensibilidade ao hormônio adrenocorticotrófico (ACTH) de jundiá (Rhamdia quelen) em exposição sub-letal a agrotóxicos

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Contaminação de águas superficiais e subterrâneas por pesticidas em Primavera do Leste, Mato Grosso

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Ecotoxicological Evaluation of Poly(epsilon-Caprolactone) Nanocapsules Containing Triazine Herbicides

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Preparo e caracterização de nanopartículas lipídicas sólidas como sistema carreador conjunto para os herbicidas atrazina e simazina visando futuras aplicações em agricultura

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Iron(III) Porphyrin Covalently Supported onto Magnetic Amino-Functionalized Nanospheres as Catalyst for Hydrocarbon and Herbicide Oxidations

This work describes the covalent immobilization of an ironporphyrin, 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin iron(III) chloride (FeTFPP), onto maghemite/silica magnetic nanospheres covered with aminofunctionalized silica. The resulting material (gamma-Fe2O3/SiO2-NHFeP) was characterized by diffuse reflectance infrared spectroscopy (DRIFTS) and UV-Vis absorption spectroscopy. The catalytic activity of this magnetic ironporphyrin was investigated in the oxidation of hydrocarbons (styrene, (Z)-cyclooctene and R-(+)-limonene) and an herbicide (simazine) by hydrogen peroxide or 3-chloroperoxybenzoic acid. Hydrocarbon and simazine oxidation reaction products were analyzed by gas chromatography (GC) and high performance liquid chromatography (HPLC), respectively. This catalytic system proved to be efficient and selective for hydrocarbon oxidation, leading to high product yields from styrene (89%), cyclooctene (71%) and R-(+) -limonene (86%). Simazine oxidation was attained with 100% selectivity for a dechlorinated product (OEAT), while several oxidation products were obtained for the same catalyst in homogeneous media. The catalyst can be easily recovered through application of an external magnetic field and washed after reaction. Catalyst reuse experiments for R-(+)-limonene oxidation have shown that the catalytic activity is kept at 90% after 10 consecutive reactions.