Cette étude vise à développer un système de dépollution d'eau et de sédiments viticoles. Le glyphosate, diuron et 3,4-dichloroaniline (3,4-DCA) sont considérés, en tenant compte de la charge en cuivre. L'augmentation du temps de séjour des polluants dans le système et le choix de la bioaugmentation couplée à la phytoremédiation est la stratégie retenue. Chaque composante d'un triplet « sorbant-inoculum bactérien-plante » a été sélectionnée en laboratoire et le triplet mis en oeuvre en microcosmes en conditions partiellement contrôlées.La sélection de matériaux sorbants dans différentes matrices liquides en présence des polluants seuls ou en mélange montre que les capacités de sorption des différents matériaux testés varient selon le polluant, sa formulation (seul ou en mélange) et la matrice liquide. Le sédiment se révèle être le meilleur sorbant pour le glyphosate ; le sable pour le diuron et le 3,4-DCA.Les performances de dissipation des colonies tolérantes isolées varient fortement selon le polluant. Le consortium sélectionné pour le procédé dissipe le glyphosate, le diuron et le 3,4-DCA en milieu liquide et complexe par ailleurs le cuivre.L'expérience en microcosmes montre que le temps de rétention hydraulique influe sur l'efficacité du système et que les matériaux sorbants sont efficaces. De plus les performances de dissipation atteintes sont bonnes. L'effet de la bioaugmentation sur les performances de dissipation n'est pas significatif pour le glyphosate et le 3,4-DCA, mais améliore en moyenne la dissipation du diuron. Un temps d'action prolongé dans la matrice solide s'avère nécessaire pour obtenir une bonne efficacité du procédé. / This study aims at developing a depollution system for vineyard sediments and passing water. Glyphosate, diuron and 3,4-dichloroaniline (3,4-DCA) have been chosen, taking a copper load into account. Strategical choices are increased pollutant hydraulic retention time and the use of bioaugmentation together with phytoextraction. Each item on this « sorbent-bacterial inoculum-plant » triplet has been beforehand selected in the laboratory and implemented in microcosm experiments under semi-controlled conditions.Sorbent material selection in different liquid matrices with pollutants alone or in combination shows that material sorption capacities change with the type of pollutant. It has also been shown that these capacities vary with formulation (alone or in combination) and liquid matrix chosen. Sediment is awarded the best sorbent for glyphosate, sand the best sorbent for diuron and 3,4-DCA.Dissipation performances from isolated colonies are strongly related to the nature of the compound. Elected consortium degrades glyphosate, diuron and 3,4-dichloroaniline (3,4-DCA) in liquid culture as well as it complexes copper.Microcosm experiments show that hydraulic retention time weighs on pollutant concentration in water at the system outlet. Sorbents prove to be efficient. Dissipation performances are satisfactory. Bioaugmentation does not impact on glyphosate and 3,4-DCA dissipation performances significantly, but enhances diuron dissipation in average. Suitable process efficiency requires increased action time within the solid matrix.

Made available in DSpace on 2014-06-11T19:27:56Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-02-25Bitstream added on 2014-06-13T20:36:38Z : No. of bitstreams: 1 cardoso_apf_me_botfm.pdf: 463235 bytes, checksum: f5c3dd035d2b9e83db6356001aa70012 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] is a herbicide that in a previous longterm study with Wistar rats fed at 2,500 ppm concentration showed high incidence of urothelial tumors in both genders. Accordingly, USEPA categorized Diuron as a “known/likely” human carcinogen. The accepted non-genotoxic mode of action (MOA) of Diuron encompasses urothelial necrosis induced by direct cytotoxicity, followed by regenerative cell proliferation and sustained urothelial hyperplasia that may favor neoplasia development. Scanning electron microscopy (SEM), light microscopy and labeling index are essentials tools for identification and classification of cytotoxic and proliferative changes in the bladder. The present study evaluated the dose-response of Diuron regarding urothelial lesions. Sixty male Wistar rats were fed Diuron for 20 weeks mixed in the diet at 0, 60, 125, 500, 1,250, or 2,500 ppm. Simple hyperplasia was significantly increased in the Diuron 1,250 and 2,500 ppm groups, and the cell proliferation at 2,500 ppm group. By SEM, the incidences and severity of lesions were significantly greater in the 500 and 1,250 ppm. Although numerically increased, the incidence of lesions in the 2,500 ppm group did not differ significantly from the control. The present study documented a doseresponse influence of Diuron on the rat urothelium, with a no observed effect level (NOEL) of 125 ppm.

Na região de Ribeirão Preto está localizado um dos pólos produtores de cana-de-açúcar uma das principais culturas da economia brasileira, com vasta área cultivada e uso intensivo de herbicidas, dos quais é preciso destacar o diuron e a hexazinona, pois ambos possuem elevado potencial de contaminação em águas superficiais e subterrâneas. Diversas tecnologias podem ser utilizadas para remover da água esses microcontaminantes, pelo fato de, neste caso, não ser eficiente a técnica de tratamento em ciclo completo (ou convencional). Neste trabalho de pesquisa foram investigadas as combinações de preoxidação com cloro e dióxido de cloro, de adsorção em carvão ativado pulverizado e granular, associadas ao tratamento em ciclo completo. A água de estudo foi preparada em laboratório, com características similares às do rio Pardo – futuro manancial para abastecimento da cidade de Ribeirão Preto, e fortificada com diuron e hexazinona. Ensaios de bancada feitos em jarteste e filtros de laboratório permitiram concluir que a adsorção em carvão ativado (pulverizado e granular) foi eficiente na remoção dos herbicidas. Foi construída e operada uma instalação piloto com colunas de adsorção, em carvão ativado granular, cujos resultados obtidos mostraram que a difusividade intrapartícula predominante entre o carvão e os herbicidas diuron e hexazinona pode ser considerada constante, em relação ao tamanho do grão de carvão ativado. Os resultados também possibilitaram a validação do método de ensaios rápidos em coluna de carvão ativado em escala reduzida, com vista à predição do tempo de ruptura de um filtro de carvão ativado granular em escala real. Para as condições ensaiadas, a adsorção em carvão ativado granular mostrou ser 12% mais eficiente que em carvão ativado pulverizado, cujas taxas de utilização foram de 10,7 e 12,0 miligrama de carvão por litro de água tratada, respectivamente. Foram dimensionados os sistemas para utilizar carvão ativado pulverizado e granular em uma ETA de 1 m3/s e contabilizados os custos de implantação e de operação. Embora os custos de implantação do sistema de carvão ativado granular tenham resultado da ordem de 3 vezes os do pulverizado, os custos totais em valor presente seriam igualados em 5 anos, podem ser até 23% menores em 20 anos – o que mostra a viabilidade técnico-financeira desta alternativa no tratamento de águas contaminadas com herbicidas. / Sugarcane is one of the major crops of the Brazilian economy and the city of Ribeirao Preto is in one of the largest sugarcane producing regions, with a vast sugarcane plantation area and intensive use of herbicides, especially diuron and hexazinone, which have high potential to contaminate surface waters and groundwater. Several different technologies can be used to remove these micro-contaminants from water since, in this case, conventional treatment is not an efficient technique. In the present study, the combinations of pre-oxidation with chlorine and chlorine dioxide and adsorption in powdered and granular activated carbon associated with the conventional treatment were investigated. The water sample investigated in this study was prepared in a laboratory with similar characteristics to that of the Pardo river - future source of water supply for the city of Ribeirao Preto - and supplemented with diuron and hexazinone. Bench-scale experiments performed using Jartest equipment and laboratory filters showed that the adsorption in activated carbon (powdered and granular) was effective in removing the herbicides. A pilot granular activated carbon column was built and operated, and the results showed that the prevailing intraparticle diffusivity between the carbon and the herbicides diuron and hexazinone can be considered constant, do not change with particle size. The results obtained also enabled the validation of the rapid small-scale column test (RSSCT) method to predict the full scale breakthrough time of a granular activated carbon filter. Under the conditions evaluated, the adsorption in granular activated carbon proved to be 12% more efficient than that in powdered activated carbon, whose carbon usage rates were 10.7 and 12.0 milligrams per liter of treated water, respectively. The systems were designed to use powdered and granular activated carbon in a 1 m3/s conventional water treatment plant, and the implementation and operation costs were calculated. Although the capital costs of the granular activated carbon system were about 3 times higher than those of the powdered activated carbon, these costs would be the same in 5 years and could even be 22% lower in 20 years, which shows the technical-financial feasibility of this alternative to the treatment of water contaminated with herbicides.

Over the years, global agriculture has grown in acreage and productivity, accompanied by heavy use of pesticides, which also suffered from major developments. Many new molecules have emerged, with physical and chemical characteristics that provide different features and different environmental behaviors, with major changes in ecotoxicological profiles, resulting from advances and environmental pressures. This study aims to evaluate the potential for contamination of surface waters by products used in the management of cane sugar in the sub-basin of Rio Poxim / SE. The risk analysis was performed using criteria of the Environmental Protection Agency (EPA), GUS index, method and rate of GOSS Leach. These criteria are based on physicochemical properties of the active ingredients of each pesticide by providing coefficients of adsorption of organic carbon (Koc) and half-life (t ½) of the product in the soil, which is then applied to respective formulas. This study assessed the main products used in the cultivation of sugar cane, through a survey conducted in rural properties and trade of inputs in the region. It may be noted that the 17 studied 12 active probable risk of suffering leaching, this demonstrates the importance of monitoring the river to control both water quality and the frequency and volume of pesticides applied. These components are fitted in between I Toxicologic Classification Extremely Toxic (Paraquat) and IV Slightly toxic (metribuzin). After these results was done bi-monthly monitoring at sub-basin of Rio Poxim between the periods July 2009 to July 2010 in order to detect possible pesticide amount of sugar cane-sugar in the river and Poxim- Mirim Poxim. The results of the samples were analyzed by ITEP found that the presence of ametrina and diuron. In Rio Poxim-Mirim was verified the presence of diuron and ametrine especially in rainy periods for Diuron reaching maximum values of 0.9 and 0.2 for Ametrine and maximum values of 0.04 and 0.05 in May and July 2010. Your maximum permissible are not defined in current standards in Brazil. Therefore, the water quality in the sub-basin of Rio Poxim is influenced by seasonal rains in which there was an increased concentration of pesticides in surface water caused by soil runoff. So, it is recommended to expand the monitoring of groundwater and surface waters that supply the ETA, restore riparian vegetation in this sub-basin, including new rules update the pesticides, increase surveillance and thus arouse the attention of the competent authorities on water quality provided to the community of Greater Aracaju. / Ao longo dos anos, a agricultura mundial cresceu em produtividade e área cultivada, acompanhada pelo uso intenso de pesticidas. Foram produzidas muitas moléculas novas, com características físico-químicas que propiciam funcionalidades diferenciadas e comportamentos ambientais distintos, fruto dos avanços e pressões ambientalistas. O presente trabalho teve como objetivo avaliar o potencial de contaminação de águas superficiais por produtos utilizados no manejo da cana-de-açúcar na sub-bacia do rio Poxim. Esse rio é o manancial de onde é captada a água para abastecimento da cidade de Aracaju, capital do estado de Sergipe. A análise de risco foi realizada mediante critérios da Environmental Protection Agency (EPA), índice de GUS, método de GOSS e índice de Leach. Esses critérios baseiam-se em propriedades físico-químicas dos princípios ativos de cada pesticida, mediante o fornecimento de valores de coeficiente de adsorção ao carbono orgânico (Koc) e de meia-vida (t½) do produto no solo, os quais são posteriormente aplicados às fórmulas respectivas. Neste estudo, foram avaliados os principais produtos aplicados na cultura de cana-de-açúcar, por meio de levantamento realizado em propriedades rurais e comércio de insumos da região. Observou-se que, dos 17 princípios ativos estudados, 12 sofreram risco de lixiviação, demonstrando a importância do monitoramento do rio para controle tanto da qualidade da água como da frequência e volume de pesticidas aplicado. Esses componentes são enquadrados na Classificação Toxicológica entre I (Extremamente Tóxico, como Paraquat) e IV (Pouco Tóxico, como o Metribuzim). A partir desses resultados, foi feito o monitoramento bimensal na sub-bacia do rio Poxim, durante o período de julho de 2009 a julho de 2010, com o objetivo detectar possíveis pesticidas à montante das plantações de canade- açúcar, no rio Poxim-Mirim e Poxim. Os resultados das amostras foram analisados pelo ITEP, que constatou a presença de Ametrina e Diuron. No rio Poxim-Mirim, foi constatada a presença de Diuron e Ametrina, principalmente nos períodos chuvosos, com valores máximos de 0,9 e 0,2 (μ.gL-1), para o Diuron e valores máximos de 0,04 e 0,05 (μ.gL-1), para a Ametrina, nos meses de maio e julho de 2010. Os limites máximos permitidos, para o Diuron e Ametrina, não estão definidos nas normas vigentes no Brasil.A qualidade da água na sub-bacia do rio Poxim está sendo influenciada pela sazonalidade das chuvas, visto que houve um aumento da concentração de pesticidas na água superficial, durante um período do ano, provocado pelo escoamento superficial do solo. Então, recomenda-se ampliar o monitoramento das águas subterrâneas e superficiais que abastecem a cidade; recompor a mata ciliar dessa sub-bacia; atualizar as normas, incluindo novos pesticidas; intensificar a fiscalização e, por fim, despertar a atenção das autoridades competentes para a qualidade da água fornecida para a comunidade da Grande Aracaju.

No description available.

Orientador: Eleni Gomes / Banca: Elen Aquino Perpetuo / Banca: Dávila de Souza Zampieri / Resumo: Restaurar ecossistemas degradados por compostos xenobióticos é um dos desafios atuais, que implica no desenvolvimento de metodologias eficazes que minimizem os danos e não interfiram nos processos naturais. A biorremediação é uma tecnologia que utiliza organismos vivos e/ou seus derivados para eliminar ou reduzir os níveis de poluentes de um determinado ambiente. Dentro dessa proposta, o emprego dos fungos para a recuperação de áreas contaminadas com xenobióticos de variados grupos químicos, tem sido bastante explorado, em função de suas características biológicas e morfológicas, além de suas enzimas extracelulares. A ação de um microrganismo sobre um determinado composto é desejável no sentido da redução de sua complexidade química, entretanto, a geração de compostos intermediários mais tóxicos que o original pode ocorrer, exigindo a avaliação desses derivados metabólicos antes de se inferir sobre o uso de uma determinada técnica de biorremediação. O presente trabalhou teve como objetivo avaliar a degradação do herbicida diuron pelos fungos Trichoderma harzianum G15, Trichoderma virens F28, Cunninghamella elegans B06, Fusarium sp. B19, Aspergillus sp. G25, Aspergillus brasiliensis G08, Beauveria sp. 211 e Mortierella alpina F17, e tolerância aos metabólitos gerados. T. harzianum G15, T. virens F28 e C. elegans B06 foram capazes de degradar entre 12 e 43% de diuron, acumulando no meio de cultivo os metabólitos DCPMU e DCPU, e ausência de 3,4-DCA. Quando cultivados em meio contendo esses metabólitos em substituição ao diuron, não houve efeito inibitório sobre o crescimento dos fungos e a degradação dos metabólitos foi de 42 a 73% para DCPMU, 37 a 69% para DCPU, 15 a 100% para a 3,4-DCA e de 19 a 84% para diuron. A formação de diferentes metabólitos a partir de 3,4-DCA, como o 3,4-CAC e 3,4-DCNB indicou que os fungos possuem mecanismos enzimáticos distintos de biodegradação desse composto... / Abstract: Degraded ecosystems recovery is one of the current challenges, which implies the development of effective methodologies that minimize the damage and not interfere with natural bioprocesses. Bioremediation is a technology that utilizes living organisms and/or their derivatives to eliminate or reduce the pollutant levels in an environment. The use of fungi for biodegradation of xenobiotics of various chemical groups has been extensively explored, due to its biological and morphological characteristics, and their extracellular enzymes. The action of a microorganism on the pollutant compound is desired in order to reduce its chemical complexity, however, the generation of more toxic intermediate compounds than the original may occur, requiring the evaluation of these metabolite derivatives prior to infer the use of a determined bioremediation technique. This work aimed to evaluate the herbicide diuron degradation by Trichoderma harzianum G15, T. virens F28, Cunninghamella elegans B06, Fusarium sp. B19, Aspergillus sp. G25, A. brasiliensis G08, Beauveria sp. 211 e Mortierella alpina F17 and evaluate their tolerance and ability to metabolize those generated metabolites. T. harzianum G15, T. virens F28 and C. elegans B06 were able to degrade between 12 and 43% of diuron and accumulated in the culture medium DCPMU metabolites and DCPU but not 3,4-DCA. When grown in medium containing these metabolites to replace diuron, no inhibitory effect on the growth of fungi and the degradation of DCPMU was 42 to 73%, for DCPU from 37 to 69%, for 3,4-DCA from 15 to 100%, and for diuron 19 to 84%. The formation of different metabolites from 3,4-DCA, such as 3,4-CAC and 3,4-DCNB indicated that the fungi have different enzymatic mechanisms of biodegradation of such a compound. The metabolites detected in culture media allowed to suggest that diuron degradation followed the degradation following sequence: DCPMU, DCPU, 3,4-DCA, 4-CAC, CAC 3.4-and 3.4-DCNB ... / Mestre

Orientador: Eleni Gomes / Banca: Thiago Scremin Pereira / Banca: Marcio Luis Busi da Silva / Banca: Marcelo de Freitas Lima / Resumo: A intensificação da agricultura tem levado um aumento da utilização de pesticidas, o que pode carrear esses compostos e seus derivados do solo para ambientes aquáticos. Para minimizar a presença desses compostos xenobióticos no meio, tem se sugerido técnicas de biorremediação que utiliza a atividade de micro-organismos para eliminação ou redução desses poluentes. O ataque de compostos aromáticos e clorados por micro-organismos ou por suas enzimas livres no meio podem levar ao desejável processo de biodegradação, originando derivados quimicamente mais simples e menos tóxicos até a mineralização total do composto. O objetivo do trabalho foi estudar a degradação do diuron por cepas bacterianas previamente isoladas de solos de cultivo de cana-de-açúcar com histórico de aplicação desse herbicida, em fermentação submersa e em microcosmos e avaliar a toxicidade dos compostos derivados do diuron gerados pelo metabolismo microbiano. Todas as bactérias testadas foram capazes de degradá-lo quando cultivadas em meio líquido. Quando se utilizou sistemas de cultivo em solo acrescido de diuron (microcosmos) obteve-se até 50% do composto. Nos testes de toxicidade dos metabólitos do diuron sobre peixes foi utilizada a atividade enzimática da 7-etoxiresorufina-O-deetilase (EROD) e teste do cometa como referência. Foi observada uma inibição da atividade da EROD, possivelmente relacionada a uma inibição das isoenzimas... / Abstract: The intensification of agriculture has led an increase in the use of pesticides, which may carry these compounds and their derivatives from soil to aquatic environments. To minimize the presence of xenobiotics in the environment, it has been suggestes bioremediation techniques that use the activity of microorganisms to eliminate or reduce these pollutants. The attack of aromatic and chlorinated compounds by microorganisms or their enzymes free in the medium can lead to desirable biodegradation process, yielding chemically simpler and less toxic derivatives until the total mineralization of the compound. The aim of this work was to study the degradation of diurom by bacterial strains previously isolated from cane sugar cultivation of soils with application history of this herbicide in submerged fermentation and in microcosms and evaluate the toxicity of diuron derived from compounds generated by metabolism microbial. All bacteria tested were able to grow in the presence of diuron, but not all were able to degrade it when cultured in liquid medium. When used in a soil cultivation systems plus diuron (microcosms) afforded 50% compound. In the tests of toxicity of the metabolites of diuron was used fish the enzymatic activity of 7-O-etoxiresorufina deetilase (EROD) and comet assay as a reference. Was observed inhibition of EROD activity, possibly related to... / Mestre

Resumo: Não disponível. / Abstract: Diuron [3-(3,4-dichlorophenyl)-1,1-dimethyl urea] is a herbicide with carcinogenic activity in rats and mice which have developed respectively urothelial and mammary gland tumors in long-term studies. Accordingly, diuron has been categorized as a "likely human carcinogen" by the USEPA. Although the carcinogenesis initiating activity of diuron has been reported in an early initiation-promotion mouse skin study, its genotoxic potential has been disputed. It is necessary to clarify the mode of action through which it has caused rodent neoplasia and verify its relevance to humans. Herein, two experiments were developed to verify the initiating and promoting potentials of diuron in a 23- and a 21-week long mouse skin carcinogenesis protocol. In one, dimethylsulphoxide (DMSO) was the solvent for the herbicide; in the other, acetone was the alternative solvent in order to verify if DMSO had inhibitory influence on a potential cutaneous carcinogenic activity. The adopted schedule for the tumor promoting agent 12-O-tetradecanoylphorbol 13-acetate (TPA) resulted in skin ulcers, evidencing the need for careful selection of TPA dose levels and frequency of application in this model. In both studies diuron did not exert any influence on the skin carcinogenesis process, in contrast with results already reported in the literature. / Orientador: João Lauro Viana de Carmargo / Coorientador: Deilson Elgui de Oliveira / Banca: Maria Lucia Zaidan Dagli / Banca: Heidge Fukumasu / Mestre

Graduation date: 1995

Italian ryegrass growth and production from positionally selective applications and sublethal rates of a nonselective herbicide were compared to growth and production when treated with diuron applied preemergence as a broadcast treatment and safened by activated carbon applied over the crop row. In the positionally selective treatments, herbicide spray was directed to leave an untreated zone over the crop row at planting. Growth analysis indicated no detectable differences when Italian ryegrass safened by directed spray was compared to Italian ryegrass safened by activated carbon. The major difference between systems was greater weed control in the crop row for carbon-safened treatments. The non-safened application superimposed sublethal diuron rates over Italian ryegrass and rattail fescue grown in varying densities and proportiors. Growth analysis of monoculture stands indicated differences due to planted density, species, and herbicide, whereas growth analysis of plants grown as space-planted individuals indicated difference due to species only. Diuron at the rates applied did not affect seed yield or above ground dry weight. Soil samples were taken in crop rows where diuron was applied as directed spray or broadcast spray safened by carbon. Samples were assayed and soil profile concentrations mapped. To assist future investigators' understanding of the role rainfall plays in herbicide movement from directed applications, elementary rainfall depth and occurrence models were examined. The Markov and mixed-exponential models adequately described rainfall occurrence and depth patterns for Corvallis, Oregon. / Graduation date: 1992