Submitted by Adriana Martinez (amartinez@unoeste.br) on 2016-10-11T12:17:24Z No. of bitstreams: 1 Jaqueline Nascimento da Silva.pdf: 2368376 bytes, checksum: b34072cdd99331d11d5544ee10f94320 (MD5) / Made available in DSpace on 2016-10-11T12:17:24Z (GMT). No. of bitstreams: 1 Jaqueline Nascimento da Silva.pdf: 2368376 bytes, checksum: b34072cdd99331d11d5544ee10f94320 (MD5) Previous issue date: 2016-04-25 / Brazil produces approximately 1% of natural rubber derived from rubber tree (Hevea brasiliensis) in the world, and Sao Paulo state is the major producer. The plantation of rubber tree might be stricken by fungal diseases, specially Antracnose. This fact requires the necessity of agriculture defenders as Cerconil WP®, composed by thiophanate methyl and chlorothalonil, one of the most used. Facing the large exposure to these compounds of workers and population that live near plantations, it is extremely important evaluate its possible toxicity and health impacts. Once that, the present work had as objective identify potential teratogenic effects and maternal toxicity of exposure to Cerconil WP® fungicide in different doses, using rat as an experimental model. Moreover, the study also aimed to identify effects of this fungicide on the chemistry structure latex of rubber tree, via Raman Spectroscopy. Therefore, Winstar female rats, adults and pregnant were divided into 4 experimental groups, that received 0 (control), 400 (EA), 800 (EB) or 1200mg/kg/day (EC) of Cerconil WP®, via gavage, from 6º to 15º gestational day (GD). In GD20, pregnant rats were euthanized and submitted to laparotomy for collection of uterus and maternal organs. The fetuses were collect, processed to skeletal and visceral analysis. Rats that were exposure to the fungicide presented clinical signs of toxicity. Reduction in weight evidenced in all groups in comparison to the Control group in GD12. Weight of maternal liver was lower in group EC than Control and histopathologic analysis of hepatic tissue presented areas of focal necrosis, inflammatory infiltrate, picnotic nuclei in hepatocytes and microvesicular fat degeneration areas moderated in groups EB and EC. The percentage of fetuses with adequate weight for gestational age was lower in groups EA and EB, in relation to the Control and EC groups. Porcentage of little fetuses increased in group EA, in relation to the other experimental groups, and in group EB in comparison to Control. In addition, there was an increase of total incidence of skeletal anomalies in groups exposure in relation to the control. Skeletal alterations observed in higher frequency were: decrease in esternal centres, absence of xiphoid process and caudal vertebrae, malformation of suppra-occiptal and reduction on number of anterior and metatarsus phalanges. Measures of Raman Spectroscopy (laser island of 514,5 nm, 25 seconds of exposure and 3 to 5 accumulations) did not show significant chemistry alterations on the latex exposure in vitro to 2g/L of Cerconil WP®. Results demonstrated that the oral exposure of pregnant rats to Cerconil WP®, during organogenesis, might affect on the embrio-fetal development and cause low toxicity to general maternal health. However, the molecular structure of latex exposed to the fungicide was not affect on the experimental study conditions. / O Brasil produz aproximadamente 1% da borracha natural derivada de seringueira (Hevea brasiliensis) no mundo, sendo o estado de São Paulo o maior produtor. O plantio de seringueira pode ser acometido por doenças fúngicas, especialmente a Antracnose. Isto leva à necessidade do uso de defensivos agrícolas, sendo o Cerconil WP®, composto por tiofanato metílico e clorotalonil, um dos mais utilizados. Diante da ampla exposição de trabalhadores rurais e da população do entorno das plantações a estes compostos, torna-se extremamente importante avaliar a sua possível toxicidade e impactos à saúde. Assim, o presente trabalho teve como objetivo identificar os potenciais efeitos teratogênicos e de toxicidade materna da exposição ao fungicida Cerconil WP® em diferentes doses, utilizando o rato como modelo experimental. Além disso, o estudo também pretendeu identificar os efeitos deste composto sobre a estrutura química do látex de seringueira, via Espectroscopia de Espalhamento Raman. Para tanto, ratas Wistar adultas prenhes foram divididas em 4 grupos experimentais, que receberam 0 (controle), 400 (EA), 800 (EB) ou 1200mg/kg/dia (EC) de Cerconil WP®, via gavagem, do 6º ao 15º dia gestacional (DG). No DG20, as ratas prenhes foram mortas e submetidas à laparotomia para coleta do útero gravídico e órgãos maternos. Os fetos coletados foram processados para análise esquelética e visceral. Ratas expostas ao fungicida apresentaram sinais clínicos de toxicidade. Houve redução no peso das ratas no DG12 em todos os grupos expostos em relação ao grupo controle. O peso do fígado materno foi reduzido no grupo EC em relação ao controle e a análise histopatológica do tecido hepático apresentou áreas com necrose focal, infiltrado inflamatório, presença de hepatócitos com núcleo picnótico e área com formação de degeneração gordurosa microvesicular de moderada intensidade nos grupos EB e EC. A porcentagem de fetos com peso adequado para a idade gestacional foi menor nos grupos EA e EB, em relação aos grupos controle e EC. Além disso, a porcentagem de fetos pequenos aumentou no grupo EA, em relação aos demais grupos experimentais, e no grupo EB em relação ao controle. Foi observado um aumento na incidência total de anomalias esqueléticas nos grupos expostos em relação ao grupo controle. As alterações esqueléticas observadas em maior frequência foram: diminuição dos centros esternais, ausência de processo xifoide e vertebras caudais, malformação do supra-occipital e redução no número de falanges anteriores e metatarsos. As medidas de Espectroscopia de Espalhamento Raman (linha de laser de 514,5 nm, 25 segundos de exposição e 3 a 5 acumulações) não apresentaram alterações químicas significativas no látex exposto in vitro a 2g/L de Cerconil WP®. Os resultados demonstram que a exposição oral de ratas prenhes ao Cerconil WP®, durante a organogênese, pode afetar o desenvolvimento embrio-fetal e causar toxicidade leve sobre a saúde geral materna. No entanto, a estrutura molecular do látex exposto ao fungicida não foi afetada nas condições experimentais do estudo.

Senegal ranks second for mango production among West African countries and has the potential to competitively produce mangoes for the European market. Colletotrichum gloeosporioides Penz. and Sacc. has historically been considered the causal pathogen of anthracnose of mango and other fruits, but is now known to represent a species complex. Field trials to examine the efficacy of fungicides and biofungicides were conducted in southern and northern production regions of Senegal. In three southern trials, Sonata (Bacillus pumilus strain QST 2808), Serenade Optimum (Bacillus subtilis strain QST 713), and sodium molybdate provided 63%, 67% and 76% control of disease severity, respectively, whereas thiophanate methyl and azoxystrobin provided 77% and 78% control, respectively. Disease severities of all treatments were significantly lower than that of the control. Thiophanate methyl and azoxystrobin produced more disease-free mangoes (64 and 62%, respectively) than Serenade (49%), sodium molybdate (44%), and Sonata (38%). Differences within each trial were not statistically significant, but when all trials were combined, all treatments resulted in significantly more disease-free mangoes than the control. Among treatments, thiophanate methyl and azoxystrobin resulted in significantly more disease-free mangoes than Sonata. No results were obtained in the northern orchards due to an absence of disease development. Sequencing of the ITS gene region of 30 Colletotrichum isolates from mangoes from different regions in Senegal indicated that all belonged to the C. gloeosporioides species complex. Sequencing of the ApMat intergenic region identified all of them as most closely resembling C. siamense. / Master of Science in Life Sciences

L’objectif principal de cette thèse était de mieux comprendre le comportement photochimique des pesticides pulvérisés dans les serres agricoles à Menyeh-Liban Nord. La première partie du travail a été consacrée à l’analyse des échantillons de poivrons verts, concombres, tomates, des films de plastique et de l’air récupérés dans ces serres agricoles. Nous avons quantifié et suivi par HPLC-HR-MS les résidus de 4 pesticides: bifénazate (BIF), acétamipride, imidaclopride et thiophanate méthyl (TM) dans les échantillons de légumes extraits par la méthode QUECHERS. Les quantités retrouvées durant les 6 jours suivant la pulvérisation étaient bien supérieures aux MRLs imposées pour chaque pesticide. Par ailleurs, des photoproduits de TM, BIF et de l’imidaclopride ont été détectés dans les solutions de rinçage de la surface des tomates, des concombres et des poivrons verts, démontrant ainsi la possibilité de photodégradation des pesticides à l’intérieur d’une serre agricole. L’analyse de la phase gazeuse par GC-MS a révélé la libération de terpènes, d’alcanes et d’aldéhydes comme réponse des plantes au stress de température et de pulvérisation. Dans une deuxième partie, on a détaillé les mécanismes de transformation photochimique du BIF et du TM sous irradiations simulées. La photodégradation de TM avait un caractère autoaccéléré qui n’a jamais été rapporté dans la littérature. Une étude détaillée nous a permis de démontrer que cette auto-accélération est due à la formation d’un photoproduit photosensibilisateur dérivé de la quinoxaline. Quant au BIF, sa vitesse de dégradation et la nature des produits dépendaient du milieu (ACN, eau, cire et poivron verts). Ces travaux ont mis en évidence l’effet de support et de mélange sur le comportement photochimique des pesticides. / The main purpose of this work was to better understand the photochemical behavior of pesticides used in agricultural greenhouses in Menyeh-North Lebanon. The first part was dedicated to the analysis of green peppers, cucumbers, tomatoes, plastic films and air samples from these agricultural greenhouses. HPLC-HR-MS was used to quantify and monitor the residues of 4 pesticides: bifenazate (BIF), acetamiprid, imidacloprid and thiophanate methyl (TM) after QUECHERS extraction of the vegetables samples. The quantities of pesticides found within 6 days after spraying were well above the MRLs imposed for each one. Then, the photoproducts of TM, BIF and imidacloprid were identified after rinsing the surface of tomatoes, cucumbers and green peppers. This demonstrated the possibility of photodegradation of pesticides even inside an agricultural greenhouse. Gas phase analysis by GC-MS revealed the presence of terpenes, alkanes and aldehydes as the response of plants to temperature and spraying stresses. In a second part, we studied the photochemical mechanisms of BIF and TM in the laboratory under simulated irradiation. The auto-accelerated photodegradation of TM was reported for the first time. A detailed study enabled us to demonstrate that this auto-acceleration was due to the formation of a photosensitizing photoproduct derived from quinoxaline. The rate of degradation of BIF and the nature of the products were dependent on the medium (ACN, water, wax and green peppers). These results highlighted the effect of support and mixture on the photochemical behavior of pesticides.

Made available in DSpace on 2014-12-17T15:01:26Z (GMT). No. of bitstreams: 1 TalithaAB_DISSERT.pdf: 2174474 bytes, checksum: 5fc9b46f49baf0082200961f74eed779 (MD5) Previous issue date: 2011-08-23 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / Effluents from pesticide industries have great difficulty to decontaminate the environment and, moreover, are characterized by high organic charge and toxicity. The research group Center for Chemical Systems Engineering (CESQ) at the Department of Chemical Engineering of Polytechnical School of University of S?o Paulo and Department of Chemical Engineering, Federal University of Rio Grande do Norte have been applying the Advanced Oxidation Processes (AOP's) for the degradation of various types of pollutants. These processes are based on the generation of hydroxyl radicals, highly reactive substances. Thus, this dissertation aims to explore this process, since it has been proven to be quite effective in removing organic charge. Therefore, it was decided by photo-Fenton process applied to the degradation of the fungicide Thiophanate methyl in aqueous system using annular reactor (with lamp Philips HPLN 125W) and solar. The samples were collected during the experiment and analyzed for dissolved organic carbon (TOC) using a Shimadzu TOC (Shimadzu 5050A e VCP). The Doehlert experimental design has been used to evaluate the influence of ultraviolet radiation, the concentrations of methyl thiophanate (C12H14N4O4S2), hydrogen peroxide (H2O2) and iron ions (Fe2+), among these parameters, was considered the best experimental conditions, [Fe2+] = 0.6 mmol/L and [H2O2] = 0.038 mol/L in EXP 5 experiment and in SOL 5 experiment, obtaining a percentage of TOC removal of 60% in the annular reactor and 75% in the solar reactor / Os efluentes das ind?strias de agrot?xicos apresentam grande dificuldade quanto ? sua descontamina??o no meio ambiente e, al?m disso, s?o caracterizados por possu?rem alta carga org?nica e toxicidade. O grupo de pesquisa do Centro de Engenharia de Sistemas Qu?micos (CESQ) do Departamento de Engenharia Qu?mica da Escola Polit?cnica da Universidade de S?o Paulo e do Departamento de Engenharia Qu?mica da Universidade Federal do Rio Grande do Norte vem aplicando os Processos Oxidativos Avan?ados (POA) ? degrada??o de diversos tipos de poluentes. Estes processos s?o baseados na gera??o de radicais hidroxila, subst?ncias altamente reativas. Desta forma, buscou-se explorar esse processo, j? que o mesmo vem se apresentando bastante eficaz na remo??o de carga org?nica. Portanto, decidiu-se pelo processo foto- Fenton aplicado na degrada??o do fungicida tiofanato met?lico em sistema aquoso, utilizando reator anular (com l?mpada Philips, HPLN de 125W) e solar. As amostras foram coletadas durante o experimento e analisadas quanto ao teor de carbono org?nico dissolvido (COT) utilizando um analizador TOC (Shimadzu 5050A e Shimadzu VCH). O planejamento experimental Doehlert utilizado para avaliar a influ?ncia da radia??o ultravioleta, das concentra??es do tiofanato met?lico (C12H14N4O4S2), do per?xido de hidrog?nio (H2O2) e dos ?ons de ferro [Fe2+]. Dentre estes par?metros, foram consideradas as melhores condi??es experimentais, sendo: [Fe2+] = 0,600 mmol/L e [H2O2] = 0,038 mol/L no experimento EXP 5 e no experimento SOL 5, obtendo um percentual de remo??o de COT de 60% no reator anular e de 75% no reator solar

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Pesticides are widely used in agriculture and public health for pest control and prevention. The indiscriminate use of these compounds can trigger environmental contamination by pesticides and increase the risk of human exposure. Human exposure to pesticides can occur directly, through occupational activity, or indirectly, through the environment and food. Chronic exposure to pesticides may result in neurological, reproductive, teratogenic and immunological disorders. Mancozeb, chlorothalonil and thiophanate methyl are fungicides widely used in the world. Despite their characteristics of low acute toxicity and low persistence in the environment, in vitro and in vivo studies demonstrate the cytotoxic effects of these compounds. However, the immunological effects that these pesticides can trigger are unexplored. Therefore, the objective of this study was to evaluate in vitro the pro-inflammatory and oxidative effects of mancozeb, chlorothalonil and thiophanate methyl pesticides. RAW 264.7 (ATCC® TIB-71™) macrophages were exposed to different concentrations (0.1-100 μg/mL) of each pesticide for 72 hours, and maintained in 5% CO2 atmosphere at 37°C. The pesticides were dissolved in dimethylsulfoxide, which was used as negative control. Phytohemagglutinin was used as positive control for inflammatory activation. The evaluation of cell proliferation, oxidative metabolism and pro-inflammatory cytokines (IL-1β, IL-6, TNF-α and IFN-γ), anti-inflammatory cytokine (IL-10) and caspases (Casp1, Casp3, Casp8) levels were performed by fluorimetric and molecular tests. The results showed a significant pro-inflammatory effect of mancozeb, chlorothalonil and thiophanate methyl pesticides at respective concentrations of 1, 3 and 100 μg/mL, with increase in cell proliferation and pro-inflammatory cytokines and caspases levels. However, the oxidative effect was only observed in macrophages exposed to chlorothalonil at 3 μg/mL. Thus, in these analysis conditions, the studied pesticides acted by activation of the immune system. The results found contribute to better understanding of immunological effects caused by exposure to these pesticides. / Os pesticidas são amplamente utilizados na agricultura e na saúde pública para o controle e prevenção de pragas. O uso indiscriminado desses compostos pode desencadear a contaminação ambiental por agrotóxicos e aumentar o risco de exposição dos seres humanos. A exposição aos agrotóxicos pelos humanos pode ocorrer de forma direta, através de atividade ocupacional, ou de forma indireta, pelo ambiente e pela alimentação. A exposição crônica aos pesticidas pode resultar em distúrbios neurológicos, reprodutivos, teratogênicos e imunológicos. Os pesticidas mancozebe, clorotalonil e tiofanato metílico são fungicidas amplamente utilizados no mundo. Apesar de suas características de baixa toxicidade aguda e baixa persistência no ambiente, estudos in vitro e in vivo demonstram os efeitos citotóxicos desses compostos. Entretanto, os efeitos imunológicos que esses pesticidas podem desencadear são pouco explorados. Diante disso, o objetivo deste estudo foi avaliar in vitro o efeito pró-inflamatório e oxidativo dos pesticidas mancozebe, clorotalonil e tiofanato metílico. Os macrófagos RAW 264.7 (ATCC® TIB-71™) foram expostos a diferentes concentrações (0,1 – 100 μg/mL) de cada pesticida por 72 horas, sendo mantidos em atmosfera com 5% CO2 a 37oC. Os pesticidas foram dissolvidos em dimetilsulfóxido, o qual foi utilizado como controle negativo. Como controle positivo para a ativação inflamatória, utilizou-se a fitohemaglutinina. A avaliação da proliferação celular, do metabolismo oxidativo e dos níveis das citocinas pró-inflamatórias (IL-1β, IL-6, TNF-α e IFN-γ), da citocina anti-inflamatória (IL-10) e das caspases (Casp1, Casp3, Casp8) foi realizada por testes fluorimétricos e moleculares. Os resultados obtidos demonstraram efeito pró-inflamatório significativo dos pesticidas mancozebe, clorotalonil e tiofanato metílico nas respectivas concentrações de 1, 3 e 100 μg/mL, ocorrendo aumento da proliferação celular e dos níveis de citocinas pró-inflamatórias e caspases. Entretanto, o efeito oxidativo somente foi observado nos macrófagos expostos ao clorotalonil na concentração de 3 μg/mL. Assim, nessas condições de análise, os pesticidas estudados atuam ativando o sistema imune. Os resultados encontrados contribuem para a melhor compreensão dos efeitos imunológicos que a exposição a estes pesticidas pode desencadear.