Esta tese descreve o desenvolvimento de metodologias eletroanalíticas, em especial a voltametria de onda quadrada com o eletrodo de gota pendente de Hg, para determinação de atrazina em águas de rios do Estados de São Paulo e em amostras de solo. A exatidão das metodologias foi avaliada por comparação com HPLC e estudos de recuperação. Inicialmente desenvolveu-se o método em modo estático, no qual a maior sensibilidade foi obtida em pH 2 e freqüência de 400 Hz, com limites de detecção e determinação de 2 e 10 microgramas L-1, respectivamente. O estudo do comportamento eletroquímico revelou que a atrazina comporta-se reversivelmente em altas freqüências de onda quadrada. Dentre os metabólitos da atrazina, a desetilatrazina e desiosopropilatrazina, também são eletroativas nas condições estudadas, sendo possíveis interferentes, ao contrário da hidroxiatrazina e didealquilatrazina. Sistemas em fluxo contínuo e de injeção seqüencial foram desenvolvidos para determinação de atrazina em extrato de solo e águas naturais, bem como em estudos de adsorção. Em águas, os limites de detecção e determinação obtidos por injeção seqüencial foram de 4,5 e 15 microgramas L-1. Estudos de adsorção revelaram que atrazina liga-se mais fortemente a solos em meios ácidos. As metodologias em fluxo permitiram um significativo aumento da velocidade analítica e economia de reagentes, automatizando as determinações. / This thesis describes the development of electroanalytical methodologies, especially the square wave voltammetry with the hanging mercury drop electrode, for determination of the herbicide atrazine in river waters of the São Paulo state and soil samples. The accuracy of the methodologies was evaluated by comparison with HPLC and recovery studies. Initially, a stationary method was developed, in which the highest sensitivity was attained at pH 2 and at frequency of 400 Hz, with detection and quantification limits of 2 and 10 micrograms L-1, respectively. The electrochemical behavior of atrazine was reversible at the higher square wave frequencies. Among the atrazine metabolites, deethylatrazine and deisopropylatrazine are also electroactive under the studied conditions, being possible interferences, contrary to hydroxyatrazine and didealkylatrazine. Continuous flow and sequential injection systems were developed for determination of atrazine in soil extracts and natural waters, as well as in adsorption studies. In waters, the detection and quantification limits attained by sequential injection were 4.5 and 15 micrograms L-1. Adsorption studies showed that atrazine binds more strongly to soil in acidic media. The flow analysis methodologies lead to significant increase in the sampling throughput and reagent saving, automating the determinations.

Neste estudo foi avaliada a remoção de metil paration - inseticida e atrazina - herbicida presentes em água, em reatores de bancada, com fungos. A pesquisa foi dividida em quatro etapas: operação em batelada com metil paration e micélio fúngico, com e sem glicose; teste de toxicidade em placas com Aspergillus niger AN400; operação em batelada com os pesticidas atrazina e metil paration e esporos de Aspergillus niger AN400, com e sem glicose; e operação em reatores de leito fixo e fluxo ascendente. Na primeira etapa, a remoção de metil paration foi de 97% nos reatores sem glicose e 94% nos reatores com glicose com 32 dias de reação. Na operação em batelada, com esporos, um modelo cinético de primeira ordem representou bem a velocidade de decaimento de metil paration nesta fase, principalmente, nos reatores que continham glicose. Para os experimentos sem adição de glicose, a constante cinética foi de 0,063 &#177 0,005/h, enquanto que para os experimentos com glicose a constante foi de 0,162 &#177 0,014/h. Dessa forma, a adição de glicose resultou efetivamente em aumento na velocidade de conversão do inseticida. Na fase experimental, com atrazina e esporos de Aspergillus niger AN400, a presença do substrato primário (glicose) não teve influência na remoção de atrazina, sendo que os percentuais de remoção foram muito próximos aos percentuais encontrados nos reatores sem glicose. O estudo cinético, nessa fase com atrazina e esporos, revelou que para os experimentos sem a adição de glicose, o valor da velocidade de conversão de atrazina (RATZo) foi de 0,023/d, enquanto que para os experimentos com glicose (RATZo) foi 0,022/d. Portanto, a adição de glicose parece não ter influenciado significativamente a velocidade de remoção do herbicida por Aspergillus niger AN400. O teste de toxicidade demonstrou que metil paration e atrazina não inibiram o crescimento do fungo nas várias concentrações testadas, inclusive nas mais elevadas, que foram 60 mg/L e 25 mg/L para metil paration e atrazina, respectivamente. No reator de leito fixo a remoção de metil paration foi de 40% com 12 h de tempo de detenção hidráulica, e 0,5 g glicose/L. Porém, quando a concentração de glicose foi duplicada a remoção de metil paration diminuiu para 35%. Neste reator o pH se manteve na faixa ácida 3,4 a 5,2, considerada ideal para os fungos. Os resultados encontrados mostram a viabilidade dos fungos para remoção desses pesticidas, considerados persistentes no ambiente. / In this study the removal of methyl parathion was evaluated - insecticide and atrazine - herbicide present in water, in reactors with fungi. The research was divided in four stages: operation in batch reactors with methil parathion and micelium fungus, with and without glucose; toxicity test in plates with Aspergillus niger AN400; operation in batch reactors with the pesticides atrazine and methyl parathion and spore of Aspergillus niger AN400, with and without glucose; and operation in reactors of fixed bed and ascending flow. In the first stage the removal of methyl parathion was 97% in reactors without glucose and 94% in reactors with glucose in 32 days of reaction time. In the operation in batch with spores, a kinetic model of first order represented very well the speed of decline of the methyl parathion in this step, in the reactors that contained glucose, mainly. For the experiments without the glucose addition, the kinetic constant was 0,063 &#177 0,005/h, and for the experiments with glucose the constant was of 0,162 &#177 0,014/h. In that way, the glucose addition resulted in increase in the speed of conversion of the insecticide. In the experimental step with atrazine and spores of Aspergillus niger AN400, the presence of the primary substratum (glucose) didn\'t have influence in the atrazine removal, and the percentile removal lays very close to the percentile found in the reactors without glucose. The kinetic study, in that step with atrazine and spores, revealed that for the experiments without the glucose addition, the value of the speed conversion of atrazine (RATZo) was 0,023/d, and for the experiments with glucose (RATZo) was 0,022/d. Therefore, the glucose addition seems not to have influenced significantly the speed of removal of the herbicide for Aspergillus niger AN400. The toxicity test demonstrated that methyl parathion and atrazine didn\'t inhibit the growth of fungi in the several concentrations, including in high concentrations, that were tested 60 mg/L and 25 mg/L to methyl parathion and atrazine, respectively. The reactor of fixed bed got removal of methyl parathion of 40% in 12 hours of detention hydraulic, in 0,5 g glicose/L. However, when the glucose concentration was doubled the removal of methyl parathion decreased to 35%. In this reactor the pH kept in the acid strip (3,4 - 5,2), considered ideal for the fungi, and conductivity values didn\'t favor the hydrolysis of the insecticide. The found results show the viability of the fungi for removal of those pesticides, considered recalcitrant to the environment.

[pt] O impacto dos pesticidas sobre a qualidade das águas subterrâneas tem sido objeto de preocupação de cientistas e autoridades públicas do nosso planeta. O uso intensivo de pesticidas na agricultura e a alta persistência de muitos deles tem requerido um rigoroso controle para evitar possíveis contaminações das águas subterrâneas e superficiais. O herbicida atrazina é um poluente freqüentemente encontrado nas águas subterrâneas em muitos países e foi selecionado para este estudo. O objetivo principal deste trabalho foi avaliar a efetividade, em escala de laboratório, da remediação de águas subterrâneas contaminadas com atrazina a partir do tratamento com ozônio produzido eletroquimicamente in situ. O anodo de β-PbO2 foi empregado na produção do ozônio por via eletroquímica e foi obtido por eletrodeposição sobre um substrato de titânio. A análise do depósito de PbO2 pela técnica de difração de raios-X confirmou apenas a presença das fases α e β do PbO2 e apontou a fase β como a principal. Foi comprovado que o aumento da corrente elétrica aumenta a taxa de produção de ozônio. Taxas de produção de O3 de 4,4; 19,5 e 39,1 mg h(-1) foram obtidas a partir de valores de densidades de correntes de 0,5, 1,0 e 1,5 kA m(-2),respectivamente. Os experimentos de degradação em batelada de uma solução de atrazina com concentração igual a 1 mg L(-1) para densidades de corrente de 0,5, 1 e 1,5 kA m(−2) mostraram que, com o aumento da densidade da corrente ocorreu um acréscimo na taxa de degradação da atrazina. Isto indica que o maior poder de oxidação do anodo, na medida em que se incrementa a corrente aplicada, é devido à maior eletrogeração dos oxidantes O3/.OH. A partir da análise cinética dos resultados obtidos nos experimentos de degradação foram obtidas boas correlações lineares quando os dados foram ajustados seguindo um modelo de pseudo-primeira ordem. As constantes cinéticas de pseudo- primeira ordem calculadas foram 6,2×10(−3), 8,8×10(−3) e 1,21×10(−2) min (−1) para 0,5, 1 e 1,5 kA m(−2), respectivamente. Os experimentos de degradação de atrazina em fluxo contínuo foram realizados numa coluna de acrílico de forma cilíndrica (26 cm x 4cm DI) preenchida com areia lavada, simulando o material do aqüífero, contendo um anodo de Ti/β-PbO2 e um catodo de Ti/RuO2. Durante os experimentos houve uma diminuição progressiva da concentração de atrazina no efluente de saída da coluna. Após 8 horas, as concentrações de atrazina na saída da coluna foram 75% e 80% menores do que a concentração de atrazina na entrada da coluna quando se aplicaram correntes de 0,4 e 0,6 A, respectivamente. Estes resultados confirmam a potencial aplicação deste tipo de estratégia de controle de plumas de contaminação e proporciona as bases para o desenvolvimento futuro desta técnica de remediação de aqüíferos. / [en] The impact of pesticides on the quality of groundwater has been the subject of scientific and public health concerns in the entire planet, especially in areas where groundwater is mainly used for human consumption. The intensive use of pesticides in agriculture and the high persistence of several of these chemicals have required a rigorous control of possible environmental contaminations, especially of drinking water sources. The herbicide atrazine is frequently detected in natural waters of many countries and was selected for investigation. A laboratory scale study on the evaluation of the effectiveness of remediation of atrazine in groundwater utilizing in situ electrochemical generated ozone was conducted. β-PbO2 was used as anode for ozone generation. β-PbO2 electrodes were prepared by electrodeposition on Ti plates. X-ray diffraction analysis confirmed that the deposit contained only the α and β PbO2 with the β phase prevailing. The electrochemical ozone production increases with incrementing the current density. The rate of ozone production during the electrolysis was 4.4, 19.5 and 39.1 mg h-1 for current densities of 0.5, 1.0 and 1.50 kAm(-2), respectively. In the experiments of atrazine degradation by electrochemically generated ozone a difference in atrazine degradation was found when the applied current density was varied. The results evidenced that the atrazine degradation rates increased with augmenting the current density. This is indicative of a greater oxidation ability of the anode with increasing the current applied due to the production of more electrogenerated active oxidant (O3/.OH). The kinetic analysis of the above results related to different reaction orders gave good linear correlations when the data was fitted with a pseudo first-order reaction rate equation. The pseudo first-order rate constants obtained were 6.2×10(−3), 8.8×10(−3), and 1.21×10(−2) min(−1) for 0.5, 0.1, and 1.5 kA m(−2), respectively. The acrylic column (26 cm x 4 cm ID) used in flow degradation experiments was packed with clean sand and contained a single set of electrodes. Two expanded titanium mesh coated with β-PbO2 and RuO2 served as anode and cathode, respectively. During the experiments the atrazine effluent concentration progressively diminished. After 8 hours of electrolysis the effluent atrazine concentration was reduced by 75% and 80% applying current densities of 0.4 and 0.6, respectively. These results confirm the potential applicability of this type of groundwater plume control strategy. The study constitutes a foundation to the future developing of this aquifer remediation technique.

BackgroundAtrazine suppression of the LH surge slowly develops over time and peaks after 4 days; sensitivity to atrazine decreases after 8 or 14 days of dosing. Adaptation of the LH response was correlated with increased phase I and phase II liver enzyme activity/expression. MethodsThe effect of atrazine on the LH surge was evaluated in female Sprague-Dawley rats administered 100 mg/kg/day atrazine by gavage for 1, 2, 3, or 4 consecutive days or 6.5, 50, or 100 mg/kg/day atrazine for 4, 8, or 14 days. ResultsNo statistically significant effects of atrazine were seen on peak plasma LH or LH area under the curve (AUC) after one, two, or three doses of 100 mg/kg/day. Four daily doses of 50 or 100 mg/kg atrazine significantly reduced peak LH and LH AUCs, whereas 6.5 mg/kg/day had no effect. After 8 or 14 days of treatment, statistically significantly reduced peak LH and LH AUC were observed in the 100 mg/kg/day dose group, but not in the 6.5 or 50 mg/kg/day dose groups, although significantly reduced LH was observed in one sample 9 hr after lights-on in the 50 mg/kg/day dose group on day 14. The number of days of treatment required to achieve a significant suppression of the LH surge is consistent with the repeat-dose pharmacokinetics of the chlorotriazines. ConclusionThe apparent adaptation to the effect of atrazine on the LH surge after 8 or 14 days may be related to the induction of phase I or, more likely, phase II metabolism observed in this study after 8 days, or to a decreased sensitivity of the hypothalamic-pituitary-adrenal axis or an homeostatic adaption of the effect of atrazine on the LH surge mechanism. Birth Defects Research 110:246-258, 2018. (c) 2017 The Authors. Birth Defects Research Published by Wiley Periodicals, Inc.

The toxicity of methanol, atrazine, and copper to Pseudokirchneriella subcapitata (Korshikov) Hindák historically referred to as Selenastrum capricornutum Printz were determined following 96 hrs growth in a modified Goram's growth media. Methanol and atrazine inhibited fluorescence readings in the cultures by 50% (IC50) at concentrations of 2% and 82 µg/l respectively. These toxicity values compared favorably to other published reports. The IC50 for copper was 160 µg/l which is substantially higher than reported values. This is understandable because of the high chelating capacity of Goram's media. The use of stereologically derived relative volume in the chloroplasts, mitochondria, lipid bodies, phosphate bodies, and nucleus was investigated to determine if it could be used as a sensitive endpoint in toxicity tests. The volume fractions for the chloroplasts and mitochondria were normally distributed in control cells while the nuclei, phosphate bodies, and lipid bodies were not. The chloroplasts were the most dominate organelle occupying a mean relative volume of 46% and mitochondria occupied a mean relative volume of 3%. The nucleus and phosphate bodies occupied a median relative volume of 7% and 2% respectively. The lipid bodies were rare in section profile and no meaningful median relative volume could be calculated. Up to the 82nd percentile of sectioned profiles contained no recognizable lipid bodies. The use of relative volume was not a sensitive endpoint for use in toxicity tests. No significant differences in relative volume could be detected in the nucleus or phosphate bodies following any treatment. Limited differences were detected in the mitochondria, chloroplasts, and lipid bodies. The only significant differences that appear to be biologically significant occurred in methanol treated cells where an increase in the lipid bodies' relative volume was apparently concentration dependent. Significant differences in the relative volume of mitochondria and chloroplasts do not appear to be biologically significant.

Orientador: José de Alencar Simoni / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-26T20:46:57Z (GMT). No. of bitstreams: 1 Curti_GabrielJeronymo_D.pdf: 2740453 bytes, checksum: e587cb4af6da5b69a349e04e62b2a63c (MD5) Previous issue date: 2014 / Resumo: Sabe-se que na agricultura a qualidade de um solo é dependente do tipo de manejo. No presente trabalho foi aplicada a microcalorimetria isotérmica para se investigar a influência do herbicida atrazina na atividade microbiana de um solo envelhecido de mata nativa, mantido a aproximadamente 4 °C, durante três anos. Além da utilização da microcalorimetria isotérmica, foram realizadas as análises de DSC e TG com a finalidade de se avaliar a quantidade de matéria orgânica presente no solo estudado, cujo valor quantificado foi de (3,5 ± 0,2)% g/g. Também foi realizado o cálculo da humidade do solo e as análises elementares [CHN e EDS (Energy Dispersive X-Ray Detector) acoplado ao MEV (Microscópio Eletrônico de Varredura)]. As amostras de solo utilizadas na análise microcalorimétrica foram previamente incubadas com acetonitrila e com soluções de atrazina em acetonitrila nas concentrações de 1000 e 2000 ppm, durante aproximadamente 48 horas. Em seguida, foi descoberto com o emprego da microcalorimetria isotérmica que a acetonitrila ainda permanecia no solo após o período de incubação, além do fato de que o efeito da atrazina sobre os microrganismos do solo não era detectável, uma vez que os valores para o calor gerado durante a incubação com aquele solvente e com as soluções de atrazina em acetonitrila nas concentrações de 1000 e 2000 ppm, respectivamente, eram iguais a: (-12,8 ± 0,8), (-12,9 ± 0,9) e (-13,5 ± 0,6) J, enquanto que os valores da constante do crescimento microbiano eram iguais a: (5,9 ± 1,4), (6,8 ± 1,6) e 6,37 min-1. A análise microbiológica também indicou que a atrazina não estaria influenciando os microrganismos, diferentemente do caso da acetonitrila, a qual foi responsável por uma redução nas quantidades dos microrganismos. No presente trabalho também foi investigada a influência do herbicida nicosulfuron sobre as atividades microbianas nos solos de mata nativa ou floresta e de cultivos do milho e do café. Foram empregadas as mesmas técnicas analíticas como no caso da atrazina, sendo que para se estudar o nicosulfuron foram investigadas as seguintes condições de incubação (durante 48 h) para cada tipo de solo: aplicação de acetonitrila, aplicação de uma solução de nicosulfuron em acetonitrila com uma concentração igual a 64 ppm e aplicação de uma solução com a mesma natureza, mas com uma concentração igual a 120 ppm. Os resultados indicaram que o solo de floresta era o mais rico em termos de matéria orgânica (4,0 ± 0,1)%, enquanto que o solo de cultivo do café era o mais rico em termos de humidade (21 %). Preliminarmente, as análises térmicas realizadas com o auxílio da microcalorimetria isotérmica indicaram que a acetonitrila foi novamente a espécie mais biodegradada, ao passo que nos casos das condições em que havia adição de água ao invés da solução de glicose pôde ser concluído que o solo cultivado com café foi aquele que mais sofreu influência do nicosulfuron do que nos casos dos outros solos, uma vez que para o valor de concentração mais elevado, i.e., 120 ppm, o valor da energia dissipada (calor; Q) foi estatisticamente superior (-6,6±0,3)J do que no caso da solução da mesma natureza com concentração igual a 64 ppm (-4,8±0,9)J. Para os solos de floresta ou mata nativa e de cultivo do milho o nicosulfuron não exerceu influência detectável. As análises microbiológicas para os solos de cultivo do café e do milho não indicam que ocorram diferenças estatisticamente significativas para algumas das condições estudadas, de tal maneira que para o estudo com o nicosulfuron podemos concluir que a microcalorimetria isotérmica se mostra uma técnica promissora que pode permitir estudos com xenobióticos como os pesticidas / Abstract: It is known in agriculture that soil quality does dependent on the kind of soil management. In the present work was applied the isothermal microcalorimetry to investigate the influence of the herbicide atrazine on the microbial activity of a forest soil that was aged (resting along 3 years under about 4°C). Besides the application of isothermal microcalorimetry it were performed the DSC and TG analyses with the purpose to evaluated the amount of organic matter present in the soil whose value was equal to (3.5±0.2) % to the studied soil. It were also performed the calculation of humidity in the soil and the elemental analyses [CHN and EDS (Energy Dispersive X-Ray Detector) coupled to SEM (Scanning Electron Microscopy)]. The soil samples used for the microcalorimetric analysis were previously incubated with acetonitrile and atrazine solutions in acetonitrile (1000 ppm and 2000 ppm), during approximately 48 hours. Afterwards, with the aid of the Isothermal Microcalorimetry it was discovered that actually the acetonitrile was remaining in the soil, even after the incubation period and that the effect of atrazine on the soil microorganisms was undetectable, once the heat generated for the incubation with acetonitrile and with atrazine solutions in acetonitrile of 1000 and 2000 ppm were equal respectively to: (-12.8 ± 0.8); (-12.9 ± 0.9) and (-13.5 ± 0.6) J, whilst that the values of the microbial growth constant were equal to: (5.9±1.4); (6.8±1.6) and 6.37 min-1. The microbiological analysis also indicated that the atrazine was not influencing the microorganisms, differently for the case of acetonitrile that was responsible for a decrease on the amounts of them. It was also investigated in that work the influence of the herbicide nicosulfuron on the microbial activities of soils under forest, and under maize and coffe tree crops. The same kind of analyses were performed as for the case of atrazine, but the investigations occured after a previous period of incubation along 48 h, and the conditions evaluated were: application of acetonitrile, application of nicosulfuron solution in acetonitrile with concentration equal to 64 ppm and application of a solution with the same nature but with concentration equal to 120 ppm. The results indicated that the forest soil was the richest one in terms of organic matter ( 4.0 ± 0.1) % , whilst the soil that lies under a coffe tree crop was the richest one in terms of humidity (21 % ). The thermal analyses with the aid of the Isothermal Microcalorimetry indicated preliminary that again acetonitrile was biodegradated mostly. However, for the soil tilled under coffe tree crop, considering the same conditions discussed previously for nicosulfuron but with the addition of deionized water after 48 h, the microbial activity was more stimulated by the nicosulfuron than respect to the other conditions, once with the solution of nicosulfuron with the highest concentration, i. e., 120 ppm, the value for the heat dissipated (Q) was statistically higher (-6.6±0.3) than for the concentration equal to 64 ppm (- 4.8 ± 0.9), while that in the forest soil and for the soil tilled with maize crop its influence was undetectable. The microbiological analysis for the forest soil and for the soil under maize crop shown that there are no differences that are statistically significant for some conditions studied, in such a way that for the study with nicosulfuron we can conclude that the Isothermal Microcalorimetry shows itself a promising technique that can allow studies with xenobiotics as the pesticides / Doutorado / Físico-Química / Doutor em Ciências

Orientador: Antonio Francisco Godinho / Resumo: O herbicida atrazina (ATR) é um praguicida usado intensivamente na agricultura, que persiste no meio ambiente e causa toxicidade em espécies não-alvo, inclusive seres humanos. Considerando o potencial da ATR para produzir efeitos no sistema nervoso central (SNC) e a falta de informações na literatura corrente sobre esse tipo de toxicidade, o objetivo deste projeto de pesquisa foi avaliar os efeitos da exposição subcrônica ao herbicida ATR sobre parâmetros neurocomportamentais específicos e estabelecer sua correlação com o estresse oxidativo (EO) em tecido cerebral de ratos e com o sistema dopaminérgico em regiões específicas do cérebro, nominalmente córtex pré-frontal (CPF), hipocampo (HIP) e corpo estriado. Ratos Wistar machos receberam solução salina (0,3 ml; controle - Ct), atrazina (ATR; 100 mg/kg), atrazina mais vitamin E (ATR; 100 mg/Kg + VE; 200 mg/kg), apenas vitamina E (VE; 200 mg/kg), atrazina mais levodopa (ATR; 100 mg/Kg + LEV; 20 mg/kg) e apenas levodopa (LEV; 20 mg/kg), por gavage, durante 28 dias. O comportamento foi avaliado utilizando arena de campo aberto (ACA), labirinto em cruz elevado (LCE) e hole-board (HB). O teste de estresse oxidativo no tecido cerebral avaliou os níveis de malondialdeído (MDA), capacidade antioxidante hidrofílica (CAH) e atividade das enzimas superóxido dismutase (SOD) e catalase (CAT). A dopamina (DA) foi quantificada por HPLC, em áreas cerebrais específicas (CPF, HIP e estriado). Exposição à ATR provocou ansiedade, diminuiu a coord... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Atrazine (ATR) herbicide is a pesticide used intensively in agriculture that persists in environment and causes toxicity on non-target species, include humans. Considering the potential of ATR to produce effects on the central nervous system (CNS) and the lack of information in the current literature about this type of toxicity, the aim of this research project was to evaluate the effects of subchronic exposure to ATR herbicide on specific neurobehavioral parameters and to establish its correlation with oxidative stress (OE) in rat brain tissue and with the dopaminergic system in specific brain regions, nominally prefrontal cortex (PFC), hippocampus (HIP) and striatum. Male Wistar rats received saline (0.3 ml; control - Ct), atrazine (ATR; 100 mg/kg), atrazine plus vitamin E (ATR; 100 mg/Kg + VE; 200 mg/kg) only vitamin E (VE; 200 mg/kg), atrazine plus levodopa (ATR; 100 mg/Kg + LEV; 20 mg/kg) and only levodopa (LEV; 20 mg/kg), via gavage, during 28 days. Behavior was assessed using open field arena (OF), elevated plus-maze (EPM) and hole-board (HB) apparatus. Oxidative stress assay in brain tissue evaluated malondialdehyde (MDA) levels, hydrophilic antioxidant capacity (HAC), and superoxide dismutase (SOD) and catalase (CAT) enzymes activity. Dopamine (DA) was quantified using HPLC, in specific brain areas (PFC, HIP and striatum). ATR exposure caused anxiety-like behavior, decreased motor coordination and did not alter the locomotor activity of the animals. ATR did not chang... (Complete abstract click electronic access below) / Doutor

The application of commercial herbicide restricts weed growth and significantly improves control over crop vitality and yield. Despite their utility in the agriculture sector, herbicides have the potential to contaminate local water sources. To minimize environmental impacts, the development of efficient separation processes to clean-up contaminated water bodies is necessary. However, complex speciation and conformational flexibility in the condensed phase poses a significant challenge. In this work, we investigate structure and speciation of three common organic herbicides (glyphosate, atrazine, and metolachlor) in aqueous solution. We employ the PBE-D3 density functional to perform ab initio molecular dynamics (MD) simulations in the canonical and isothermal-isobaric ensembles. We analyze MD trajectories to understand hydrogen bonding dynamics and lifetime as well as diffusional and vibrational characteristics. To enhance configurational sampling, we conduct metadynamics simulations to obtain the free energies of dissociation and intramolecular proton transfer of glyphosate.

No description available.

A disposal system for pesticide waste was examined for the ability to isolate waste pesticides onto lignocellulosic matrices, such as peat moss (PM) or steam-exploded wood fibers (SEW) by sorption processes, and to detoxify the pesticide during solid state fermentation (SSF) in contained bioreactors. Emulsions formed from typical pesticide formulations acts as a barrier for pesticide sorption. Adding Ca(OH)₂ for demulsification ofDursban® 4E and filtering suspended particulates was the most effective steps for decreasing chlorpyrifos concentration. Activated carbon (AC) and rubber (R) were better at sorbing chlorpyrifos than the PM and SEW, even though the two sorbents were capable of removing approximately 95% chlorpyrifos from solution. Secondary columns of AC or R could be employed to further remove chlorpyrifos or similar pesticides from the waste water. Atrazine and chlorpyrifos dissipation in field SSF bioreactors increased with higher bioreactor temperatures (65 °C). Dissipation time for 50% parent compound disappearance (DT₀) of atrazine in 1 m³, cylindrical (1 m diameter), and plastic bag (189L) bioreactors were 2, 14, and days, respectively. The chlorpyrifos DT₀ values for the same bioreactors were 59, 20, and 50 days, respectively. Chlorpyrifos did not volatilize outside the compost as expected, but was found condensed in the cooler outer regions of the bioreactor matrix. Supplemental energy and fertilizer sources (com meal, vegetable oil, and chicken manure) enhanced microbial activity and pesticide degradation in field bioreactors. The dissipation of atrazine was not enhanced by nutrient amendment in laboratory studies involving ¹⁴C-radiolabeled atrazine and chlorpyrifos at 40 °C over 16 weeks. The DT₀ values were 4 weeks for nutrient amended and unamended bioreactors. Nutrient amendment increased chlorpyrifos dissipation with DT so values of approximately 11 and 17 weeks for nutrient and unamended bioreactors but not in the atrazine bioreactors. Dissipation of chlorpyrifos was mainly through volatility and degradation, whereas atrazine dissipated by degradation and unextractably associated with the matrix. It is important to keep pesticide waste bioreactors well aerated, moist, and mixed with additions of nitrogen and fresh biomass to facilitate the dissipation and detoxification of pesticides. The remaining residue can be land applied, land filled, or incinerated. / Ph. D.