No description available.

Atmospheric transport and air-water exchange of organochlorine pesticides (OCPs) were investigated in temperate North America and the Arctic. OCPs studied were hexachlorocyclohexanes (HCHs, a-, b- and g-isomers), components of technical chlordane (trans- and cis-chlordane, trans-nonachlor), dieldrin, heptachlor exo-epoxide and toxaphene. Air and water samples were taken on cruises in the Great Lakes and Arctic to determine concentrations and gas exchange flux direction and magnitude. The Henry’s law constant, which describes the equilibrium distribution of a chemical between air and water, was determined for several OCPs as a function of temperature and used to assess the net direction of air-water exchange. Air samples were collected in Alabama to investigate southern U.S. sources of OCPs. Chemical markers (isomers, and enantiomers of chiral OCPs) were employed to infer sources and trace gas exchange. Elevated air concentrations of toxaphene and chlordanes were found in Alabama relative to the Great Lakes, indicating a southern U.S. source. Profiles of toxaphene compounds in air were similar to those in soil by being depleted in easily degraded species, suggesting that soil emissions control air concentrations. Gas exchange fluxes in the Great Lakes indicated near-equilibrium between air and water with excursions to net volatilization or deposition. Net volatilization of a-HCH from the Arctic Ocean was traced by evasion of non-racemic a-HCH into the atmosphere.

Vinclozolin (VCZ), an antiandrogenic fungicide, is an endocrine disrupting chemical that is known to possess high affinity for the androgen receptor (AR) and modulate expression of critical androgen-dependant genes in the prostate. In this study, viability and expression of AR, NKX3.1 and CYP3A4 genes were measured in androgen-sensitive prostate cells LNCaP after exposure to VCZ and VCZ treated with S9 microsomes in a time and dose dependent manner. NKX3.1 is an androgen regulated gene that plays a vital role in prostate development. CYP3A4 is involved in xenobiotic metabolism. VCZ decreased the viability at high doses after 48 hours which was slightly mitigated by treatment with S9 metabolites. Expression of NKX3.1 and CYP3A4 was upregulated while an initial downregulation of AR was observed. NKX3.1 upregulation corroborates with possibility of antiandrogens to act as androgens in LNCaP. The results illustrate that VCZ can interfere with the expression of critical prostate genes.

In recent years there has been a great deal of scientific interest in processes that affect the fate of organic chemicals in the environment. one main reason for this increased interest is due to greater environmental concern over accidental or purposeful release of these chemicals into the environment by man. A major environmental concern is the increased use of pesticides over the last few years. In the thirty years prior to 1978 the use of pesticides has increased by a factor of forty (Ridgeway et al., 1978). Recently the use of herbicides has been increasing, but that of insecticides has stabilized (Willis, 1983). Detectable amounts of organic pesticides can be found in many areas of the biosphere. For toxic organic chemicals to be used safely, researchers must have a clear understanding of the fate and persistence of these chemicals when they are released into the environment. This understanding will also allow the development of new products that, when properly used, will not produce adverse effects to man or the environment (Weber, 1972). According to the Toxic Substance Control Act (TSCA) any new or expanded-use chemical that might be released into the environment must be tested for environmental hazard.

Call number: LD2668 .T4 1986 S36 / Master of Science / Horticulture, Forestry, and Recreation Resources

Thesis (M. Tech. - Dept. of Chemistry, Faculty of Applied and Computer Sciences) -- Vaal University of Technology, 2010 / The increased production and application of pesticides for agricultural and non-agricultural purposes has caused the pollution of air, soil, ground and surface water. This has a negative impact on the environment as well as human health due to direct exposure or through residues in food and drinking water. The continuous monitoring of pesticides residues in environmental samples has great importance and demands high efficiency, unique selectivity and high sensitivity techniques. Gas chromatography and high performance liquid chromatography have been established for years as the techniques for the analysis of pesticides residues. The dissertation deals with the qualitative and quantitative determination of selected pesticides in the Southern Gauteng region using Liquid- liquid extraction solid-phase extraction, high performance liquid chromatography, gas chromatography equipped with electron capture detector and gas chromatography mass spectrometry. Liquid-liquid extraction and solid-phase extraction using dichloromethane, hexane and ethyl acetate as the extracting solvent were optimized and evaluated for the determination of pesticides in surface water in the Southern Gauteng region. From the developed method the techniques were applied to water samples taken from different rivers selected namely: Zuikerbosch, Rand Water barrage and Kliprivier for sampling. Dichloromethane was used as a solvent in this study since a recovery test was done between dichloromethane, Ethyl acetate and n-hexane. The percentage recovery test for 4,4-DDT, 4,4-DDE, 2,4-DDD and Endosulfan 1 & 2 ranged from 89.9% -97.3% for dichloromethane, 87.3%-96.8% for hexane 88.4%-97.1% for ethyl acetate. The extracts obtained were subjected to column chromatography for clean up. Thereafter 1µl of the cleaned extracts were injected into the Gas chromatography equipped with an electron capture detector. Organochlorines 4,4-DDT and its metabolites, Organophosphate Chlorypyriphos and carbamates were detected using Gas chromatography electron capture, Gas chromatography mass spectrometry and high performance liquid chromatography.

[pt] A partir do trabalho de campo feito na região agrícola de Nova Friburgo, RJ, determinou-se que o pesticida Paraquat é altamente usado. Investigou-se o processo de adsorção com carvão ativado e carvão vegetal deste pesticida em solução aquosa, como uma alternativa para o tratamento de águas residuarias da região. Foi utilizado um resíduo de carvão vegetal, denominado carvão A; e dois carvões ativados comerciais de procedências distintas, denominados respectivamente de carvão B (Brasil) e carvão C (EUA). Realizou-se uma oxidação química com HNO3 do carvão brasileiro, sendo o carvão assim tratado denominado carvão B1. Os estudos de adsorção foram precedidos de um estudo de caracterização dos carvões utilizados, através de microscopia eletrônica de varredura (MEV) e espectroscopia de dispersão de raios X (EDS), para a sua caracterização morfológica. Da isoterma de adsorção de nitrogênio a 77 K, obtiveram-se dados do volume de microporos, área superficial e distribuição de tamanhos dos poros. Espectros de FT-IR detectaram a presença de grupos funcionais nas superfícies e medições de potencial zeta permitiram a determinação do ponto isoelétrico para cada carvão estudado. No processo de adsorção em batelada foram avaliados os efeitos do pH e do tempo para se alcançar o equilíbrio. Foram levantadas experimentalmente isotermas de adsorção para os quatro tipos de carvão. Os carvões ativados B, B1 e C se ajustaram satisfatoriamente ao modelo de isoterma de Freundlich. Estas isotermas forneceram informação a respeito das capacidades de carregamento desses carvões. No estudo da cinética de adsorção, foram avaliadas as correlações dos modelos de pseudo-primeira ordem e pseudo-segunda ordem com os dados experimentais obtidos. Finalmente, os testes preliminares em coluna, em regime contínuo, permitiram a obtenção da curva de carregamento (curva de breakthrough) para o carvão ativado comercial de fabricação brasileira. / [en] According to the work performed in the agricultural region in Nova Friburgo, RJ; it was determined that the Paraquat Pesticide is highly used. There have investigated the adsorption process with activated carbon and vegetal charcoal for pesticide treatment in aqueous solution, this will an alternative for the wastewater treatment in this region. The experimental study was conducted for a vegetal charcoal and two kinds of porous carbonaceous materials. The first of those was a charcoal made of Eucalyptus spp. wood shavings (carbon A). The second was Brazilian activated carbon (carbon B) made of coconut shell. The third material was an American coconut shell activated carbon (carbon C). The Brazilian activated carbon was further submitted to chemical modification treatment procedure with HNO3 (carbon B1). The tests of adsorption were preceded by study of characterization of the used carbons, through techniques such as scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS), for its morphologic characterization. The nitrogen adsorption isotherm at 77 K, obtained data of micropore volume, superficial area and poro size distribution. Besides, the FT-IR spectroscopy detected the surfaces functional groups and the Zeta Potential Zeta determinate of the isoelectric point for each carbon. The main parameters influencing adsorption treatment process, pH and equilibrium time have been examined. There have been experimentally made adsorption isotherms for the four types of carbons, which for the carbons (B, B1 and C) adjust to the Freundlich isotherm model. The uptakes capacities information of carbons was originated by these isotherms. The pseudo-first order model and pseudo-second order model was used for evaluated the kinetic data experimental in this process. Finally, the preliminary tests in column had given a vision about of the continue adsorption and the breakthrough curve formation.

Os polietilenoglicóis (PEGs) são polímeros sintéticos não iônicos, solúveis em água, que possuem diferentes propriedades físico-químicas devido ao efeito de sua cadeia longa, conferindo assim uma vasta disposição na aplicação industrial do PEG. Como exemplos de aplicação destacam-se o uso como lubrificante solúvel em água para moldes de borracha, fibras têxteis e operações de formação de metais, sendo também usado em tintas à base de água, revestimento de papéis, polimento, na indústria cerâmica, na confecção de fases estacionárias para cromatografia, entre inúmeras outras. O PEG também pode ser adicionado às dietas de ruminantes baseadas em foragem com alto teor de taninos, onde ele se insere como um agente complexante do tanino. Contudo, devido à ampla aplicação do PEG, mostra-se uma maior preocupação com seu uso e disposição no meio ambiente, uma vez que sua concentração, seja no solo ou água, possa ser grande. No entanto, pouco se sabe acerca do seu destino no ambiente, principalmente em condições tropicais, sendo que não foram encontrados na literatura estudos de monitoramento de águas subterrâneas e superficiais, e nem mesmo estudos de impacto ambiental. Neste contexto, este projeto se insere na busca sobre o destino do PEG-4000 no ambiente, buscando informações sobre sua mobilidade, degradação e sorção em solos, utilizando técnicas radiométricas (14C-PEG). Complementando o estudo do PEG, foi avaliado o transporte de pesticidas na presença do PEG, uma vez que ele possui uma alta solubilidade, podendo atuar como co-solvente, avaliando assim o papel do PEG na presença de contaminantes / Polyethylene glycols (PEGs) are non-ionic synthetic polymer, soluble in water, which have different physical and chemical properties because of its long chain, thereby providing a broad industrial application of PEG. Examples of application are the use as water-soluble lubricant for rubber molds, textile fibers and metallurgy, also used in water-based paints, paper coating, polishing, ceramic industry, in construction of stationary phases for chromatography, and numerous others. PEG can also be added to the diets of ruminants based on forage with a high content of tannins, where it comes as a complexing agent of tannin. However, due to the wide application of PEG, it is a greater concern about its use and disposal in the environment, since their concentration, either in soil or water, can be large. However, little is known about their fate in the environment, especially in tropical conditions, which were not found in the literature studies for monitoring underground and surface water, and even environmental impact studies. In this context, this project falls in the search on the fate of PEG-4000 in the environment, seeking information on their mobility, degradation and sorption in soils, using radiometric techniques (14C-PEG). Complementing the study of PEG, was evaluated the pesticides transport in the presence of PEG, since it has a high solubility and can act as co-solvent, thereby assessing the role of PEG in the presence of contaminants

A intervenção das atividades antrópicas ao meio ambiente tem repercutido na estrutura e funções dos ecossistemas, sendo que o uso de aditivos químicos, como agrotóxicos e fertilizantes, destacam-se pela parcela de responsabilidade que assumem diante desses desequilíbrios. O agrotóxico Vertimec® 18CE, cuja toxicidade para diversas taxóns já é conhecida, é amplamente utilizado em lavouras agrícolas, e têm-se conhecimento a respeito das intensas práticas de manuseio, muitas vezes irregulares, o que pode fazer com que concentrações muito maiores do que as previstas atinjam o ambiente aquático. Um dos grupos que nos últimos anos vem se destacando pelo declínio crescente associado ao uso destes produtos são os anfíbios. Os anfíbios possuem papel central na cadeia alimentar, e muitos estudos relatam o desequilíbrio ecológico causado pelo declínio desse grupo em relação a adição de contaminantes, incluindo os agrotóxicos. No presente estudo foram desenvolvidos testes laboratoriais a fim de determinar o estágio dos girinos de Lithobates catesbeianus mais suscetível à intervenção do agrotóxico e à concentração capaz de causar mortalidade em 50% dos indivíduos (CL50, 96h). A partir desses resultados, experimentos in situ (mesocosmos) com girinos no estágio mais avançado (25 da tabela de Gosner) foram desenvolvidos com o intuito de comparar as diferenças de toxicidade do Vertimec® 18CE quando manipulado em campo e laboratório, e quais os efeitos causados por uma única aplicação do produto e por aplicações múltiplas. Os testes laboratoriais demonstraram que os girinos em estágios mais precoce (21G) foram mais sensíveis ao agrotóxico Vertimec® 18CE do que àqueles mais avançados (25G). O experimento em campo indicou que a CL50, 96h para L. catesbeianus (25G) foi muito mais agressiva quando próxima às condições naturais, causando a mortalidade de todos os indivíduos no mesmo estágio de desenvolvimento em um período inferior a 24 horas. Entretanto, a concentração inferior à CL50, 96h (0,002 ml de Vertimec.L-1) quando ministrada em campo, assim como no laboratório, não causou mortalidade, mas implicou em atraso no desenvolvimento e maior período larval do que àqueles organismos que não estiveram em contato com o agrotóxico, já que atingiu os recursos disponíveis, promovendo um efeito indireto no sucesso dessa espécie. Não foi possível observar diferença entre as aplicações única e múltipla do Vertimec® 18CE, em decorrência da morte dos girinos do tratamento em dosagem múltipla, porém observou-se desequilíbrio das condições limnológicas do sistema ao sofrer nova intervenção do Vertimec® 18CE. Diante dos resultados obtidos é possível concluir que o Vertimec® 18CE é capaz de afetar diretamente (mortalidade, estágios de desenvolvimento e comportamento) e indiretamente (redução de recursos alimentares) a população de Lithobates catesbeianus, contribuindo para o declínio de anfíbios nos sistemas naturais. / The intervention of anthropogenic activities to the environment has reflected in the structure and functions of ecosystems and the use of chemical additives, such as pesticides and fertilizers, has contributed for the disequilibrium. The Vertimec® 18EC, whose toxicity is described to different taxa, is widely used in agricultural crops, and it has been known about the intense handling practices, often irregular, which can reach higher concentrations than those expected in the aquatic environment. One group that has been highlighted in recent years by the increasing decline associated with the use of these products is the amphibians. Amphibians plays a central role in the food chain and several studies have related the ecological disequilibrium caused by the decline of this group due to the addition of contaminants, including pesticides. In this study, laboratory bioassays were developed to determine the more susceptible stage and the LC50,96h of Lithobates catesbeianus to Vertimec® 18EC. From these results, in situ experiments (mesocosms) were conducted with tadpoles in more advanced stage (25 of Gosner table) in order to compare the differences in toxicity of Vertimec® 18EC when manipulated both in field and in laboratory. Also, the effects caused by a single and multiple application of the pesticides were evaluated. The laboratorial results showed that earlier stages (21G) were more sensitive than more developing tadpoles (25G), and the effects of the pesticide were more aggressive under natural conditions (mesocoms), with 100% of mortality before 24 hours, at the same developmental stage. The results of laboratorial and in situ bioassays indicated that the lower concentration (0.002 ml Vertimec.L-1) didn\'t cause mortality, but alterations on development stage and larval period time were observed, indicating indirect effects (available resources) on the success of this species. On the other hand, no difference was found between the single and multiple applications of Vertimec® 18EC because all organisms died in the unique dosage treatment, but it was possible to verify limnological alterations after the second application of the pesticide. Considering the results obtained we conclude that Vertimec® 18EC can affect directly (mortality, development stages and behavior) and indirectly (food reduction) the population of Lithobates catesbeianus, contributing to the decline of amphibians in the natural systems.

Neste trabalho foi investigado o potencial de modelos metaloporfirínicos em mimetizar a ação do citocromo P450 na oxidação de um herbicida, a atrazina. Foram utilizadas as metaloporfirinas comerciais de segunda geração solúveis em solvente orgânico, cloreto de 5,10,15,20-tetrakis(2,6-diclorofenil)porfirina metal(III) [M(TDCPP)Cl] e cloreto de 5,10,15,20-tetrakis(pentafluorofenil) porfirina metal(III) [M(TFPP)Cl] (metal = ferro e manganês), tanto em solução homogênea como suportadas em montmorilonita K-10 aminofuncionalizadas; e metaloporfirinas solúveis em água, como a cloreto de 5,10,15,20-tetrakis-(N-metil-4-piridil) porfirina ferro(III), [Fe(TMPy)Cl], e cloreto de [5,10,15,20-tetra(4-carboxifenil)porfirina] ferro(III), [Fe(TCPP)Cl]. Os oxidantes testados foram iodosilbenzeno, ácido metacloroperbenzóico e peróxido de hidrogênio em água, metanol e acetonitrila. Os produtos de oxidação da atrazina foram identificados por cromatografia líquida de alta eficiência (CLAE). Os resultados mostraram que as metaloporfirinas foram capazes de oxidar a atrazina, um herbicida com características de persistência no meio ambiente, e mimetizar a ação da enzima in vivo e in vitro com formação de dois metabólitos: DEA e DIA, resultado da N-desalquilação das cadeias etila e propila do substrato, respectivamente. O DEA correspondeu a um dos principais produtos da reação, e formou-se apenas traços de DIA, mostrando a preferência das metaloporfirinas em oxidar a cadeia etila da atrazina. Verificou-se também a formação de cinco produtos desconhecidos, sendo possível a identificação de apenas um deles por espectrometria de massas, devido à baixa concentração dos demais, o qual corresponde à formação de uma amida na cadeia etila da atrazina (COA). Esse composto correspondeu ao produto de maior rendimento na maioria das reações. O monitoramento das reações em diferentes intervalos de tempo e a variação nas condições reacionais mostraram que os principais produtos de oxidação do herbicida, DEA e COA, são formados por mecanismos independentes e por espécies catalíticas distintas. O DEA é formado via espécie ativa Me(V)OP [Mn(V)OP ou Fe(IV)OP+], enquanto o COA é originado via Me(IV)OP [Mn(IV)OP ou Fe(IV)OP]. Estudos de intermediários por UV-Vis e EPR mostraram que a espécie ferril predomina como intermediário de reação para os sistemas Fe(TFPP)Cl/ACN com os dois oxidantes, iodosilbenzeno e ácido metacloroperbenzóico. Para as metaloporfirinas Fe(TCPP)Cl e Fe(TMPy)Cl o estudo da oxidação do herbicida ficou comprometido devido à baixa solubilidade da atrazina em água, o que provocava sua precipitação e destruição do catalisador. Para as metaloporfirinas suportadas em montmorilonita K-10 aminofuncionalizada também não foi observada formação de produtos, resultado atribuído à dificuldade do substrato, considerado bastante inerte, atingir o sítio catalítico. Todos esses resultados mostraram o potencial de aplicação desses modelos biomiméticos em estudos que buscam elucidar o metabolismo de herbicidas in vivo, tendo em vista a dificuldade de se trabalhar com as enzimas in vitro, e resultaram na proposição de um esquema de reação da oxidação da atrazina catalisada pelas metaloporfirinas nas condições estudadas. / In this work we investigated the ability of metalloporphyrin model systems to mimic the action of cytochrome P450 in the oxidation of a herbicide, atrazine. To this end, we employed the second generation commercially available metalloporphyrins metal (III) 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin chloride [M(TDCPP)Cl] and metal (III) 5,10,15,20- tetrakis(pentafluorophenyl)porphyrin chloride [M(TFPP)Cl] (metal = iron or manganese), all soluble in organic solvents, as well as the water soluble metalloporphyrins iron (III) 5,10,15,20-tetrakis(N-methyl-4-pyridyl)porphyrin chloride [Fe(TMPy)Cl] and iron (III) 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin chloride [Fe(TCPP)Cl]. These metalloporphyrins were used both in homogeneous solution and supported on montmorillonite K-10. Iodosylbenzene, metachloroperbenzoic acid, and hydrogen peroxide were tested as oxidants, using one of the following reaction media: water, methanol, and acetonitrile. Products generated during atrazine oxidation were identified by high performance liquid chromatography. Our results show that the metalloporphyrins are able to oxidize atrazine, a highly persistent herbicide in the environment, as well as mimic the action of P450 enzymes both in vivo and in vitro, with formation of two metabolites, namely DEA and DIA, which result from the N-dealkylation of the ethyl and propyl chains of the substrate, respectively. We also detected the formation of five unknown products, and we were able to identify only one of them by means of mass spectrometry, which corresponds to the formation of an amide on the atrazine ethyl chain (COA) and was the compound obtained in highest yields in most of the reactions. The other four unknown products were obtained in very low concentrations, which prevented us from determining their structures. By monitoring the reactions at different time intervals and varying the reactional conditions, we were able to see that the main herbicide oxidation products, DEA and COA, are generated via distinct mechanisms and different active catalytic species. DEA is formed via the species Me(V)OP [Mn(V)OP or Fe(IV)OP.+], while COA results from the action of the species Me(IV)OP [Mn(IV)OP or Fe(IV)OP]. Studies of the reaction intermediates by UV-VIS and EPR showed that the ferryl species is the main reaction intermediate in the case of Fe(TFPP)Cl/ACN systems and the oxidants, iodosylbenzene and metachloroperbenzoic acid. Studies of herbicide oxidation were difficult to carry out in the case of the metalloporphyrins Fe(TCPP)Cl and Fe(TMPy)Cl due to the low solubility of atrazine in water, which led to its precipitation and catalyst destruction. With respect to the metalloporphyrins supported on montmorillonite K-10, no reaction products were obseved because of the difficult diffusion of the inert substrate into the catalytic site. All these results demonstrate the potential application of these biomimetic model systems in studies that pursue the elucidation of herbicide metabolism in vivo, especially when one bears in mind the difficulty in working with enzymes in vitro. Our data enabled the proposition of a scheme for metalloporphyrin-catalyzed atrazine oxidation under the conditions used herein.