Glutathione transferases (GSTs, EC.2.5.1.18) are multifunctional enzymes that are universally distributed in all cellular life forms. They play important roles in metabolism and detoxication of endogenously produced toxic compounds and xenobiotics. GSTs have gained considerable interest over the years for biomedical and biotechnological applications due to their involvement in the conjugation of glutathione (GSH) to a vast array of chemical species. Additionally, the emergence of non-detoxifying functions of GSTs has further increased their biological significance. The present work encompasses four scientific studies aimed at investigating human as well as fruit fly Drosophila melanogaster GSTs. Paper I presents the immobilization of GSTs on nanoporous alumina membranes. Kinetic analyses with 1-chloro-2,4-dinitrobenzene followed by specificity screening with alternative substrates showed a good correlation between the data obtained from immobilized enzymes and the enzymes in solution. Furthermore, immobilization showed no adverse effects on the stability of the enzymes. Paper II presents inhibition studies of human hematopoietic prostaglandin D2 synthase (HPGDS), a promising therapeutic target for anti-allergic and anti-inflammatory drugs. Our screening results with an FDA-approved drug library revealed a number of effective inhibitors of HPGDS with IC50 values in the low micromolar range. Paper III concerns the toxicity of organic isothiocyanates (ITCs) that showed high catalytic activities with GSTE7 in vitro. The in vivo results showed that phenethyl isothiocyanate (PEITC) and allyl isothiocyanate in millimolar dietary concentrations conferred toxicity to the adult fruit flies leading to death or shortened life-span. The transgenic female flies overexpressing GSTE7 showed increased tolerance against PEITC toxicity compared to the wild-type. However, the effect was opposite in male flies overexpressing GSTE7 after one week exposure. Notably, the transgene enhanced the oviposition activity of flies with and without ITCs exposure. Paper IV highlights Drosophila GSTs as efficient catalysts of the environmental pollutant and explosive 2,4,6-trinitrotoluene and the related 2,4-dinitrotoluene degradation. This result suggests the potential of GST transgenes in plants for biotransformation and phytoremediation of these persistent environmental pollutants.

Small water reservoirs in urban areas have important landscape-forming and environmental roles. However, numerous anthropogenic activities can influence the water quality in these urban ponds. This thesis evaluates and compares the water quality in selected ponds in Prague area (Motol, Stodůlky, Háje) by means of regular water monitoring between May and November 2013. Parameters commonly used as indicators of anthropogenic load were monitored (NO3 - , NH4 + , PO4 3- , Cl- , dissolved oxygen, chemical oxygen demand) and supplemented with the investigation of other chemical and physico-chemical parameters (alkalinity, acidity, water hardness, pH, Ca2+ , NO2 - , specific conductivity). Data were evaluated using Czech technical norm (ČSN - EN 75 7221), which defines five categories of surface water quality. Our data indicated that surface water from reservoirs in Motol exhibited the best water quality (1st category), reservoirs from Stodůlky were slightly polluted and reservoirs from Háje exhibited the poorest water quality (with some parameters exhibiting values corresponding to the 4th category). We found statistically significant correlations between the alkalinity, water hardness, COD and concentrations of NO3 - , Ca2+ , Cl- and PO4 3- . Moreover, numerous parameters are dependent on cumulative...

Les substances pharmaceutiques sont classées comme contaminants environnementaux émergents et suscitent une attention croissante du fait de leurs effets potentiellement néfastes sur les écosystèmes. Après excrétion ou élimination inappropriée, les médicaments vont se retrouver dans les eaux de surface, souterraines voire de consommation. De nombreuses études écotoxicologiques ont pour objet la mesure de leurs impacts sur les écosystèmes. Pour autant, ces études portent essentiellement sur le médicament lui-même alors que nombre d'entre eux sont susceptibles de se transformer dans l'environnement selon des processus biotiques (microorganismes) et/ou abiotiques (traitements chimiques, photodégradation). Les produits de transformations (PTs) ainsi formés vont d'une part, progressivement remplacer le médicament parent dans l'environnement, et d'autre part y exprimer une écotoxicité potentielle. Face à ce problème, nous nous proposons à partir d'un médicament largement utilisé, de procéder à la synthèse de ses PTs plausibles et à la mise au point de méthode de détection dans des matrices complexes. L'accès aux PTs suivra une approche pluridisciplinaire faisant appel à la bioconversion, l'électro-Fenton et l'oxydation électrochimique. L'analyse comparative des composés obtenus par ces différentes approches permettra de sélectionner les PTs les plus probables / Pharmaceuticals as well as personal care products are classified as emerging pollutants of increasing concern due to possible negative impacts on ecosystems. They are constantly introduced in sewage treatment plants either through excretion, or disposal by flushing of unused or expired medication, or directly within the sewage effluents of plants or hospitals. They end up in surface and ground waters and can even be found in drinking water. Many studies report on adverse effects on terrestrial and aquatic organisms. Pharmaceuticals have complex chemical structures capable of reacting in an aqueous medium under the action of chemical, biological or physical agents. Thus, the transformation products (TPs) gradually replace the parent drug in the environment. In addition these transformation products constitute markers of past or current presence of the drug in the environment. Faced with this problem, we believe it is necessary to synthesize the transformation products of the parent compounds to development their detection. The proposed method consists, firstly, to prepare the largest number of (TPs) of a particular drug using three complementary approaches : bioconversion, electro-Fenton and electrochemical oxidation. A second step is to identify the structures which are the most likely present in the environment. Expected advances are the development of a predictive methodology applicable to the study of any molecule involved in environmental risk

One of the primary modes for pollutants to reach the human body is through their release into the atmosphere and dispersion in the nearby areas. This makes air emissions one of the important components of an environmental assessment. They are frequently of interest to the people living in the vicinity of the site. The analysis carried out in this research provides a framework for atmospheric dispersion modeling of air pollutants using AERMOD, the United States Environmental Protection Agency (US EPA) approved regulatory model, for modeling port related emissions. There are various sources of emissions from the ports, however for this study, emissions from roadways, small equipment, and marine related sources are considered. AERMOD was used to estimate ambient pollutant concentrations of selective criteria pollutants such as NOx, SO2, CO and PM10 from a hypothetical port.

Philosophiae Doctor - PhD / Persistent organic pollutants (POPs) are very tenacious wastewater contaminants with negative impact on the ecosystem. The two major sources of POPs are wastewater from textile industries and pharmaceutical industries. They are known for their recalcitrance and circumvention of nearly all the known wastewater treatment procedures. However, the wastewater treatment methods which applied advanced oxidation processes (AOPs) are documented for their successful remediation of POPs. AOPs are a group of water treatment technologies which is centered on the generation of OH radicals for the purpose of oxidizing recalcitrant organic contaminants content of wastewater to their inert end products. Circumvention of the reported demerits of AOPs such as low degradation efficiency, generation of toxic intermediates, massive sludge production, high energy expenditure and operational cost can be done through the application of the combined AOPs in the wastewater treatment procedure. The resultant mineralisation of the POPs content of wastewater is due to the synergistic effect of the OH radicals produced in the combined AOPs. Hydrodynamic cavitation is the application of the pressure variation in a liquid flowing through the venturi or orifice plates. This results in generation, growth, implosion and subsequent production of OH radicals in the liquid matrix. The generated OH radical in the jet loop hydrodynamic cavitation was applied as a form of advanced oxidation process in combination with hydrogen peroxide, iron (II) oxides or the synthesized green nano zero valent iron (gnZVI) for the treatment of simulated textile and pharmaceutical wastewater.

Annually, the global environment receives enormous amounts of persistent organic pollutants (POPs) that include polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs), in addition to polycyclic aromatic hydrocarbons (PAHs). Their ubiquity has made them identifiable contaminants in almost every environmental compartment of the global system. In particular, aquatic systems have been adversely affected by these pollutants. Therefore, effective monitoring, both in ground and surface water, that can reliably assess their environmental impacts is required. Passive samplers have been proposed as suitable options to the traditional grab/spot/bottle sampling approach because they simultaneously sample, isolate and enrich target analytes. Moreover, apart from successfully detecting very low water dissolved analyte concentrations (trace and sub-trace levels), the devices can also provide time weighted average (TWA) concentrations that take into account episodic events. This is usually not practical with other sampling techniques.

Conventional ecotoxicological tests (forced exposure) are an important tool when what is sought are the possible acute and chronic effects of environmental pollutants on each individual that is exposed. The disadvantage of this approach lies in the fact that the organisms are kept enclosed within containers of the same concentration for several hours and / or days. The forced exposure test has no ecological relevance when the modeled environment exhibits a contamination gradient and organisms can move along this gradient. In many aquatic ecosystems, it is common to observe a contamination gradient, with concentrations decreasing with distance from the discharge zone, so that organisms do not necessarily exhibit continuous and forced exposure to the contaminant. The objective of this work was to analyze how aquatic pollutants (e.g Triclosan, Bisphenol, Atrazine and Copper) influence the dispersion / habitat selection pattern of two species of fish: Poecilia reticulata and Danio rerio, using a static system (non-forced exposure) with several compartments, forming a gradient of contamination with the compound to be analyzed. All pollutants tested triggered an avoidance response in fish at environmentally relevant concentrations. The concentrations that caused avoidance on the organisms are lower than those that cause sub-lethal effects on aquatic organisms, including fish. We also find in one of our approaches the potential for the formation of a chemical barrier (habitat fragmentation) by the release of pollutants into the water bodies, reducing the migration potential of aquatic organisms. Finally, one of the most important findings is the interaction of the species with each other when exposed to a pollution gradient. In this case, the presence of one species interfered in the distribution of the other (reduction of the migration potential), when both were in the same system. Thus, the non-forced approach demonstrates to be a powerful tool in the evaluation of environmental risk, complementary to the traditional ecotoxicological tests / Os testes ecotoxicológicos convencionais (exposição forçada) são uma ferramenta importante quando o que se busca são os possíveis efeitos agudos e crônicos dos poluentes ambientais sobre cada indvíduo que é exposto. A desvantagem dessa abordagem está no fato de que os organismos são mantidos enclausurados dentro de recipientes com uma mesma concentração por várias horas e/ou dias. O teste de exposição forçada não tem relevância ecológica quando o ambiente modelado apresenta um gradiente de contaminação e os organismos podem se mover ao longo deste gradiente. Em muitos ecossistemas aquáticos, é comum observar um gradiente de contaminação, com as concentrações diminuindo com a distância da zona de descarga, de modo que os organismos não apresentam obrigatoriamente uma exposição contínua e forçada ao contaminante. Desta forma, este trabalho teve como objetivo a análise de como os poluentes aquáticos (e.g. Triclosan, Bisfenol, Atrazina e Cobre) influenciam o padrão de dispersão / seleção de habitat por duas espécies de peixes: Poecilia reticulate e Danio rerio, utilizando um sistema estático (não forçado) com vários compartimentos, formando um gradiente de contaminação com o composto a ser analisado. Todos os poluentes testados dispararam uma resposta de fuga nos peixes em concentrações ambientalmente relevantes. As concentrações que causaram a fuga dos organismos são menores do que aquelas que causam efeitos sub-letais em organismos aquáticos, incluindo peixes. Encontramos também em uma de nossas abordagens o potencial de formação de uma barreira quimica (fragmentação de habitat) pela liberação de poluentes nos corpos hídricos, reduzindo o potencial de migração dos organismos aquáticos. Por fim, um dos achados mais importantes está na interação das espécies entre si quando expostas a um gradiente de poluição. Nesse caso, a presença de uma espécie interferiu na distribuição da outra (redução do potencial de migração), quando ambas se encontravam no mesmo sistema. Sendo assim, a abordagem não forçada demonstra ser uma ferramenta poderosa na avaliação de risco ambiental, complementar aos testes ecotoxicológicos tradicionais

Orientador: Luíz Vicente de Andrade Scalvi / Banca: Valmor Roberto Mastelaro / Banca: Joelma Perez / Banca: Fenelon Martinho Lima Pontes / Banca: Luiz Henrique Dall'Antonia / Resumo: Os semicondutores BiVO4 e NiO vem sendo bastante estudados nos últimos anos para aplicação em fotoeletrocálise, mais especificamente na degradação de poluentes orgânicos em meio aquoso, implicando em sustentabilidade ambiental. Neste trabalho, estes materiais foram obtidos na forma de filmes finos pelas técnicas: Síntese de Combustão em Solução e Co-precipatação, combinadas ao processo de deposição via molhamento (dip-coating). A composição, microestrutura e morfologia dos filmes foram avaliadas por TG-DTA, DTX e MEV. Os resultados de TG-DTA e DRX permitiram verificar a temperatura de formação das classes desejadas, 287ºC para o BiVO4 e 305ºC NiO. Imagens MEV mostram que os filmes são compostos por partículas de formato aproximadamente eférico, com boa dispersão sobre o suporte. Espectros UV-VIS mostraram que filmes de BiVO4 absorvem na região do visível com bandgap da ordem de 2,5 eV, e filmes de NiO absorvem no ultravioleta no ultravioleta com bandgap da ordem de 3,0 eV. A caracterização elétrica, trouxe resultados surpreendentes, particularmente no filme de NiO, onde iluminação com luz de energia acima do gap aumentou a resistividade do material, o que está ligado a variâncias de Ni2+. A caracterização eletroquímica, realizada por voltametria cíclica e cronoamperometria, mostrou que ambos os filmes respondem à excitação à excitação com luz de determinado comprimento de onda, além de apresentar estabilidade na corrente fotogerada. Ambos os filmes se mostraram eletroativos frente à reação de degradação do azul de metileno, sendo que na presença de luz ocorre a maior degradação. Um eletrodo com heterojunção p-n foi confeccionado utilizando estes dois materiais. O eletrodo FTO/p-NiO/n-BiVO4 apresentou excelente desempenho frente à degradação do azul de metileno, em... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The semiconductor BiVO4 and NiO have been extensively studied in recent years for the photoelectrocatalysis application, more specifically in the organics polluants degradation in aqueous solution, which leads to sustainability environment. In this work, these materials were obtained in the form of thin films by Solution Combustion Systhesis and co-precipitation techniques, combinee with the dip-coating deposition process. The composition, microstructure and morphology of these films was evaluated by TG-DTA, XRD and SEM. TG-DTA and XRD results were important to verify the temperature of the desired phase formation, which tuned out as 287ºC and 305ºC for the BiVO4 and NiO, respectively. SEM images show that the films consist of spherical particles with good dispersion on the support . UV-VIS Spectroscopy, have shown that BiVO4 thin film absorbs in the viable region with bandage energy of about 2.5 eV, whereas the NiO thin film absorbs in the ultraviolet region with bandagap energy about 3.0 eV. The electrical characterization has shown striking results, particularly on the NiO film, where irradiation with above bandgap light leads to a resistivity increase, which was related to the presence of Ni2+ vacancies. The electrochemical characterization, carried out by cyclic voltammetry and chronoamperometry, has shown that both the films respond to excitation with light of specific wavelength and provides stability in the photocurrent. Both the films are electroactive in the methylene blue dedradation reaction and that the greatest degradation takes place in the presence of light. A p-n heterojunction electrode was made using these two materials. The FTO/p-NiO/n-BiVO4, electrode showed excellent performance in the methylene blue degradation in different electrolytes under visible and UV light ilumination. The percentages of... (Complete abstract click electronic access below) / Doutor

Orientador: Dionei Ramos / Resumo: Introdução: A poluição atmosférica é um assunto discutido mundialmente, causando um impacto na saúde humana e se tornando um grave problema de saúde pública, condições meteorológicas como temperatura, e umidade relativa do ar, também podem influenciar na magnitude dos efeitos adversos da poluição atmosférica na saúde humana.Objetivo:Verificar impactos da exposição aos poluentes atmosféricos sobre internações hospitalares por doenças cardiovasculares em uma população adulta, e o efeito da realização de exercício aeróbico em ambiente aberto e fechado com diferentes concentrações de MP2,5, temperatura e umidade relativa do ar na toxicidade pulmonar de indivíduos sedentários e ativos.Métodos: Registros de internações hospitalares por doenças cardiovasculares captados a partir da base de dados referentes ao sistema único de saúde no período de janeiro de 2014 a dezembro de 2015. Níveis de MP10, NO2, temperatura e umidade relativa foram registrados. No segundo estudo foram avaliados 27 indivíduos, divididos em dois grupos: ativos e sedentários submetidos a um exercício aeróbico em ambiente aberto e fechado. Níveis séricos de CC16, monóxido de carbono no ar exalado (COex), e parâmetros hemodinâmicos foram coletados antes e após a prática da atividade, concentrações de MP2,5, temperatura e umidade relativa do ar foram mensurados durante todo exercício. O nível de significância foi considerado p<0,05. Conclusões: Foi concluído que o impacto da exposição aos poluentes atmosféricos, pri... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Introduction: Air pollution is a subject discussed world wide, inducing an impact on human health and becoming a severe public health problem, weather conditions such as temperature and relative humidity can also influence the magnitude of the adverse effects of air pollution on human health. Objective: To verify the impact of exposure to air pollutants on hospital admissions due to cardiovascular diseases in an adult population and the effect of aerobic exercise in outdoor and indoor ambient with different concentrations of PM2.5, temperature and relative air humidity in pulmonary toxicity of sedentary and active individuals. Methods: Records of hospital admissions for cardiovascular diseases collected from Brazilian Unified Health System (SUS) database from January 2014 to December 2015. Levels of PM10, NO2, temperature and relative humidity were recorded. In the second study, 27 subjects were evaluated, splited into two groups: active and sedentary subjects submitted to an aerobic exercise in an outdoor and indoor ambient. Serum levels of CC16, carbon monoxide in the exhaled air (COex), and hemodynamic parameters were collected before and after the practice of the activity, concentrations of PM2.5, temperature and relative humidity were measured throughout the exercise. The significance level was considered p<0.05. Conclusions: It was concluded that the impact of exposure to air pollutants mainly PM10 on hospital admissions for cardiovascular diseases in adults, and PM2.5 ... (Complete abstract click electronic access below) / Mestre

Grandes cidades, como São Paulo, são afetadas de forma significante pela poluição atmosférica. É de grande importância a caracterização das fontes emissoras da poluição atmosférica, não somente nas regiões centrais, mas também nas regiões periféricas, pois a composição da poluição pode não ser homogênea em toda a extensão da cidade. Neste estudo foram caracterizados os componentes da poluição atmosférica em quatro regiões dentro cidade de São Paulo. Para este fim foram Coletados Material Particulado (PM2.5) durante vinte dias no período de inverno de 2011 e vinte dias durante o período de verão de 2011. O material foi coletado através de filtros de policarbonato com 24 h de exposição, e foi submetido a análises gravimétricas, determinação da concentração de Black Carbon por refletância e determinação da composição elementar por Fluorescência de Raios-X. A identificação das diferentes fontes geradoras de material particulado foi baseada na análise de Componentes Principais (ACP). A variação da concentração da massa do material particulado fino (PM2.5) em g/m3 não teve diferença significativa entre os locais amostrados, mas mostrou diferença entre as estações do ano, sendo maior no período do inverno em todos os locais. A proporção do Black Carbon teve um comportamento diferente da massa. O Black Carbon não variou significantemente entre as estações do ano, porém apresentou diferença entre os locais amostrados, destacando-se no Parque do Ibirapuera e na Zona Leste. Foram encontrados 3 Fatores que explicam 75% da variabilidade. O Fator 1 é constituído pelos elementos Ti, V, Mn, Fe, Ni, Pb, P, S Cr e K e foi atribuído como sendo associado à ressuspensão de solo e emissões veiculares, O Fator 2 é composto por V, P, BC, e S e foi interpretado como sendo representativo de emissões veiculares de combustíveis com alto teor de enxofre. O Fator 3 é 7 associado aos elementos BC e Ni e foi interpretado como sendo produzido por emissões veiculares em geral / Large cities such as São Paulo are significantly affected by air pollution. It is of great importance to characterize the emission sources of air pollution, not only in the central regions of the city of São Paulo, but also in peripheral regions, do to the fact that the composition of pollution may not be homogeneous across the city area. This study shows the Characterized the components of air pollution in four different areas of the metropolitan region of São Paulo. Particulate matter (PM 2.5) was collected during the winter of 2011 and summer of 2011. It was collected 24-h PM2.5 samples, employing gravimetry to determine PM2.5 mass concentrations; reflectance to quantify black carbon concentrations and X-ray fluorescence to characterize elemental composition. A receiver model based on principal component analysis (PCA) was used to identify the involvement of the different sources for the generation of particulate matter. The fine particulate matter (PM2.5) in g/m3 did not differ significantly among the locations. However, the results collected showed differences according the seasons evaluation, being higher in the winter for all regions sampled. The proportion of Black Carbon behaves differently than the mass. It does not vary significantly between the seasons, but between the different regions. The proportion of Black Carbon was higher in Ibirapuera Park and the East Zone. Was found 3 factors explaining 75% of the variability. Factor 1 consists of the elements Ti, V, Mn, Fe, Ni, Pb, P, S Cr e K and was related to crustal emission (soil) and vehicle emissions, Factors 2 consists of the elements V, P, BC, e S and can be related to vehicular emissions of fuels with high sulfur content. Factor 3 consists of the elements BC and Ni was associated to vehicle emission