The effect of ionic Co presence on the structural, optical and photocatalytic properties of modified cobalt–titanate nanotubes

With the aim of producing materials with enhanced optical and photocatalytic properties, titanate nanotubes (TNTs) modified by cobalt doping (Co-TNT) and by Na+ -> Co ion-exchange (TNT/Co) were successfully prepared by a hydrothermal method. The influence of the doping level and of the cobalt position in the TNT crystalline structure was studied. Although no perceptible influence of the cobalt ion position on the morphology of the prepared titanate nanotubes was observed, the optical behaviour of the cobalt modified samples is clearly dependent on the cobalt ions either substituting the Ti4+ ions in the TiO6 octahedra building blocks of the TNT structure (doped samples) or replacing the Na+ ions between the TiO6 interlayers (ion-exchange samples). The catalytic ability of these materials on pollutant photodegradation was investigated. First, the evaluation of hydroxyl radical formation using the terephthalic acid as a probe was performed. Afterwards, phenol, naphthol yellow S and brilliant green were used as model pollutants. Anticipating real world situations, photocatalytic experiments were performed using solutions combining these pollutants. The results show that the Co modified TNT materials (Co-TNT and TNT/Co) are good catalysts, the photocatalytic performance being dependent on the Co/Ti ratio and on the structural metal location. The Co(1%)-TNT doped sample was the best photocatalyst for all the degradation processes studied.

Balanço energético da operação de uma caldeira a biomassa

A pressão causada sobre os recursos energéticos é impulsionada pela evolução demográfica e pelo crescimento económico, que se vem registando principalmente nos países em desenvolvimento. Segundo várias estatísticas, a procura pela energia incide principalmente sobre os combustíveis fósseis, os quais, representam cerca de do mix de consumo mundial de energia primária. A incerteza sobre as reservas das fontes energéticas não renováveis, e os problemas ambientais derivados da sua conversão noutros tipos de energia, levaram a uma implementação de medidas com rumo à sustentabilidade e eficiência energética. Desta forma, o aumento da utilização sobre as fontes energéticas renováveis é de extrema importância. A biomassa é uma das fontes energéticas de maior relevo. A utilização de biomassa em caldeiras, oferece benefícios económicos, sociais e ambientais, tais como poupança financeira no combustível, conservação dos recursos fósseis e redução de emissões poluentes. As caldeiras desenvolvidas por empresas como a Ventil, são uma solução para a produção de energia térmica pela combustão da biomassa. Estes sistemas caracterizam-se por serem energeticamente eficientes nas várias componentes da sua operação. Assim, pretende-se fazer uma caracterização dos consumos energéticos associados à operação de uma caldeira Ventil de, nomeadamente o consumo de energia elétrica de equipamentos associados. Também será considerado um balanço energético da caldeira e determinado o seu rendimento. Desta forma, concluiu-se que a potência do sistema é de MJ/s, apresentando um rendimento de. Foram detetados motores mal dimensionados e apresentadas alternativas de substituição. Com um investimento de seria possível reduzir a fatura energética em, obtendo um payback de anos. No entanto, a fatura energética do sistema ultrapassa os anuais, sendo que do investimento é na compra do combustível e os restantes são relativos ao consumo de energia elétrica.

Evaluación de vetiver (Chrysopogon zizanioides) y la elefanta (Pennisetum purpureum) en el diseño de humedales artificiales

En este trabajo se presenta la descripción e investigación en la evaluación de vetiver (Chrysopogon zizanioides) y la elefanta (Pennisetum purpureum) en el diseño de humedales artificiales. Para el tratamiento de aguas residuales de origen doméstico, siendo la vegetación uno de los principales componentes de estos sistemas de tratamientos no convencionales. Muchos \sistemas naturales" están siendo considerados con el propósito del tratamiento del agua residual y control de la contaminación del agua, debido a su alta fiabilidad ambiental y los bajos costos de construcción y mantenimiento, es el caso de los humedales artificiales. El interés en los sistemas naturales está basado en la conservación de los recursos asociados con estos sistemas como opuesto al proceso de tratamiento convencional de aguas residuales que es intensivo respecto al uso de energía y químicos. Los wetlands o humedales artificiales constituyen una alternativa de tratamiento debido a su alta eficiencia de remoción de contaminantes, a su bajo costo de instalación y mantenimiento y a su alta fiabilidad ambiental, generalmente un humedal artificial esta constituido por un medio de soporte el cual generalmente es arena o grava, vegetación y microorganismos o biopelícula los cuales llevan los diferentes procesos bioquímicos para remover los contaminantes del afluente. El objetivo general de este trabajo ha sido: Evaluar la eficiencia de remoción de materia orgánica, sólidos, nitrógeno y fósforo total de dos especies de plantas: vetiver (Chrysopogon zizanioides) y la elefanta (Pennisetum purpureum), en el diseño de humedales artificiales para el tratamiento de aguas residuales de origen doméstico. Los humedales artificiales o sistemas pilotos, se encuentran ubicados en la universidad de Medellín y reciben una preparación de agua sintética, que asemeja a las características de un agua residual de origen doméstico. En el presente trabajo se evalúa el porcentaje de remoción de la carga orgánica de aguas residuales, en un sistema de tratamiento por humedales artificiales con dos especies vegetales. El sistema fue diseñado con tres módulos instalados de manera adjunta. En el primero no se integra ninguna especie vegetal, solo el medio de sustrato el cual constituye el blanco (-), en el segundo se integraron organismos de la especie vetiver (Chrysopogon zizanioides), en el tercer sistema piloto, organismos de la especie elefanta (Pennisetum purpureum) y en el cuarto organismos de la especie papiro japones (Cyperus alternifolius), los cuales constituyen el control positivo (+). Los módulos experimentales fueron limpiados, cortados y adecuados acorde al montaje inicial de las plantas y al espacio requerido para su disposición. A cada sistema piloto se le agrega medio de soporte constituido por grava (5 a 10 cm) y arena (15 a 20 cm), el sustrato es evaluado y caracterizado por su diámetro nominal, posterior en cada sistema se siembran las especies en un área de 3x3 y cada humedal por dos semanas se adecua bajo la solución de Hoagland y Arnon y régimen de humedad. En el agua sintética se analizaron los siguientes parámetros: pH, sólidos totales, sólidos suspendido totales, sólidos disueltos totales, demanda química de oxígeno (DQO), demanda bioquímica de oxígeno (DBO5), nitrógeno total (NTK) y fosforo total (PT). También se realizó la determinación del crecimiento de las plantas a partir del incremento de biomasa, porosidad de la raíz y de igual forma se determina NTK y PT. Los resultados demostraron que el sistema es una opción para la remoción de la carga orgánica y de nutrientes en aguas residuales de origen doméstico, de bajo costo de operación y mantenimiento, especialmente se observa que las plantas que crecen en sistemas de régimen de humedad ácuico y ústico, tienden a tener una mayor recepción y adaptación en los humedales artificiales pilotos, es el caso de la elefanta (Pennisetum purpureum), el cual presenta las más altas tasas de remoción de contaminantes y nutrientes en el afluente, seguido por el papiro japonés (Cyperus alternifolius) y el vetiver (Chrysopogon zizanioides), respecto a tasas de remoción. La remoción de contaminantes que se presentan más altos respectivamente, constituyen sólidos en primera instancia, seguido por la demanda bioquímica de oxigeno (DBO5), demanda química de oxígeno (DQO), nitrógeno total (NTK) y fósforo total (PT), estos últimos presentan una baja tasa de remoción, debido a la naturaleza misma del contaminante, a los organismos que realizan la remoción y absorción y al tiempo de retención que se elige, el cual influye en la tasa de remoción del contaminante siendo menor en la concentración de fósforo, pero se encuentranen el rango esperado para estos sistemas de tratamiento no convencionales.

Functional alkali tantalate 2D structures for microelectronics and related applications

Alkali tantalates and niobates, including K(Ta / Nb)O3, Li(Ta / Nb)O3 and Na(Ta / Nb)O3, are a very promising ferroic family of lead-free compounds with perovskite-like structures. Their versatile properties make them potentially interesting for current and future application in microelectronics, photocatalysis, energy and biomedics. Among them potassium tantalate, KTaO3 (KTO), has been raising interest as an alternative for the well-known strontium titanate, SrTiO3 (STO). KTO is a perovskite oxide with a quantum paraelectric behaviour when electrically stimulated and a highly polarizable lattice, giving opportunity to tailor its properties via external or internal stimuli. However problems related with the fabrication of either bulk or 2D nanostructures makes KTO not yet a viable alternative to STO. Within this context and to contribute scientifically to the leverage tantalate based compounds applications, the main goals of this thesis are: i) to produce and characterise thin films of alkali tantalates by chemical solution deposition on rigid Si based substrates, at reduced temperatures to be compatible with Si technology, ii) to fulfil scientific knowledge gaps in these relevant functional materials related to their energetics and ii) to exploit alternative applications for alkali tantalates, as photocatalysis. In what concerns the synthesis attention was given to the understanding of the phase formation in potassium tantalate synthesized via distinct routes, to control the crystallization of desired perovskite structure and to avoid low temperature pyrochlore or K-deficient phases. The phase formation process in alkali tantalates is far from being deeply analysed, as in the case of Pb-containing perovskites, therefore the work was initially focused on the process-phase relationship to identify the driving forces responsible to regulate the synthesis. Comparison of phase formation paths in conventional solid-state reaction and sol-gel method was conducted. The structural analyses revealed that intermediate pyrochlore K2Ta2O6 structure is not formed at any stage of the reaction using conventional solid-state reaction. On the other hand in the solution based processes, as alkoxide-based route, the crystallization of the perovskite occurs through the intermediate pyrochlore phase; at low temperatures pyrochlore is dominant and it is transformed to perovskite at >800 °C. The kinetic analysis carried out by using Johnson-MehlAvrami-Kolmogorow model and quantitative X-ray diffraction (XRD) demonstrated that in sol-gel derived powders the crystallization occurs in two stages: i) at early stage of the reaction dominated by primary nucleation, the mechanism is phase-boundary controlled, and ii) at the second stage the low value of Avrami exponent, n ~ 0.3, does not follow any reported category, thus not permitting an easy identification of the mechanism. Then, in collaboration with Prof. Alexandra Navrotsky group from the University of California at Davis (USA), thermodynamic studies were conducted, using high temperature oxide melt solution calorimetry. The enthalpies of formation of three structures: pyrochlore, perovskite and tetragonal tungsten bronze K6Ta10.8O30 (TTB) were calculated. The enthalpies of formation from corresponding oxides, ∆Hfox, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -203.63 ± 2.84 kJ/mol, - 358.02 ± 3.74 kJ/mol, and -1252.34 ± 10.10 kJ/mol, respectively, whereas from elements, ∆Hfel, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -1408.96 ± 3.73 kJ/mol, -2790.82 ± 6.06 kJ/mol, and -13393.04 ± 31.15 kJ/mol, respectively. The possible decomposition reactions of K-deficient KTa2.2O6 pyrochlore to KTaO3 perovskite and Ta2O5 (reaction 1) or to TTB K6Ta10.8O30 and Ta2O5 (reaction 2) were proposed, and the enthalpies were calculated to be 308.79 ± 4.41 kJ/mol and 895.79 ± 8.64 kJ/mol for reaction 1 and reaction 2, respectively. The reactions are strongly endothermic, indicating that these decompositions are energetically unfavourable, since it is unlikely that any entropy term could override such a large positive enthalpy. The energetic studies prove that pyrochlore is energetically more stable phase than perovskite at low temperature. Thus, the local order of the amorphous precipitates drives the crystallization into the most favourable structure that is the pyrochlore one with similar local organization; the distance between nearest neighbours in the amorphous or short-range ordered phase is very close to that in pyrochlore. Taking into account the stoichiometric deviation in KTO system, the selection of the most appropriate fabrication / deposition technique in thin films technology is a key issue, especially concerning complex ferroelectric oxides. Chemical solution deposition has been widely reported as a processing method to growth KTO thin films, but classical alkoxide route allows to crystallize perovskite phase at temperatures >800 °C, while the temperature endurance of platinized Si wafers is ~700 °C. Therefore, alternative diol-based routes, with distinct potassium carboxylate precursors, was developed aiming to stabilize the precursor solution, to avoid using toxic solvents and to decrease the crystallization temperature of the perovskite phase. Studies on powders revealed that in the case of KTOac (solution based on potassium acetate), a mixture of perovskite and pyrochlore phases is detected at temperature as low as 450 °C, and gradual transformation into monophasic perovskite structure occurs as temperature increases up to 750 °C, however the desired monophasic KTaO3 perovskite phase is not achieved. In the case of KTOacac (solution with potassium acetylacetonate), a broad peak is detected at temperatures <650 °C, characteristic of amorphous structures, while at higher temperatures diffraction lines from pyrochlore and perovskite phases are visible and a monophasic perovskite KTaO3 is formed at >700 °C. Infrared analysis indicated that the differences are due to a strong deformation of the carbonate-based structures upon heating. A series of thin films of alkali tantalates were spin-coated onto Si-based substrates using diol-based routes. Interestingly, monophasic perovskite KTaO3 films deposited using KTOacac solution were obtained at temperature as low as 650 °C; films were annealed in rapid thermal furnace in oxygen atmosphere for 5 min with heating rate 30 °C/sec. Other compositions of the tantalum based system as LiTaO3 (LTO) and NaTaO3 (NTO), were successfully derived as well, onto Si substrates at 650 °C as well. The ferroelectric character of LTO at room temperature was proved. Some of dielectric properties of KTO could not be measured in parallel capacitor configuration due to either substrate-film or filmelectrode interfaces. Thus, further studies have to be conducted to overcome this issue. Application-oriented studies have also been conducted; two case studies: i) photocatalytic activity of alkali tantalates and niobates for decomposition of pollutant, and ii) bioactivity of alkali tantalate ferroelectric films as functional coatings for bone regeneration. Much attention has been recently paid to develop new type of photocatalytic materials, and tantalum and niobium oxide based compositions have demonstrated to be active photocatalysts for water splitting due to high potential of the conduction bands. Thus, various powders of alkali tantalates and niobates families were tested as catalysts for methylene blue degradation. Results showed promising activities for some of the tested compounds, and KNbO3 is the most active among them, reaching over 50 % degradation of the dye after 7 h under UVA exposure. However further modifications of powders can improve the performance. In the context of bone regeneration, it is important to have platforms that with appropriate stimuli can support the attachment and direct the growth, proliferation and differentiation of the cells. In lieu of this here we exploited an alternative strategy for bone implants or repairs, based on charged mediating signals for bone regeneration. This strategy includes coating metallic 316L-type stainless steel (316L-SST) substrates with charged, functionalized via electrical charging or UV-light irradiation, ferroelectric LiTaO3 layers. It was demonstrated that the formation of surface calcium phosphates and protein adsorption is considerably enhanced for 316L-SST functionalized ferroelectric coatings. Our approach can be viewed as a set of guidelines for the development of platforms electrically functionalized that can stimulate tissue regeneration promoting direct integration of the implant in the host tissue by bone ingrowth and, hence contributing ultimately to reduce implant failure.

Viabilidade do biodiesel de microalgas: otimização de técnicas de extração

Os problemas relacionados com o consumo energético e as emissões de poluentes relativas ao setor dos transportes representam seguramente a maior preocupação ao nível Europeu no que respeita aos gases com efeito de estufa e à poluição atmosférica. Uma das formas de resolver/minimizar estes problemas é através da aposta em combustíveis alternativos. Em particular, os biocombustíveis poderão ser uma alternativa interessante aos combustíveis convencionais. As microalgas, como matéria-prima para produção de biodiesel, apresentam-se com excelentes perspetivas de futuro e com vantagens competitivas no campo das energias renováveis. É nesta perspetiva que se enquadra o presente trabalho, cujos objetivos consistiram na extração de biodiesel a partir de microalgas secas (Nannochloropsis gaditana e Scenedesmus sp.) e na otimização das respetivas técnicas de extração lipídica. Verificou-se que, em função dos métodos e condições utilizadas, a espécie Nannochloropsis gaditana apresenta um potencial de produção de biodiesel superior à espécie Scenedesmus sp. (eficiências de extração de 24,6 (wt.%) e 9,4 (wt.%) respetivamente). Um método de rotura celular conjugado com o processo de extração lipídica via solvente orgânico é essencial, pois conseguiu-se um acréscimo de 42% no rendimento de extração, sendo 10 minutos o tempo ideal de operação. Solventes como o metanol e sistema de solventes diclorometano/metanol mostraram ser mais eficazes quando se pretende extrair lípidos de microalgas, com valores de eficiência de remoção de 30,9 (wt.%) e 23,2 (wt.%) respetivamente. De forma a valorizar os resultados obtidos no processo de extração recorreu-se à sua conversão em biodiesel através da transesterificação catalítica ácida, onde se obteve uma eficiência de conversão de 17,8 (wt.%) para a espécie Nannochloropsis gaditana.

Lifetime and distribution of ozone and related pollutants in the eastern United States

Most major cities in the eastern United States have air quality deemed unhealthy by the EPA under a set of regulations known as the National Ambient Air Quality Standards (NAAQS). The worst air quality in Maryland is measured in Edgewood, MD, a small community located along the Chesapeake Bay and generally downwind of Baltimore during hot, summertime days. Direct measurements and numerical simulations were used to investigate how meteorology and chemistry conspire to create adverse levels of photochemical smog especially at this coastal location. Ozone (O3) and oxidized reactive nitrogen (NOy), a family of ozone precursors, were measured over the Chesapeake Bay during a ten day experiment in July 2011 to better understand the formation of ozone over the Bay and its impact on coastal communities such as Edgewood. Ozone over the Bay during the afternoon was 10% to 20% higher than the closest upwind ground sites. A combination of complex boundary layer dynamics, deposition rates, and unaccounted marine emissions play an integral role in the regional maximum of ozone over the Bay. The CAMx regional air quality model was assessed and enhanced through comparison with data from NASA’s 2011 DISCOVER-AQ field campaign. Comparisons show a model overestimate of NOy by +86.2% and a model underestimate of formaldehyde (HCHO) by –28.3%. I present a revised model framework that better captures these observations and the response of ozone to reductions of precursor emissions. Incremental controls on electricity generating stations will produce greater benefits for surface ozone while additional controls on mobile sources may yield less benefit because cars emit less pollution than expected. Model results also indicate that as ozone concentrations improve with decreasing anthropogenic emissions, the photochemical lifetime of tropospheric ozone increases. The lifetime of ozone lengthens because the two primary gas-phase sinks for odd oxygen (Ox ≈ NO2 + O3) – attack by hydroperoxyl radicals (HO2) on ozone and formation of nitrate – weaken with decreasing pollutant emissions. This unintended consequence of air quality regulation causes pollutants to persist longer in the atmosphere, and indicates that pollutant transport between states and countries will likely play a greater role in the future.

Hydrothermal carbonization in the synthesis of sustainable porous carbon materials

Carbon materials are found versatile and applicable in wide range of applications. During the recent years research of carbon materials has focussed on the search of environmentally friendly, sustainable, renewable and low-cost starting material sources as well as simple cost-efficient synthesis techniques. As an alternative synthesis technique in the production of carbon materials hydrothermal carbonization (HTC) has shown a great potential. Depending on the application HTC can be performed as such or as a pretreatment technique. This technique allows synthesis of carbon materials i.e. hydrochars in closed vessel in the presence of water and self-generated pressure at relatively low temperatures (180-250 ˚C). As in many applications well developed porosity and heteroatom distribution are in a key role. Therefore in this study different techniques e.g. varying feedstock, templating and post-treatment in order to introduce these properties to the hydrochars structure were performed. Simple monosaccharides i.e. fructose or glucose and more complex compounds such as cellulose and sludge were performed as starting materials. Addition of secondary precursor e.g. thiophenecarboxaldehyde and ovalbumin was successfully exploited in order to alter heteroatom content. It was shown that well-developed porosity (SBET 550 m2/g) can be achieved via one-pot approach (i.e. exploitation of salt mixture) without conventionally used post-carbonization step. Nitrogen-enriched hydrochars indicated significant Pb(II) and Cr(VI) removal efficiency of 240 mg/g and 68 mg/g respectively. Sulphur addition into carbon network was not found to have enhancing effect on the adsorption of methylene blue or change acidity of the carbon material. However, these hydrochars were found to remove 99.9 % methylene blue and adsorption efficiency of these hydrochars remained over 90 % even after regeneration. In addition to water treatment application N-rich high temperature treated carbon materials were proven applicable as electrocatalyst and electrocatalyst support. Hydrothermal carbonization was shown to be workable technique for the production of carbon materials with variable physico-chemical properties and therefore hydrochars could be applied in several different applications e.g. as alternative low-cost adsorbent for pollutant removal from water.

Coupling of Chemical Kinetics with Computational Fluid Dynamics in a Three-Dimensional Engine Model

The role of computer modeling has grown recently to integrate itself as an inseparable tool to experimental studies for the optimization of automotive engines and the development of future fuels. Traditionally, computer models rely on simplified global reaction steps to simulate the combustion and pollutant formation inside the internal combustion engine. With the current interest in advanced combustion modes and injection strategies, this approach depends on arbitrary adjustment of model parameters that could reduce credibility of the predictions. The purpose of this study is to enhance the combustion model of KIVA, a computational fluid dynamics code, by coupling its fluid mechanics solution with detailed kinetic reactions solved by the chemistry solver, CHEMKIN. As a result, an engine-friendly reaction mechanism for n-heptane was selected to simulate diesel oxidation. Each cell in the computational domain is considered as a perfectly-stirred reactor which undergoes adiabatic constant- volume combustion. The model was applied to an ideally-prepared homogeneous- charge compression-ignition combustion (HCCI) and direct injection (DI) diesel combustion. Ignition and combustion results show that the code successfully simulates the premixed HCCI scenario when compared to traditional combustion models. Direct injection cases, on the other hand, do not offer a reliable prediction mainly due to the lack of turbulent-mixing model, inherent in the perfectly-stirred reactor formulation. In addition, the model is sensitive to intake conditions and experimental uncertainties which require implementation of enhanced predictive tools. It is recommended that future improvements consider turbulent-mixing effects as well as optimization techniques to accurately simulate actual in-cylinder process with reduced computational cost. Furthermore, the model requires the extension of existing fuel oxidation mechanisms to include pollutant formation kinetics for emission control studies.

Simulação do transporte de poeiras radioactivas resultantes de um acidente no complexo de Angra dos Reis, Brasil

O objetivo da avaliação de impactos ambientais (AIA) é permitir uma análise integrada de possíveis impactos diretos ou indiretos ao meio ambiente decorrentes da implantação e operação de empreendimentos, de forma a propor de medidas ou programas que visem evitar, mitigar ou compensar tais impactos. Para tanto é necessário conhecer as diversas características das áreas direta e indiretamente afetadas pela instalação de um projeto, tais como as condições meteorológicas e climatológicas. Estas também são relevantes no estudo das emissões em cenários de operação regular ou acidental de empreendimentos, dada sua influência nas condições de transporte e de dispersão de poluentes na atmosfera. Neste trabalho é realizado um estudo das condições de dispersão de poluentes na atmosfera para a região da Central Nuclear Almirante Álvaro Alberto (CNAAA) em Angra dos Reis, no Estado do Rio de Janeiro, utilizando o modelo WRF, considerando um cenário acidental com liberações por 48 horas. Os dois episódios simulados representam os regimes de tempo predominantes na região obtidos a partir da análise pelo o método k-means sobre as EOFs para o campo de pressões ao nível médio do mar entre os anos de 1985 e 2014. A aplicação da metodologia dos regimes de tempo permite observar os fenômenos meteorológicos de grande escala persistentes e recorrentes sobre uma dada região, servindo como uma ferramenta para a elaboração de estudos e documentos técnicos que fundamentem a decisão dos órgãos reguladores.

An Integrated approach to street canyon pollution modelling.

An integrated method for the prediction of the spatial pollution distribution within a street canyon directly from a microscopic traffic simulation model is outlined. The traffic simulation package Paramics is used to model the flow of vehicles in realistic traffic conditions on a real road network. This produces details of the amount of pollutant produced by each vehicle at any given time. The authors calculate the dispersion of the pollutant using a particle tracking diffusion method which is superimposed on a known velocity and turbulence field. This paper shows how these individual components may be integrated to provide a practical street canyon pollution model. The resulting street canyon pollution model provides isoconcentrations of pollutant within the road topography.

Genomic and biochemical investigation of soybean antioxidant metabolism in response to growth at elevated carbon dioxide and elevated ozone

Metabolism in an environment containing of 21% oxygen has a high risk of oxidative damage due to the formation of reactive oxygen species. Therefore, plants have evolved an antioxidant system consisting of metabolites and enzymes that either directly scavenge ROS or recycle the antioxidant metabolites. Ozone is a temporally dynamic molecule that is both naturally occurring as well as an environmental pollutant that is predicted to increase in concentration in the future as anthropogenic precursor emissions rise. It has been hypothesized that any elevation in ozone concentration will cause increased oxidative stress in plants and therefore enhanced subsequent antioxidant metabolism, but evidence for this response is variable. Along with increasing atmospheric ozone concentrations, atmospheric carbon dioxide concentration is also rising and is predicted to continue rising in the future. The effect of elevated carbon dioxide concentrations on antioxidant metabolism varies among different studies in the literature. Therefore, the question of how antioxidant metabolism will be affected in the most realistic future atmosphere, with increased carbon dioxide concentration and increased ozone concentration, has yet to be answered, and is the subject of my thesis research. First, in order to capture as much of the variability in the antioxidant system as possible, I developed a suite of high-throughput quantitative assays for a variety of antioxidant metabolites and enzymes. I optimized these assays for Glycine max (soybean), one of the most important food crops in the world. These assays provide accurate, rapid and high-throughput measures of both the general and specific antioxidant action of plant tissue extracts. Second, I investigated how growth at either elevated carbon dioxide concentration or chronic elevated ozone concentration altered antioxidant metabolism, and the ability of soybean to respond to an acute oxidative stress in a controlled environment study. I found that growth at chronic elevated ozone concentration increased the antioxidant capacity of leaves, but was unchanged or only slightly increased following an acute oxidative stress, suggesting that growth at chronic elevated ozone concentration primed the antioxidant system. Growth at high carbon dioxide concentration decreased the antioxidant capacity of leaves, increased the response of the existing antioxidant enzymes to an acute oxidative stress, but dampened and delayed the transcriptional response, suggesting an entirely different regulation of the antioxidant system. Third, I tested the findings from the controlled environment study in a field setting by investigating the response of the soybean antioxidant system to growth at elevated carbon dioxide concentration, chronic elevated ozone concentration and the combination of elevated carbon dioxide concentration and elevated ozone concentration. In this study, I confirmed that growth at elevated carbon dioxide concentration decreased specific components of antioxidant metabolism in the field. I also verified that increasing ozone concentration is highly correlated with increases in the metabolic and genomic components of antioxidant metabolism, regardless of carbon dioxide concentration environment, but that the response to increasing ozone concentration was dampened at elevated carbon dioxide concentration. In addition, I found evidence suggesting an up regulation of respiratory metabolism at higher ozone concentration, which would supply energy and carbon for detoxification and repair of cellular damage. These results consistently support the conclusion that growth at elevated carbon dioxide concentration decreases antioxidant metabolism while growth at elevated ozone concentration increases antioxidant metabolism.

Projeto, implementação e análise de um conversor CC-CC de alto ganho e alto rendimento para aplicações fotovoltaicas

In recent years the photovoltaic generation has had greater insertion in the energy mix of the most developed countries, growing at annual rates of over 30%. The pressure for the reduction of pollutant emissions, diversification of the energy mix and the drop in prices are the main factors driving this growth. Grid tied systems plays an important role in alleviating the energy crisis and diversification of energy sources. Among the grid tied systems, building integrated photovoltaic systems suffers from partial shading of the photovoltaic modules and consequently the energy yield is reduced. In such cases, classical forms of modules connection do not produce good results and new techniques have been developed to increase the amount of energy produced by a set of modules. In the parallel connection technique of photovoltaic modules, a high voltage gain DC-DC converter is required, which is relatively complex to build with high efficiency. The current-fed isolated converters explored in this work have some desirable characteristics for this type of application, such as: low input current ripple and input voltage ripple, high voltage gain, galvanic isolation, feature high power capacity and it achieve soft switching in a wide operating range. This study presents contributions to the study of a high gain and high efficiency DC-DC converter for use in a parallel system of photovoltaic generation, being possible the use in a microinverter or with central inverter. The main contributions of this work are: analysis of the active clamping circuit operation proposing that the clamp capacitor connection must be done on the negative node of the power supply to reduce the input current ripple and thus reduce the filter requirements; use of a voltage doubler in the output rectifier to reduce the number of components and to extend the gain of the converter; detailed study of the converter components in order to raise the efficiency; obtaining the AC equivalent model and control system design. As a result, a DC-DC converter with high gain, high efficiency and without electrolytic capacitors in the power stage was developed. In the final part of this work the DC-DC converter operation connected to an inverter is presented. Besides, the DC bus controller is designed and are implemented two maximum power point tracking algorithms. Experimental results of full system operation connected to an emulator and subsequently to a real photovoltaic module are also given.

Metal measurement in aquatic environments by passive sampling methods: Lessons learning from an in situ intercomparison exercise

Passive sampling devices (PS) are widely used for pollutant monitoring in water, but estimation of measurement uncertainties by PS has seldom been undertaken. The aim of this work was to identify key parameters governing PS measurements of metals and their dispersion. We report the results of an in situ intercomparison exercise on diffusive gradient in thin films (DGT) in surface waters. Interlaboratory uncertainties of time-weighted average (TWA) concentrations were satisfactory (from 28% to 112%) given the number of participating laboratories (10) and ultra-trace metal concentrations involved. Data dispersion of TWA concentrations was mainly explained by uncertainties generated during DGT handling and analytical procedure steps. We highlight that DGT handling is critical for metals such as Cd, Cr and Zn, implying that DGT assembly/dismantling should be performed in very clean conditions. Using a unique dataset, we demonstrated that DGT markedly lowered the LOQ in comparison to spot sampling and stressed the need for accurate data calculation.

A cost-efficiency and health benefit approach to improve urban air quality

When ambient air quality standards established in the EU Directive 2008/50/EC are exceeded, Member States are obliged to develop and implement Air Quality Plans (AQP) to improve air quality and health. Notwithstanding the achievements in emission reductions and air quality improvement, additional efforts need to be undertaken to improve air quality in a sustainable way - i.e. through a cost-efficiency approach. This work was developed in the scope of the recently concluded MAPLIA project "Moving from Air Pollution to Local Integrated Assessment", and focuses on the definition and assessment of emission abatement measures and their associated costs, air quality and health impacts and benefits by means of air quality modelling tools, health impact functions and cost-efficiency analysis. The MAPLIA system was applied to the Grande Porto urban area (Portugal), addressing PM10 and NOx as the most important pollutants in the region. Four different measures to reduce PM10 and NOx emissions were defined and characterized in terms of emissions and implementation costs, and combined into 15 emission scenarios, simulated by the TAPM air quality modelling tool. Air pollutant concentration fields were then used to estimate health benefits in terms of avoided costs (external costs), using dose-response health impact functions. Results revealed that, among the 15 scenarios analysed, the scenario including all 4 measures lead to a total net benefit of 0.3M€·y(-1). The largest net benefit is obtained for the scenario considering the conversion of 50% of open fire places into heat recovery wood stoves. Although the implementation costs of this measure are high, the benefits outweigh the costs. Research outcomes confirm that the MAPLIA system is useful for policy decision support on air quality improvement strategies, and could be applied to other urban areas where AQP need to be implemented and monitored.