UV-induced stress in bacterioneuston : mechanisms and ecological implications

As bactérias desempenham um papel chave na reciclagem de energia e matéria nas teias tróficas aquáticas. No entanto, as suas pequenas dimensões, curto tempo de geração e o facto de os seus genomas constituírem uma grande porção do seu volume celular, tornam as bactérias mais suscetíveis às alterações ambientais que os organismos superiores. O aumento dos níveis de radiação UVB (280-320 nm) constitui uma ameaça particularmente importante para as comunidades bacterianas dos sistemas aquáticos, uma vez que a radiação consegue penetrar até profundidades consideráveis. No entanto, os mecanismos através dos quais a radiação causa danos nas bactérias ainda não são claros, o que impede a modelação precisa dos efeitos da radiação UV nas comunidades bacterianas naturais. O bacterioneuston habita a microcamada superficial (primeiro milímetro da coluna de água), estando naturalmente exposto a níveis de radiação UV superiores aos que o bacterioplâncton está exposto. Deste modo, a microcamada superficial pode ser vista como um nicho ecológico modelo para estudar as interações entre as bactérias e a radiação UV. Os objetivos deste trabalho foram (i) avaliar a influência do nível de exposição natural à radiação das comunidades bacterianas na sua sensibilidade à radiação UV, através da comparação das respostas fotobiológicas do bacterioneuston e bacterioplâncton; (ii) aprofundar o conhecimento acerca dos mecanismos através dos quais a radiação UV causa danos, bem como dos fatores que afetam a interação entre a radiação UV e as bactérias; e (iii) avaliar o potencial da proteína RecA, que medeia a resposta SOS das bactérias, para ser usada como marcador de danos induzidos por UV nas comunidades bacterianas. Verificou-se que o bacterioneuston é mais resistente à radiação UVB que o bacterioplâncton e recupera de modo mais eficiente dos danos induzidos por UV, particularmente em condições de escassez de nutrientes, indicando assim que o nível de exposição natural das comunidades bacterianas à radiação afeta a sua sensibilidade à radiação UV. Os resultados das análises independentes do cultivo revelaram o potencial da radiação UV para afetar a estrutura das comunidades bacterianas ao selecionar bactérias resistentes. A análise do perfil de utilização de fontes de carbono usando o sistema de Ecoplacas Biolog ® e a determinação das taxas de incorporação de leucina e timidina permitiu também verificar que a radiação UV modifica o funcionamento das comunidades bacterianas. Os resultados obtidos indicam a possibilidade do bacterioneuston conter um conjunto de estirpes resistentes a UV que, mediante as condições meteorológicas apropriadas, podem ser selecionadas aquando da exposição à radiação.

Seismic vulnerability and risk assessment of historic masonry buildings

Seismic risk evaluation of built-up areas involves analysis of the level of earthquake hazard of the region, building vulnerability and exposure. Within this approach that defines seismic risk, building vulnerability assessment assumes great importance, not only because of the obvious physical consequences in the eventual occurrence of a seismic event, but also because it is the one of the few potential aspects in which engineering research can intervene. In fact, rigorous vulnerability assessment of existing buildings and the implementation of appropriate retrofitting solutions can help to reduce the levels of physical damage, loss of life and the economic impact of future seismic events. Vulnerability studies of urban centresshould be developed with the aim of identifying building fragilities and reducing seismic risk. As part of the rehabilitation of the historic city centre of Coimbra, a complete identification and inspection survey of old masonry buildings has been carried out. The main purpose of this research is to discuss vulnerability assessment methodologies, particularly those of the first level, through the proposal and development of a method previously used to determine the level of vulnerability, in the assessment of physical damage and its relationship with seismic intensity.

Avaliação ecológica do efeito combinado de contaminantes ambientais

The assessment of ecological status of lotic freshwater bodies, based on stringent criteria of classification, has been defined by the Water Framework Directive (WFD), as a result of the implementation and optimization of methodologies that integrate physico-chemical, biological, and hydromorphological parameters. It is recognized that the application of this methodology is not easy, because it requires deep technical and scientific knowledge; it is time consuming in its application involving high financial costs. Thus, the main objective of this study was the development of cheaper and faster complementary methodologies that may contribute to the technical application of the classification criteria defined by the WFD, achieving the same final results of evaluation. In order to achieve this main goal, the river Mau, a small mountain river subjected to different stressors (eg, metals, pesticides), was established as the main sampling area. This thesis reviewed the historical development of various biotic indexes and its application in assessing water quality, especially highlighting the new paradigm defined by the WFD, and the corresponding actions developed for optimization and intercalibration of methodologies, evaluating the final state of water bodies. The ecological spatiotemporal characterization of the river Mau focused on the application of the WFD methodology, using at this stage only macroinvertebrates collected during four seasons. Results were compared with historical data of the last three years and they demonstrated that the river is in good condition. However, the ecological quality decreased at certain locations indicating that organisms were subjected to some type of disturbance. As the ecological quality can be conditioned by pulses of contamination from the sediments, in environmental adverse conditions, assays were performed with elutriates, obtained from sediments collected near the mining complex Braçal-Palhal. Results showed that this method was effective achieving the state of contamination, which may be important in prioritizing/scoring of critical areas within river ecosystems potentially impacted, using the WFD methodology. However, this methodology requires the collection of sediment which can promote the modification and / or loss of contaminants. To solve this potential problem, we developed a new methodology to obtain similar results. For this, we used a benthic microalga, belonging to the Portuguese flora, sensitive to organic pollution and metals. This methodology was optimized for application in situ, by immobilization of diatom in calcium alginate beads. The results showedthat their sensitivity and normal growth rate are similar to data obtained when used free cells of diatom. This new methodology allowed the achievement of a very quick response on the degree of contamination of a site, providing a complementary methodology to WFD.

Design and performance of wireless cooperative relaying

In recent years, a new paradigm for communication called cooperative communications has been proposed for which initial information theoretic studies have shown the potential for improvements in capacity over traditional multi-hop wireless networks. Extensive research has been done to mitigate the impact of fading in wireless networks, being mostly focused on Multiple-Input Multiple-Output (MIMO) systems. Recently, cooperative relaying techniques have been investigated to increase the performance of wireless systems by using diversity created by different single antenna devices, aiming to reach the same level of performance of MIMO systems with low cost devices. Cooperative communication is a promising method to achieve high spectrum efficiency and improve transmission capacity for wireless networks. Cooperative communications is the general idea of pooling the resources of distributed nodes to improve the overall performance of a wireless network. In cooperative networks the nodes cooperate to help each other. A cooperative node offering help is acting like a middle man or proxy and can convey messages from source to destination. Cooperative communication involves exploiting the broadcast nature of the wireless medium to form virtual antenna arrays out of independent singleantenna network nodes for transmission. This research aims at contributing to the field of cooperative wireless networks. The focus of this research is on the relay-based Medium Access Control (MAC) protocol. Specifically, I provide a framework for cooperative relaying called RelaySpot which comprises on opportunistic relay selection, cooperative relay scheduling and relay switching. RelaySpot-based solutions are expected to minimize signaling exchange, remove estimation of channel conditions, and improve the utilization of spatial diversity, minimizing outage and increasing reliability.

Abordagens ao ensino e práticas de questionamento no ensino superior

A emergência de uma nova Sociedade baseada na Informação e no Conhecimento despoletou transformações pedagógicas profundas nas instituições de Ensino Superior. Esta agenda para a inovação, no sentido de um ensino mais centrado nos alunos e no desenvolvimento de competências, tem exigido um esforço acrescido de toda a comunidade académica e, sobretudo, por parte dos professores universitários. Num contexto de recetividade para a mudança, mas com dificuldade de operacionalização da mesma, este estudo visa contribuir para a compreensão e superação de fatores que parecem dificultar a transposição da inovação para as práticas de ensino-aprendizagem correntes, através de duas frentes investigativas: i) caracterizar os docentes na sua dimensão conceptual, o que pensam e o que os motiva, e na sua dimensão prática, isto é, as estratégias didáticas que adotam e adaptam; e ainda, ii) criar oportunidades de concretização de inovação através do desenho de estratégias promotoras de questionamento dos alunos, e também dos docentes. A formulação de questões, e a procura de respostas, é reconhecida como sendo fundamental no desenvolvimento e na aplicação de competências centrais, tais como o pensamento crítico e reflexivo, sendo igualmente importante na resolução de problemas. Assim, numa articulação dinâmica entre conhecer, compreender e agir, a investigação envolveu uma colaboração próxima com um grupo de quatro docentes universitários, ao longo de dois anos letivos consecutivos (2009/2010 e 2010/2011), na conceptualização e implementação de diversas estratégias didáticas impulsionadoras do questionamento dos alunos, promovendo-se igualmente o questionamento reflexivo nos docentes. O trabalho foi desenvolvido no contexto de duas unidades curriculares semestrais (Microbiologia e Temas e Laboratórios em Biologia), destinadas sobretudo a alunos do primeiro ano. Enquanto estudo longitudinal de casos múltiplos, com características etnográficas e de investigação-ação, o trabalho de campo envolveu a combinação de diversos métodos de recolha de dados. Realizaram-se várias observações de aulas, assim como entrevistas semi-estruturadas, aos quatro professores colaboradores, e a alguns dos seus alunos. Aplicou-se ainda, em momentos específicos da investigação, uma versão portuguesa do Approaches to Teaching Inventory – ATI (Trigwell, Prosser, & Ginns, 2005) aos docentes. Recolheram-se também todos os documentos escritos produzidos pelos alunos e pelos professores no âmbito da investigação. Todo o desenho investigativo, assim como a análise dos dados, nomeadamente análise de conteúdo e análise documental, encontra-se fundamentado na literatura teórico-empírica de três áreas da especialidade: estudo do questionamento, análise do discurso oral em contexto de aulas de ciências e estudo das conceções e práticas de ensino dos docentes universitários, destacando-se nesta última a linha investigativa das Abordagens ao Ensino. Os resultados obtidos, assim como a reflexão sobre o percurso investigativo, possibilitaram a obtenção de contributos inovadores e úteis no sentido da promoção de um Ensino Superior de qualidade. Por um lado, são de salientar as evidências recolhidas com os quatro casos (docentes) que apontam para uma natureza integrativa das conceptualizações de ensino, constituindo um contributo teórico relevante para o debate académico desta área. Por outro, foi possível aceder a dinâmicas associadas à formulação de questões por docentes universitários em contexto de aulas teórico-práticas e práticas, através do desenvolvimento e aplicação de um modelo de categorização de questionamento. Por fim, a conjugação de evidências do campo das ‘teorias de ensino’ (observação indireta) com as ‘práticas de ensino’ (observação direta) dos docentes possibilitou a identificação e caracterização de uma possível relação entre Práticas de Questionamento e Abordagens ao Ensino de professores universitários, ampliando desta forma o modelo conceptual de Keith Trigwell e colaboradores (Trigwell, Prosser, & Taylor, 1994). Enquanto investigação híbrida que se orientou por princípios do paradigma interpretativo-naturalista, e, também, do paradigma sócio-crítico, foi igualmente possível identificar um conjunto de recomendações específicas para a inovação e para a reflexividade, no sentido de estimular a comunidade académica, e os professores universitários em particular, a agirem como promotores de estratégias didáticas centradas no desenvolvimento de competências.

Toxicidade de químicos em mistura: o caso da albufeira do Alqueva

In the environment humans and biota are generally exposed to chemical mixtures rather than individual chemicals. Therefore, when assessing the environmental risk of chemicals, it is important to consider chemical mixtures and their possible interactions. The main objective of this work focused on the environmental risk assessment of pesticides found in the water of the Alqueva reservoir and their binary combinations. In this aquatic ecosystem several pesticides were above of the environmental quality standards. But in addition, there were several sampling points of the reservoir where ecotoxicity was observed despite the presence of these contaminants at low concentrations. Here, a component-based approach was used to assess the effects of the pesticide mixtures. The effects of the binary combinations of four herbicides, atrazine (ATR), terbuthylazine (TER), simazine (SIM) and metolachlor (MET), on the growth rate of the microalgae Pseudokirchneriella subcapitata and the effects of the binary combinations of the s-triazine herbicides ATR and TER and the insecticide chlorpyrifos (CPF) on the swimming behaviour and acetylcholinesterase (AChE) activity of the zebrafish Danio rerio were assessed using the two reference models of concentration addition (CA) and independent action (IA). Moreover, the combined effects of the herbicides (ATR, TER and MET) and the insecticide CPF were also tested on the swimming behaviour and AChE activity of the aquatic midge Chironomus riparius after the cholinesterases characterization. In this risk characterization, the calculated risk quotients for the herbicides ATR, TER, SIM and MET were higher than 1, meaning that these herbicides present a high risk for the Alqueva ecosystem. As expected, the microalgae P. subcapitata was the most sensitive species to the herbicides. However, despite these herbicides pose no or low risk to other aquatic organisms tested in this study, with EC50 values much higher than the concentrations found in this aquatic ecosystem, they are able to increase the toxic effects of CPF when they are tested in binary mixtures. Moreover, the risk quotients of mixtures of these herbicides present simultaneously in three different locations of the reservoir were also higher than 1, so this confirms the fact that these herbicides when present in mixtures, present a greater risk for this ecosystem than the expected considering each single chemical by its own.

Novel critical phenomena in optimization driven processes on networks

The work presented in this Ph.D thesis was developed in the context of complex network theory, from a statistical physics standpoint. We examine two distinct problems in this research field, taking a special interest in their respective critical properties. In both cases, the emergence of criticality is driven by a local optimization dynamics. Firstly, a recently introduced class of percolation problems that attracted a significant amount of attention from the scientific community, and was quickly followed up by an abundance of other works. Percolation transitions were believed to be continuous, until, recently, an 'explosive' percolation problem was reported to undergo a discontinuous transition, in [93]. The system's evolution is driven by a metropolis-like algorithm, apparently producing a discontinuous jump on the giant component's size at the percolation threshold. This finding was subsequently supported by number of other experimental studies [96, 97, 98, 99, 100, 101]. However, in [1] we have proved that the explosive percolation transition is actually continuous. The discontinuity which was observed in the evolution of the giant component's relative size is explained by the unusual smallness of the corresponding critical exponent, combined with the finiteness of the systems considered in experiments. Therefore, the size of the jump vanishes as the system's size goes to infinity. Additionally, we provide the complete theoretical description of the critical properties for a generalized version of the explosive percolation model [2], as well as a method [3] for a precise calculation of percolation's critical properties from numerical data (useful when exact results are not available). Secondly, we study a network flow optimization model, where the dynamics consists of consecutive mergings and splittings of currents flowing in the network. The current conservation constraint does not impose any particular criterion for the split of current among channels outgoing nodes, allowing us to introduce an asymmetrical rule, observed in several real systems. We solved analytically the dynamic equations describing this model in the high and low current regimes. The solutions found are compared with numerical results, for the two regimes, showing an excellent agreement. Surprisingly, in the low current regime, this model exhibits some features usually associated with continuous phase transitions.

Silver nanoparticles flow in an aquatic trophic chain

Silver nanoparticles (AgNP) have been produced and applied in a variety of products ranging from personal care products to food package containers, clothing and medicine utilities. The antimicrobial function of AgNP makes it very useful to be applied for such purposes. Silver (Ag) is a non-essential metal for organisms, and it has been historically present in the environment at low concentrations. Those concentrations of silver increased in the last century due to the use of Ag in the photographic industry and lately are expected to increase due to the use of AgNPs in consumer products. The presence of AgNP in the aquatic environment may pose a risk for aquatic species, and the effects can vary from lethal to sublethal effects. Moreover, the contact of aquatic organisms with AgNP may not cause immediately the death of individuals but it can be accumulated inside the animals and consequently transferred within the food chain. Considering this, the objective of this work was to study the transfer of silver nanoparticles in comparison to silver ions, which was used as silver nitrate, within an aquatic food chain model. To achieve this goal, this study was divided into four steps: the toxicity assessment of AgNP and AgNO3 to aquatic test-species, the bioaccumulation assessment of AgNP and AgNO3 by Pseudokirchneriella subcapitata and Daphnia magna under different exposure scenarios, and finally the evaluation of the trophic transfer of Ag through an experimental design that included the goldfish Carassius auratus in a model trophic chain in which all the species were exposed to the worse-case scenario. We observed that the bioconcentration of Ag by P. subcapitata is mainly driven by ionic silver, and that algae cannot internalize these AgNPs, but it does internalizes dissolved Ag. Daphnia magna was exposed to AgNP and AgNO3 through different exposure routes: water, food and both water and food. The worse-case scenario for Daphnia Ag bioaccumulation was by the joint exposure of contaminated water and food, showing that Ag body burdens were higher for AgNPs than for AgNO3. Finally, by exposing C. auratus for 10 days through contaminated water and food (supplied as D. magna), with another 7 days of depuration phase, it was concluded that the 10 days of exposure were not enough for fish to reach a plateau on Ag internal concentration, and neither the 7 days of elimination were sufficient to cause total depuration of the accumulated Ag. Moreover, a higher concentration of Ag was found in the intestine of fish when compared with other organs, and the elimination rate constant of AgNP in the intestine was very low. Although a potential for trophic transfer of AgNP cannot be suggested based in the data acquired in this study, there is still a potential environmental risk for aquatic species.

Social-aware opportunistic routing

The increased capabilities (e.g., processing, storage) of portable devices along with the constant need of users to retrieve and send information have introduced a new form of communication. Users can seamlessly exchange data by means of opportunistic contacts among them and this is what characterizes the opportunistic networks (OppNets). OppNets allow users to communicate even when an end-to-end path may not exist between them. Since 2007, there has been a trend to improve the exchange of data by considering social similarity metrics. Social relationships, shared interests, and popularity are examples of such metrics that have been employed successfully: as users interact based on relationships and interests, this information can be used to decide on the best next forwarders of information. This Thesis work combines the features of today's devices found in the regular urban environment with the current social-awareness trend in the context of opportunistic routing. To achieve this goal, this work was divided into di erent tasks that map to a set of speci c objectives, leading to the following contributions: i) an up-to-date opportunistic routing taxonomy; ii) a universal evaluation framework that aids in devising and testing new routing proposals; iii) three social-aware utility functions that consider the dynamic user behavior and can be easily incorporated to other routing proposals; iv) two opportunistic routing proposals based on the users' daily routines and on the content traversing the network and interest of users in such content; and v) a structure analysis of the social-based network formed based on the approaches devised in this work.

Polyhedral study of mixed integer sets arising from inventory problems

“Branch-and-cut” algorithm is one of the most efficient exact approaches to solve mixed integer programs. This algorithm combines the advantages of a pure branch-and-bound approach and cutting planes scheme. Branch-and-cut algorithm computes the linear programming relaxation of the problem at each node of the search tree which is improved by the use of cuts, i.e. by the inclusion of valid inequalities. It should be taken into account that selection of strongest cuts is crucial for their effective use in branch-and-cut algorithm. In this thesis, we focus on the derivation and use of cutting planes to solve general mixed integer problems, and in particular inventory problems combined with other problems such as distribution, supplier selection, vehicle routing, etc. In order to achieve this goal, we first consider substructures (relaxations) of such problems which are obtained by the coherent loss of information. The polyhedral structure of those simpler mixed integer sets is studied to derive strong valid inequalities. Finally those strong inequalities are included in the cutting plane algorithms to solve the general mixed integer problems. We study three mixed integer sets in this dissertation. The first two mixed integer sets arise as a subproblem of the lot-sizing with supplier selection, the network design and the vendor-managed inventory routing problems. These sets are variants of the well-known single node fixed-charge network set where a binary or integer variable is associated with the node. The third set occurs as a subproblem of mixed integer sets where incompatibility between binary variables is considered. We generate families of valid inequalities for those sets, identify classes of facet-defining inequalities, and discuss the separation problems associated with the inequalities. Then cutting plane frameworks are implemented to solve some mixed integer programs. Preliminary computational experiments are presented in this direction.

On the application of optimal control techniques in lossy fieldbuses

The performance of real-time networks is under continuous improvement as a result of several trends in the digital world. However, these tendencies not only cause improvements, but also exacerbates a series of unideal aspects of real-time networks such as communication latency, jitter of the latency and packet drop rate. This Thesis focuses on the communication errors that appear on such realtime networks, from the point-of-view of automatic control. Specifically, it investigates the effects of packet drops in automatic control over fieldbuses, as well as the architectures and optimal techniques for their compensation. Firstly, a new approach to address the problems that rise in virtue of such packet drops, is proposed. This novel approach is based on the simultaneous transmission of several values in a single message. Such messages can be from sensor to controller, in which case they are comprised of several past sensor readings, or from controller to actuator in which case they are comprised of estimates of several future control values. A series of tests reveal the advantages of this approach. The above-explained approach is then expanded as to accommodate the techniques of contemporary optimal control. However, unlike the aforementioned approach, that deliberately does not send certain messages in order to make a more efficient use of network resources; in the second case, the techniques are used to reduce the effects of packet losses. After these two approaches that are based on data aggregation, it is also studied the optimal control in packet dropping fieldbuses, using generalized actuator output functions. This study ends with the development of a new optimal controller, as well as the function, among the generalized functions that dictate the actuator’s behaviour in the absence of a new control message, that leads to the optimal performance. The Thesis also presents a different line of research, related with the output oscillations that take place as a consequence of the use of classic co-design techniques of networked control. The proposed algorithm has the goal of allowing the execution of such classical co-design algorithms without causing an output oscillation that increases the value of the cost function. Such increases may, under certain circumstances, negate the advantages of the application of the classical co-design techniques. A yet another line of research, investigated algorithms, more efficient than contemporary ones, to generate task execution sequences that guarantee that at least a given number of activated jobs will be executed out of every set composed by a predetermined number of contiguous activations. This algorithm may, in the future, be applied to the generation of message transmission patterns in the above-mentioned techniques for the efficient use of network resources. The proposed task generation algorithm is better than its predecessors in the sense that it is capable of scheduling systems that cannot be scheduled by its predecessor algorithms. The Thesis also presents a mechanism that allows to perform multi-path routing in wireless sensor networks, while ensuring that no value will be counted in duplicate. Thereby, this technique improves the performance of wireless sensor networks, rendering them more suitable for control applications. As mentioned before, this Thesis is centered around techniques for the improvement of performance of distributed control systems in which several elements are connected through a fieldbus that may be subject to packet drops. The first three approaches are directly related to this topic, with the first two approaching the problem from an architectural standpoint, whereas the third one does so from more theoretical grounds. The fourth approach ensures that the approaches to this and similar problems that can be found in the literature that try to achieve goals similar to objectives of this Thesis, can do so without causing other problems that may invalidate the solutions in question. Then, the thesis presents an approach to the problem dealt with in it, which is centered in the efficient generation of the transmission patterns that are used in the aforementioned approaches.

Analysis of the organic matter associated to sea salt : definition of potential molecular markers based on the volatile composition and presence of glycosidic derivatives and polysaccharides

Sea salt is a natural product obtained from the evaporation of seawater in saltpans due to the combined effect of wind and sunlight. Nowadays, there is a growing interest for protection and re-valorisation of saltpans intrinsically associated to the quality of sea salt that can be evaluated by its physico-chemical properties. These man-made systems can be located in different geographical areas presenting different environmental surroundings. During the crystallization process, organic compounds coming from these surroundings can be incorporated into sea salt crystals, influencing their final composition. The organic matter associated to sea salt arises from three main sources: algae, surrounding bacterial community, and anthropogenic activity. Based on the hypothesis that sea salt contains associated organic compounds that can be used as markers of the product, including saltpans surrounding environment, the aim of this PhD thesis was to identify these compounds. With this purpose, this work comprised: 1) a deep characterisation of the volatile composition of sea salt by headspace solid phase microextraction combined with comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (HS-SPME/GCGC–ToFMS) methodology, in search of potential sea salt volatile markers; 2) the development of a methodology to isolate the polymeric material potentially present in sea salt, in amounts that allow its characterisation in terms of polysaccharides and protein; and 3) to explore the possible presence of triacylglycerides. The high chromatographic resolution and sensitivity of GC×GC–ToFMS enabled the separation and identification of a higher number of volatile compounds from sea salt, about three folds, compared to unidimentional chromatography (GC–qMS). The chromatographic contour plots obtained revealed the complexity of marine salt volatile composition and confirmed the relevance of GC×GC–ToFMS for this type of analysis. The structured bidimentional chromatographic profile arising from 1D volatility and 2D polarity was demonstrated, allowing more reliable identifications. Results obtained for analysis of salt from two locations in Aveiro and harvested over three years suggest the loss of volatile compounds along the time of storage of the salt. From Atlantic Ocean salts of seven different geographical origins, all produced in 2007, it was possible to identify a sub-set of ten compounds present in all salts, namely 6-methyl-5-hepten-2-one, 2,2,6-trimethylcyclohexanone, isophorone, ketoisophorone, β-ionone-5,6-epoxide, dihydroactinidiolide, 6,10,14-trimethyl-2-pentadecanone, 3-hydroxy-2,4,4-trimethylpentyl 2-methylpropanoate, 2,4,4-trimethylpentane-1,3-diyl bis(2-methylpropanoate), and 2-ethyl-1-hexanol. These ten compounds were considered potential volatile markers of sea salt. Seven of these compounds are carotenoid-derived compounds, and the other three may result from the integration of compounds from anthropogenic activity as metabolites of marine organisms. The present PhD work also allowed the isolation and characterisation, for the first time, of polymeric material from sea salt, using 16 Atlantic Ocean salts. A dialysis-based methodology was developed to isolate the polymeric material from sea salt in amounts that allowed its characterisation. The median content of polymeric material isolated from the 16 salts was 144 mg per kg of salt, e.g. 0.014% (w/w). Mid-infrared spectroscopy and thermogravimetry revealed the main occurrence of sulfated polysaccharides, as well as the presence of protein in the polymeric material from sea salt. Sea salt polysaccharides were found to be rich in uronic acid residues (21 mol%), glucose (18), galactose (16), and fucose (13). Sulfate content represented a median of 45 mol%, being the median content of sulfated polysaccharides 461 mg/g of polymeric material, which accounted for 66 mg/kg of dry salt. Glycosidic linkage composition indicates that the main sugar residues that could carry one or more sulfate groups were identified as fucose and galactose. This fact allowed to infer that the polysaccharides from sea salt arise mainly from algae, due to their abundance and composition. The amino acid profile of the polymeric material from the 16 Atlantic Ocean salts showed as main residues, as medians, alanine (25 mol%), leucine (14), and valine (14), which are hydrophobic, being the median protein content 35 mg/g, i.e. 4,9 mg per kg of dry salt. Beside the occurrence of hydrophobic volatile compounds in sea salt, hydrophobic non-volatile compounds were also detected. Triacylglycerides were obtained from sea salt by soxhlet extraction with n-hexane. Fatty acid composition revealed palmitic acid as the major residue (43 mol%), followed by stearic (13), linolenic (13), oleic (12), and linoleic (9). Sea salt triacylglycerides median content was 1.5 mg per kg of dry salt. Both protein and triacylglycerides seem to arise from macro and microalgae, phytoplankton and cyanobacteria, due to their abundance and composition. Despite the variability resulting from saltpans surrounding environment, this PhD thesis allowed the identification of a sea salt characteristic organic compounds profile based on volatile compounds, polysaccharides, protein, and triacylglycerides.

Laser assisted directional solidification of zirconia-based eutectics

Directionally solidified zirconia-based eutectic (DSE) fibres were obtained using the laser floating zone (LFZ) method. Two systems were investigated: zirconia-barium zirconate and zirconia-mullite. The purpose was to take advantage of zirconia properties, particularly as an ionic conductor and a mechanical rein-forcement phase. The influence of processing conditions in the structural and microstructural characteristics and their consequences on the electrical and mechanical behaviour were the focus of this thesis. The novel zirconia-barium zirconate eutectic materials were developed in order to combine oxygen ionic conduction through zirconia with protonic conduction from barium zirconate, promoting mixed ionic conduction behaviour. The mi-crostructure of the fibres comprises two alternated regions: bands having coarser zirconia-rich microstructure; and inter-band regions changing from a homogeneous coupled eutectic, at the lowest pulling rate, to columnar colony microstructure, for the faster grown fibres. The bands inter-distance increases with the growth rate and, at 300 mm/h, zirconia dendrites develop enclosed in a fine-interpenetrated network of 50 vol.% ZrO2-50 vol.% BaZrO3. Both phases display contiguity without interphase boundaries, according to impedance spec-troscopy data. Yttria-rich compositions were considered in order to promote the yttrium incorporation in both phases, as revealed by Raman spectroscopy and corroborated by the elemental chemical analysis in energy dispersive spectros-copy. This is a mandatory condition to attain simultaneous contribution to the mixed ionic conduction. Such results are supported by impedance spectrosco-py measurements, which clearly disclose an increase of total ionic conduction for lower temperatures in wet/reduction atmospheres (activation energies of 35 kJ/mol in N2+H2 and 48 kJ/mol in air, in the range of 320-500 ºC) compared to the dry/oxidizing conditions (attaining values close to 90 kJ/mol, above 500 ºC). At high temperatures, the proton incorporation into the barium zirconate is un-favourable, so oxygen ion conduction through zirconia prevails, in dry and oxi-dizing environments, reaching a maximum of 1.3x10-2 S/cm in dry air, at ~1000 ºC. The ionic conduction of zirconia was alternatively combined with another high temperature oxygen ion conductor, as mullite, in order to obtain a broad elec-trolytic domain. The growth rate has a huge influence in the amount of phases and microstructure of the directionally solidified zirconia-mullite fibres. Their microstructure changes from planar coupled eutectic to dendritic eutectic mor-phology, when the growth rate rises from 1 to 500 mm/h, along with an incre-ment of tetragonal zirconia content. Furthermore, high growth rates lead to the development of Al-Si-Y glassy phase, and thus less mullite amount, which is found to considerably reduce the total ionic conduction of as-grown fibres. The reduction of the glassy phase content after annealing (10h; 1400 ºC) promotes an increase of the total ionic conduction (≥0.01 S/cm at 1370 °C), raising the mullite and tetragonal zirconia contents and leading to microstructural differ-ences, namely the distribution and size of the zirconia constituent. This has important consequences in conductivity by improving the percolation pathways. A notable increase in hardness is observed from 11.3 GPa for the 10 mm/h pulled fibre to 21.2 GPa for the fibre grown at 500 mm/h. The ultra-fine eutectic morphology of the 500 mm/h fibres results in a maximum value of 534 MPa for room temperature bending strength, which decreases to about one-fourth of this value at high temperature testing (1400 ºC) due to the soft nature of the glassy-matrix.

A importância da prática de orquestra no ensino especializado da música : implicações no âmbito da motivação para a aprendizagem instrumental

A ideia inicial para esta investigação era estudar o efeito da prática de orquestra na motivação intrínseca dos alunos, nomeadamente as repercussões no estudo individual do instrumento. Foram realizados dois estudos no contexto da investigação: um primeiro estudo de natureza exploratória, no qual foram entrevistados 15 professores e 15 alunos; um segundo estudo, de natureza descritiva e explanatória, no qual se administraram 274 questionários a alunos de 9 classes de orquestra em 4 escolas do ensino especializado da música, assistiu-se a um ensaio de cada uma das orquestras e realizou-se uma entrevista informal ao professor de cada classe de orquestra. Os resultados obtidos indicam que a prática orquestral pode produzir efeitos na motivação dos alunos, com implicações claras no estudo do instrumento. Também foi possível concluir que a participação dos alunos em orquestra poderá ser um fator capaz de motivar os alunos, e capaz de transformar para melhor a perspetiva dos alunos em relação à aprendizagem musical. Este facto sugere que a prática de orquestra deve ser entendida como um pilar fundamental da dinâmica das escolas do ensino especializado da música, e como uma disciplina nuclear do curriculum deste ensino.

Formação de professores e atividades práticas de astronomia no 1º CEB

Os estudos sobre astronomia e educação em astronomia com professores em serviço são escassos e o seu aumento significativo, nos últimos anos, denota a importância desta área na literacia científica dos cidadãos. Há uma necessidade de divulgar esse conhecimento para superar algumas dificuldades, tais como, a prevalência de conceções alternativas e a falta de implementação de atividades práticas no 1º Ciclo do Ensino Básico. Neste contexto, foi implementado um estudo quasi-experimental com professores e alunos dos 3º e 4º anos de escolaridade de escolas da costa norte de Portugal, que integrou aplicação de questionários diagnósticos em mais de um momento, e uma ação de formação sobre astronomia, para professores. A intenção era verificar se as conceções em relação à astronomia, de professores e alunos, estavam em conformidade com as descritas na literatura, e se a ação de formação, com base em atividades práticas, concebidas com materiais acessíveis e adequadas para colocar em prática com os alunos, foi resposta para melhorar os seus conhecimentos científicos e a prática docente. A análise dos dados a partir do pré-teste revelou conceções alternativas de acordo com a literatura. Os resultados verificados no pós-teste, administrado um ano mais tarde, para o grupo experimental de professores, e comparados com os do grupo de controlo, mostraram que a totalidade dos elementos do grupo experimental evidenciaram uma melhoria significativa no conhecimento científico e uma mudança concetual, devido ao desenvolvimento profissional implementado. Também se verificou que a realização de atividades práticas, através de metodologia de investigação, permitiu que os alunos pudessem compreender como funciona a ciência, o que se traduziu em progresso ao nível das aprendizagens e atitudes. A prática efetiva de atividades hands-on e minds-on parece ser uma maneira apropriada para construir e reforçar o conhecimento científico nesta área, acerca de fenómenos não observáveis. Advoga-se, assim, a importância da formação de professores ao longo da carreira docente como forma de atualizar o processo de ensino e aprendizagem, tendo em vista uma escola capaz de preparar os alunos para uma sociedade cada vez mais exigente e influenciada pela constante mudança no conhecimento proporcionado pelo desenvolvimento científico e tecnológico.