The recently developed technique of diffusive gradients in thin films (DGT) for speciation measurement of analytes in the environment was further developed through the development of series of new binding phases including poly(acrylamide-co-acrylic acid) copolymer hydrogel (PAM-PAA), poly(acrylamidoglycolic acid-co-acrylamide) (PAAGA-PAM) hydrogel, the Whatman P81 cellulose phosphate ion exchange membrane (P81) and a liquid binding phase of poly(4-styrenesulfonate) (PSS). A new diffusion layer, cellulose dialysis membrane, was also employed for the liquid binding phase DGT. PAM-PAA copolymer hydrogel was prepared by the controlled hydrolysis of polyacrylamide (PAM) in an alkaline solution of 10% sodium hydroxide. The capacity of the copolymer hydrogel to bind various metal ions was tested under a range of uptake conditions. Ions such as Cu2+ and Cd2+ were bound more strongly to the copolymer hydrogel than the competing ions such as Na+, K+, Ca2+ and Mg2+. Metals bound to the copolymer hydrogel can be efficiently eluted in 2 M HNO3 solution (>94%). Application of this new binding material to DGT technique was validated in a synthetic lake water (Windermere, Lake District, UK) with a recovery of 99.0% for Cu2+. PAAGA-PAM hydrogel was prepared by copolymerising 2-acrylamidoglycolic acid with acrylamide. The metal ion binding properties of the hydrogel were characterised for Cu2+, Cd2+ and competing ions under various experimental conditions. The hydrogel was shown to bind Cu2+ and Cd2+ strongly under non-competitive binding conditions, with binding capacities of 5.3 and 5.1 micromol cm-2, respectively. The binding capacity of each metal decreased, under competitive binding conditions (with a range of metal ions present at 17.8 mN), to 1.3 and 0.17 micromol cm-2, respectively, indicating a strong selective binding towards Cu2+. The metal ions were readily recovered (>94%) by eluting with 2 M HNO3. Finally, the copolymer hydrogel was tested as a binding phase with the DGT technique. A linear mass vs. time relationship was observed for Cu2+ in Windermere water with a recovery of close to 100%. The use of a commercially available solid ion exchange membrane (P81) as the binding phase in DGT analysis was demonstrated. P81 is a strong cation exchange membrane. Its performance characteristics as a new binding phase in DGT measurement of Cu2+ and Cd2+ were systematically investigated. Several advantages over the conventional ion exchange resin-embedded hydrogel based binding phases used in DGT were observed. These include: simple preparation, ease of handling, and reusability. The binding phase preferentially binds to transition metal ions rather than competing ions. Within the optimum pH range (pH 4.0 - 9.0), the maximum non-competitive binding capacities of the membrane for Cu2+ and Cd2+ were 3.22 and 3.07 micromol cm-2, respectively. The suitability of the new membrane-based binding phase for DGT applications was validated experimentally. The results demonstrated excellent agreement with theoretically predicted trends. The reusability of this binding phase was also investigated. Application of a liquid binding phase and a dialysis membrane diffusive layer were proposed for the first time. The binding phase was a 0.020 M solution of poly(4-styrenesulfonate) (PSS) polyelectrolyte using a specially designed DGT device. The binding properties of Cd2+, Cu2+, and a range of alkali and alkaline earth metal ions to the PSS solution were characterised. The PSS behaved like a cation exchanger with preferential binding to Cd2+ (6.0 micromole ml-1, log K = 9.0) and Cu2+ (2.5 micromole ml-1, log K = 8.1) under competitive binding conditions. The DGT devices were successfully validated for Cd2+ and Cu2+ in Windermere water. The speciation performance of the solid and liquid binding phases developed in this study was investigated in solutions containing ethylenediaminetetraacetic acid disodium salt (EDTA), humic acid (HA), glucose (GL), dodecylbenzenesulfonic acid (DBS) and tannic acid (TA) with Cu2+ and Cd2+. The ratios of labile metals over total metals were at good agreement with calculated theoretical values using Stability Constants Database. The results indicated that the DGT-labile concentration measured by DGT with these binding phases is essentially free metal ion concentration in the sample. All newly developed DGT binding phases were successfully applied for environmental speciation. The field deployments were carried out in both freshwater and salt-water test sites.

Batch sedimentation is a method that enables us to understand the mechanism of compaction and compression of sedimenting slurry. However, batch settling behaviour is a very complex phenomenon that is not easily described fully by a mathematical model. This causes unrealistically large empirical calculations when the thickener size estimations are required. Channelling, reverse concentration gradients and the initial concentration of the slurry have large effects on batch settling. Existing procedures do not provide clear relationships involving these three significant variables. In this study, batch sedimentation phenomena are examined in detail and possible explanations are given to clarify the complex behaviour using recent theories. Modern research has shown that channelling is an unwanted formation because channels can change the concentration at the bottom and top of the bed by carrying a great amount of flocs upwards. Batch sedimentation tests were performed using flocculated slurry of Calcium Carbonate at various initial concentrations such as 250 g/l, 500 g/l, 750 g/l and 1000 g/l to observe channelling and reverse concentration gradients. Flux plots for the batch system reveal behaviour which can be attributed to the upward flow of solids. In addition, photographic methods were used to observe settling processes, channelling mechanisms and flocs in the channels. One of the purposes of this work was to examine the phenomenological solid-liquid separation theory of Buscall and White (1987), which employs the material properties of the local volume fraction, compressive yield stress Py ()ö and hindered settling function R()ö to identify the material behaviour in batch sedimentation. Stepped-pressure filtration and batch settling tests were used to measure the material characteristics for the flocculated CaCO3 suspension. Experimental data were demonstrated using Height versus Time and Height versus Concentration graphs and displayed the possible region of reverse concentration gradients and channelling in the settling bed. Mathematical predictions adopted from Usher (2002) were performed employing material characteristics of the material and graphical documentations were presented. The results of mathematical predictions were compared to the experimental results and the modes of sedimentation explained by Lester et al. (2005). Fundamental theoretical models and experimental observations highlight that the main driving force for channelling is the high-pressure gradient at the bottom of the bed and the most important factors that cause channelling are high initial concentration of slurry and settling time. The predictions also show that the material and flocculant used for the batch settling tests demonstrate important effect on the settling process. The knowledge and information gained from this study is valuable to maximize the thickening process.

Les filtres à particules (FAP) utilisés dans les véhicules de PSA Peugeot-Citroën sont constitués d'un assemblage de modules (dits segments) de nids d'abeilles en carbure de silicium. Ces structures sont soumises à de forts gradients thermiques lors de la phase de régénération (décolmatage) par combustion des suies. En fonction de la sévérité de la régénération, les filtres sont susceptibles de présenter un endommagement mécanique qui se manifeste sous la forme de fissures, pouvant compromettre, dans certains cas extrêmes, l'efficacité de la filtration. Ce travail a eu pour but principal de développer des modélisations thermomécaniques, expérimentales et numériques, du phénomène de régénération. Les propriétés thermomécaniques des structures cellulaires constituant les FAP ont été caractérisées expérimentalement et un matériau anisotrope homogène équivalent aux nids d'abeilles a été défini, en vue de la réalisation de calculs par éléments finis. L'analyse des nombreuses mesures de températures réalisées lors d'essais de régénération sévère sur banc moteur a permis d'identifier l'évolution temporelle du champ thermique provoquée par la combustion des suies. Les instants d'apparition des fissures ont été déterminés par émission acoustique. Les lieux et les moments de fissuration ont pu être associés à la présence locale de forts gradients thermiques. Un banc d'essai simplifié à chauffage par effet Joule a été conçu dans le but de reproduire sur un segment isolé les chargements thermiques rencontrés lors des essais sur banc moteur. A partir des mesures de températures réalisées, les champs thermiques ont été reconstitués et les champs de contraintes associés calculés par éléments finis. La corrélation de ces champs avec les lieux et les instants de fissuration relevés expérimentalement a permis de proposer un critère simple d'amorçage des fissures, extrapolable aux essais sévères sur banc moteur.

Studies of seed dynamics and seedling establishment at the community level in savanna ecosystems are scant, particularly in the tropical savannas of Central Brazil. The Brazilian savannas (cerrado) have the largest diversity of plant species among Neotropical savannas. Cerrado vegetation exhibits consistent changes in tree density and tree size along shallow topographic gradients. Vegetation types differ from closed savannas with high tree density, and a nearly continuous canopy cover in the uppermost portions, to open savannas with scattered short trees in the low portions of the topographic gradients. Whether or not dynamics of seeds and seedlings of woody species are consistent with variations in tree density and tree canopy cover across the cerrado landscape has not been determined, but could potentially influence such spatial patterns of tree density and canopy cover. The main objective of this study was to evaluate seed dynamics (i.e., seed rain, soil seed banks, and seed characteristics) and seedling establishment of woody species in three major cerrado vegetation types (closed, intermediate and open savannas) which differ in tree canopy cover and tree height. These vegetation types are located along topographic gradients of approximately 30 m in elevation and 1000 m in length. I conducted field work from June 2005 to August 2008 at the Instituto Brasileiro de Geografia e Estatística (IBGE) reserve, a field experimental station located 35 Km south of Brasilia, Brazil (15˚ 56' S, 47˚ 63' W, altitude 1100 m). I established permanent plots in each of the three vegetation types to assess seed rain, seed limitation, seed predation, and seed removal. I also quantified density and composition of the soil seed bank in each vegetation type and studied seed characteristics (i.e., kind of dormancy, moisture content, longevity) of 14 common cerrado woody species. In the field, I quantified establishment of woody seedlings in fire-protected savannas as well as in accidentally burned and frequently burned savannas. In the greenhouse I performed experiments to evaluate the effect of litter cover and light level on seedling emergence of 9 common cerrado woody species. Finally, I evaluated the effect of pulses of heat on seed germination of 5 common cerrado woody species under controlled conditions. The overall results of this study show that regardless of tree canopy cover, cerrado vegetation types are limited in seeds and seedlings of woody species, but these limitations are higher in open than in closed savannas. Most woody species do not form persistent soil seed banks along cerrado vegetation types because their seeds are short-lived, predated and quickly removed from the ground. In addition, dispersal season and dormancy appear to control timing of germination at the onset of the rainy season to ensure survival of seedlings in the field. In the absence of fire, establishment of woody seedlings is higher in closed than in open savannas because canopy cover mitigates the stressful environmental conditions of open savannas and thus facilitates establishment of woody seedlings. As a result, closed savannas are likely to maintain higher density of woody elements over time than open savannas. In burned savannas, however, species composition of woody and herbaceous seedlings is significantly affected because establishment of seedlings of woody and herbaceous species decreases but vegetative reproduction increases. This dissertation study indicates that interactions of early life-history stages of woody species with environmental and disturbance factors appear to play a more significant role in maintaining woody cover variations along cerrado topographic gradients than previously recognized.

The study of waves and instabilities in quantum plasmas is of fundamental importance for understanding collective interactions in superdense astrophysical objects, in high intense laser-plasma/solid-matter interactions, in microelectronic devices and metallic nanostructures. In dense quantum plasmas, there are new pressure laws associated with the Fermi-Dirac distribution functions and new quantum forces associated with the quantum Bohm potential and the Bohr magnetization involving electron ½ spin. These forces significantly alter the collective behavior of dense quantum plasmas. This thesis contains six papers, considering several novel collective modes and instabilities at quantum scales. In Paper I, we have used the quantum hydrodynamical (QHD) model for studying the one-dimensional dust-acoustic (DA) waves incorporating the Fermi pressure law and the quantum Bohm potential. The latter modifies the DA wave dispersion relation in a collisional plasma. In Paper II, we have calculated the electrostatic potential of a test charge in an unmagnetized electron-ion quantum plasma. It is found that the Debye-Hückel and oscillatory wake potentials strongly depend upon the Fermi energy at quantum scales. The results can be of interest for explaining the charged particle attraction and repulsion in degenerate quantum plasmas, such as those in semiconductor and microelectronic devices. Paper III presents the parametric study of nonlinear electrostatic waves in two-dimensional collisionless quantum dusty plasmas. A reductive perturbation method has been employed to the QHD equations together with the Poisson equation, obtaining the cylindrical Kadomtsev-Petviashvili (CKP) equations and their stationary localized solutions. We have numerically examined the quantum mechanical and geometrical effects on the profiles of nonplanar quantum dust-ion-acoustic (DIA) and DA solitary waves. The role of static as well as mobile (negatively or positively charged) dust particles on the low-frequency electrostatic waves has also been highlighted for metallic nanostructures. Paper IV introduces the nonlinear properties of the ion-sound waves in a dense electron-ion Fermi magnetoplasma. The computational analysis of the nonlinear system reveals that the Sagdeev-like potential and the ion-sound density excitations are significantly affected by the wave direction cosine and the Mach number at quantum scales. Paper V considers the nonlinear interactions of electrostatic upper-hybrid (UH), ion-cyclotron (IC), lower-hybrid (LH), and Alfvén waves in a quantum magnetoplasma. The nonlinear dispersion relations have been analyzed analytically to obtain the growth rates for both the decay and modulational instabilities involving the dispersive IC, LH, and Alfvén waves. In Paper VI, we have identified a new drift-like dissipative instability in a collisional quantum plasma. The modified unstable drift-like mode can cause cross-field anomalous ion-diffusion at quantum scales.

The sun provides us with a surplus of energy convertible to electricity using solar cells. This thesis focuses on solar cells based on chalcopyrite (CIGSe) as well as kesterite (CZTS(e)) absorber layers. These materials yield record efficiencies of 20.4 % and 11.1 %, respectively. Especially for CZTS(e), the absorber layers often do not consist of one single desired phase but can exhibit areas with deviating material properties, referred to as secondary phases. Furthermore, several material layers are required for a working solar cell, each exhibiting interfaces. Even though secondary phases and interfaces represent a very small fraction of the solar cell they can have a profound influence on the over-all electrical solar cell characteristics. As such, it is crucial to understand how secondary phases and interfaces influence the local electrical characteristics. Characterising secondary phases and interfaces is challenging due to their small sample volume and relatively small differences in composition amongst others. This is where electronmicroscopy, especially transmission electron microscopy, offers valuable insight to material properties on the microscopic scale. The main challenge is, however, to link these material properties to the corresponding electrical characteristics of a solar cell. This thesis uses electron beam induced current imaging and introduces a new method for JV characterisation of solar cells on the micron scale. Combining microscopic structural and electrical characterisation techniques allowed identifying and characterising local defects found in the absorber layer of CIGS solar cells after thermal treatment. Furthermore, CZTSe solar cells in this thesis exhibited a low photo-current density which is traced to the formation of a current blocking ZnSe secondary phase at the front contact interface. The electron microscopy work has contributed to an understanding of the chemical stability of CZTS and has shown the need for an optimised back contact interface in order to avoid chemical decomposition reactions and formation of detrimental secondary phases. With this additional knowledge, a comprehensive picture of the material properties from the macroscopic down to the microscopic level can be attained throughout all required material layers.

<p>Coastal plain ponds are an understudied and threatened wetland ecosystem with many unique environmental attributes. Research in these ponds can investigate species-environment relationships, while simultaneously providing ecosystem-specific information crucial to their continued conservation and management. This dissertation explores patterns in coastal plain pond vegetation composition and species-environment relationships across space, through time, and in the seed bank and standing vegetation.</p><p>In a two-year field study at 18 coastal plain ponds across the island of Martha's Vineyard, Massachusetts, I investigated species-environment relationships within and among ponds. I identified vegetation species presences and abundances within 1 m2 quadrats, which ran continuously along transects established perpendicular to the water's edge. Species data were analyzed against local and landscape-scale environmental data. I also conducted a one-year seed bank study in which sediments from four coastal plain ponds were incubated in growth chambers and composition was compared to the standing vegetation. One hundred and thirty-four plant species were identified during vegetation sampling and 38 species were identified from incubated sediments.</p><p>I found significant compositional change across space in response to environmental gradients, with patterns in species composition occurring at both local and landscape scales. Elevation was the only local factor strongly correlated with species composition. Significant landscape-scale environmental factors included surficial geology and pond water salinity. Species composition was significantly correlated with hydrologic regime in 2005 but not in 2006. Overall patterns in vegetation species composition and abundance were more closely related to landscape-scale environmental variables than to local environmental variables. </p><p>I also found that coastal plain ponds undergo significant compositional change from one year to the next. Interannual variability disproportionately affected certain ponds and quadrats more than others, highlighting patterns in the relationships between compositional change and environmental attributes. Specifically, ephemeral ponds, ponds located on the moraine, ponds with high specific conductance values, and quadrats located closer to the waterline exhibited greater compositional change from 2005 to 2006 than permanent ponds, ponds located on the outwash plain, ponds with low specific conductance values, and quadrats located further from the waterline. </p><p>Finally, I found that coastal plain ponds exhibit a low degree of similarity between composition in sediments and standing vegetation. More species were identified in the standing vegetation than in the seed bank, and in most cases average species richness per quadrat was higher in the standing vegetation than in the seed bank. Seed bank and standing vegetation samples from ponds with different surficial geology were compositionally distinct. Seed bank samples from permanent and ephemeral ponds were compositionally distinct whereas standing vegetation samples were not.</p> / Dissertation

The present study investigates experimentally the laminar mixing and heat transfer of a range of helical ribbon and anchor impellers for both Newtonian and inelastic non-Newtonian fluids. The work also correlates the experimental data empirically in the form of dimensionless groups. In order to estimate the relative importance and the effect of all the geometrical parameters on the mixing power and heat transfer, data from the published literature sources will be utilized and combined with the results from this study. Thus, reliable empirical correlations will be obtained which are applicable over the widest range of operating conditions. The study also investigates the ablity of the various impellers to level out temerature distributions. The measurement of these temperature gradients and the impeller power requirements gives a measure of the mixing efficiency of the impeller used.

Blood vessels are essential for the delivery of nutrients and oxygen to tissues, as well as for the removal of waste products. Patients with tumors, wounds or diabetes all have active angiogenesis, formation and remodeling of blood vessels, a process that is initiated and manipulated by gradients of secreted signaling proteins. This thesis describes the development of new microfluidic in vitro assays where directed migration of single endothelial cells and three dimensional vascular structures can be monitored in real time. Combining these assays with live imaging microscopy we have studied the behavior of endothelial cells in gradients of proangiogenic factors as well as directed sprouting in embryonic kidneys and stem cell cultures. With the 2D assay we have quantified endothelial cell chemotaxis towards FGF2, VEGFA165 and VEGFA121 and we also demonstrate that constant levels of VEGFA165, but not of FGF2, are able to reduce chemokinesis of endothelial cells. In the 3D migration chamber we have studied directed endothelial cell sprouting in mouse embryonic kidneys and embryoid bodies in response to VEGFA gradients. In both models directed angiogenesis is detected towards increasing levels of growth factor. Using the microarray technique on differentiating embryonic stem cells we have been able to identify the gene exoc3l2 as potentially involved in angiogenesis and endothelial cell migration and we present evidence that ExoC3l2 is associated with the exocyst complex; an important regulator of cell polarity. We have also shown that siRNA mediated gene silencing of exoc3l2 results in impaired VEGFR2 phosphorylation as well as loss of directionality in response to a VEGFA gradient. / (Faculty of Medicine)

O conhecimento sobre o funcionamento e a diversidade das florestas tropicais vem crescendo nos últimos anos. Formas de quantificar as causas da diversidade beta funcional estão sendo desenvolvidas e perguntas sobre quais fatores determinam essa variação da diversidade em comunidades permanecem em aberto, sobretudo em uma escala regional. Nosso objetivo foi identificar as causas da variação da diversidade (i.e. diversidade beta) de espécies e da diversidade funcional de uma metacomunidade de árvores na Floresta Ombrófila Densa Submontana do sul do Brasil, extremo sul de seu limite de distribuição. Nossa hipótese é de que as causas da diversidade beta funcional e de espécies são distintas. A diversidade beta funcional seria explicada por fatores ambientais e a diversidade beta de espécies por fatores históricos. Para testar nossa hipótese utilizamos a análise de partição da variação através da análise de redundância canônica (ROA). Assim, quantificamos a porção da diversidade beta de espécies e funcional entre comunidades explicada pela variação de variáveis explanatórias ambientais (variáveis bioclimáticas e topológicas) ou espaciais (PCNMs). Também tivemos acesso à porção não explicada por nenhum destes fatores, possivelmente relacionada a variáveis não mensuradas ou fatores internos da comunidade como interações biológicas. Compilamos a informação da composição de espécies arbóreas de 12 sítios ao longo da metacomunidade e coletamos atributos de 104 espécies para compor a informação funcional. Como variáveis resposta utilizamos a matriz de composição de espécies, para a abordagem taxonômica, e duas matrizes para a abordagem funcional, uma de atributos médios ponderados pela abundância das espécies na metacomunidade e outra de abundâncias das espécies ponderada pelas relações difusas definidas pelas suas similaridades funcionais. Os resultados indicaram que 82 o/o da diversidade beta de espécies não foi explicada pelas variáveis explanatórias, enquanto que para as matrizes de diversidade funcional essa fração diminuiu para 43 e 37%. A fração puramente ambiental representou So/o da explicação da diversidade beta de espécies, e para a diversidade funcional ela não foi significativa. Porém, o ambiente estruturado no espaço explicou 17 e 21 o/o da variação da diversidade beta funcional e 8% da variação de espécies, e a fração espacial foi significativa para ambas as abordagens (5% na taxonômica e 42 e 44% na funcional). Diagramas de dispersão mostraram as comunidades latitudinalmente estruturadas quanto à composição de espécies, enquanto na abordagem funcional comunidades geograficamente distantes resultaram ser semelhantes. A diversidade beta de espécies é causada por uma variação latitudinal fortemente relacionada às variáveis ambientais. Fatores históricos, como a migração da floresta no sentido norte-sul podem ser os principais determinantes deste padrão. A diversidade-beta funcional, também determinada por fatores espaciais, está relacionada a escalas mais finas de variação espacial podendo estar ligada a centros de endemismo e rotas de migração regionais. Os diferentes padrões detectados analisando a diversidade funcional e de espécies mostram a importância das duas abordagens para o entendimento da metacomunidade. / In the last years, knowledge about the functionality of tropical forest has grown. Ways of quantifying beta-diversity causes are still under developing and questions about what factors determine diversity variation, especially on a regional scale, have not been answered yet. Our aim was to identify the drivers that are defining variation of functional and species diversity (i.e. functional and species beta-diversity) in a Southern Brazilian Atlantic rainforest tree metacommunity, located along the coast of Paraná, Santa Catarina and northeast Rio Grande do Sul states. We hypothesize that different drivers explain functional and species diversity variation within the metacommunity. Specifically, environmental variabies, representing niche processes, may define functional diversity patterns along the gradient whereas species diversity should be explained by metacommunity history, represented by the spatial variables. To test this we partitioned the variation of each variable set through redundancy analyses (RDA). So we used a matrix of space, represented by eight PCNM variables, and other of environment, represented by climatic and topologic variables, as explanatory matrices. The unexplained fraction of variation was further quantified, which is often related to unmeasured variables or internai community factors such as biotic interactions. We compiled tree species composition data from 12 sites and to assess functional information we sampled traits of 104 species representing plant ecological strategies. We used the species composition matrix and two functional diversity matrices, a communityweighted mean trait matrix and a functional fuzzy-weighted matrix, as response variables. A large unexplained fraction (82%) was found for species betadiversity data, whereas this fraction had lower values for functional betadiversity (43 and 37%). A pure environmental fraction represented 5% of species beta-diversity explanation and it was not significant for functional betadiversity. Spacially structured environmental fraction explains a large amount of both functional (17 and 21 %) and species (8.4%) beta-diversity, and the pure spatial fraction was significant for both (5% to species and 42 and 44% to functional). Scatter diagrams showed that species composition data is latitudinally structured, whereas functional information can be similar despite of geographical distance. Species beta-diversity was mainly caused by latitudinal variation (large spatial scale) related with climatic environmental variables. Historical factors as the north-south forest migration may be determining this pattern. Functional beta-diversity was related to this spatial variation as well, but finer spatial scale related with local endemism centers and species migration routes are also influencing. Different patterns detected by species and functional beta-diversities showed the importance of both approaches to understand tree metacommunity patterns.