Subtítulo extraído da capa / Subtítulo extraído da capa / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Geociencias / Made available in DSpace on 2018-08-09T03:32:24Z (GMT). No. of bitstreams: 1 Goulart_FernandoCosta_M.pdf: 29309722 bytes, checksum: 646e65dfcc1ca87ca64add214a34ddbf (MD5) Previous issue date: 2007 / Resumo: A questão ambiental no Brasil, em termos de administração de recursos hídricos, constitui uma questão contemporânea da maior importância e enfrenta controvérsias de competência em face da legislação e atribuições nos âmbitos federal e estadual. O presente trabalho visa traçar um panorama da atividade de transporte de água potável através de caminhões-pipa, grau de regularidade e os conflitos existentes na legislação que regulamenta a explotação de água subterrânea. Tem ainda a finalidade de sistematizar a forma como ocorre em nosso Estado o gerenciamento e a fiscalização dessa atividade, os órgãos de fiscalização e controle, além de estudar a qualidade da água dessas empresas e o nível de atendimento às legislações vigentes num quadro de monopólio legal conferido às concessionárias de abastecimento de água. Traçar um panorama da questão hídrica em termos de solução alternativa de abastecimento de água potável, em poucas linhas, é o escopo do presente estudo, que avalia como a atividade de transporte de água a granel vem se desenvolvendo nas regiões estudadas. o estudo permitiu concluir que existem empresas de porte que executam a atividade de forma estruturada e empresarial, com investimentos maciços na produção de água subterrânea e no aparato logístico. Verificou-se, através da generalização de dados comuns às empresas estudadas, que as empresas estão organizadas na forma de uma associação, que abrange todo o território paulista. Para a realização das pesquisas, foram colhidos dados perante órgãos públicos que licenciam e fiscalizam a exploração de água subterrânea, Associação Paulista dos Aguadeiros e nas visitas de campo realizada em todas as empresas associadas. Assim, este trabalho visa colaborar para que o tema seja mais difundido entre a sociedade, pois como recurso nobre e esgotável, não resta dúvida de que neste século a sociedade como um todo cumprirá um importante papel na preservação e escorreita distribuição dos recursos hídricos / Abstract: The environmental subject in Brazil, in terms of administration of water resources, constitutes a contemporary subject of the largest importance and it faces ompetence controversies in face of the legislation and attributions in the federal and state extents. The present work seeks to draw a survey of the activity of transport of drinking water through trucks, regularity degree and the existent conflicts in the legislation that regulates the exploration of underground water. It still has the purpose of systematizing the form howit happens in our State the administration and the fiscalization of this activity, the fiscalization organs and control, besides studying the quality of the water of those companies and the service levei to the effective legislations in a vision law's monopoly attributed supply water concessionaires. To draw a survey of the subject water resources in terms of alternative solution of drinkable water supply, in few lines, it is the target of the present study that evaluates as the activity of water transport in bulk comes if developing in the studied regions. The study allowed to conclude that there are companies of port who execute the activity of structuralized and enterprise form, with massive investments in the underground water production and the logistic apparatus. It was verified, through the generalization of common data to the studied companies, who the companies are organized in the form of an association, which encloses the São Paulo territory alI. For the accomplishment of the research, they had been harvested given before public agencies that permit and fiscalize the underground water exploration, Associação Paulista de Aguadeiros and in the visits of field carried through in ali the companies associates. Thus, this work aims at to collaborate so that the subject more is spread out between the society, therefore as noble and exhaustible resource, it does not remain doubt of that in this century the society as a whole will fulfill to an importantpaper in the preservation and right distribution of the water resources / Mestrado / Administração e Politica de Recursos Minerais / Mestre em Geociências

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Quantifying changes in the vulnerability of vegetation to various drought stresses in different seasons is important for rational and effective ecological conservation and restoration. However, the vulnerability of vegetation and its dynamics in a changing environment are still unknown, and quantitative attribution analysis of vulnerability changes has been rarely studied. To this end, this study explored the changes of vegetation vulnerability characteristics under various drought stresses in Xinjiang and conducted quantitative attribution analysis using the random forest method. In addition, the effects of ecological water transport and increased irrigation areas on vegetation vulnerability dynamics were examined. The standardized precipitation index (SPI), standardized precipitation-evapotranspiration index (SPEI), and standardized soil moisture index (SSMI) represent atmospheric water supply stress, water and heat supply stress, and soil water supply stress, respectively. The results showed that: (1) different vegetation types responded differently to water stress, with grasslands being more sensitive than forests and croplands in summer; (2) increased vegetation vulnerability under drought stresses dominated in Xinjiang after 2003, with vegetation growth and near-surface temperature being the main drivers, while increased soil moisture in the root zone was the main driver of decreased vegetation vulnerability; (3) vulnerability of cropland to SPI/SPEI/SSMI-related water stress increased due to the rapid expansion of irrigation areas, which led to increasing water demand in autumn that was difficult to meet; and (4) after ecological water transport of the Tarim River Basin, the vulnerability of its downstream vegetation to drought was reduced.

Constitutive relationships are developed to describe the water transport characteristics of the gas diffusion layer (GDL) of proton exchange membrane fuel cells (PEMFCs). Additionally, experimental fixtures and procedures for the determination of the constitutive relationships are presented. The water transport relationships are incorporated into analytical models that assess the impact of the water transport relations and that make PEMFC performance predictions. The predicted performance is then compared to experimental results. The new constitutive relationships are significantly different than the currently popular relationships used in PEMFC modeling because they are derived from experiments on actual PEMFC gas diffusion layer materials. In prior work, properties of the GDL materials such as absolute permeability, liquid water relative permeability, porosity, and capillary behavior are often assumed or used as adjustment parameters in PEMFC models to simplify the model or to achieve good fits with polarization data. In this work, the constitutive relations are not assumed but are determined via newly developed experimental techniques. The experimental fixtures and procedures were used to characterize common GDL materials including carbon papers and carbon cloths, and to investigate common treatments applied to these materials such as the bulk application of a hydrophobic polymer within the porous structure. A one-dimensional model is developed to contrast results based on the new constitutive relations with results based on commonly used relationships from the PEMFC literature. The comparison reveals that water transport relationships can have a substantial impact on predicted GDL saturation, and consequently a significant impact on cell performance. The discrepancy in saturation between cases can be nearly an order of magnitude. A two-dimensional model is also presented that includes the impact of the compressed GDL region under the shoulder of a bipolar plate. Results show that the compression due to the bipolar plate shoulder causes a significant increase in liquid saturation, and a significant reduction in oxygen concentration and current density for the paper GDL. In contrast, compression under the shoulder has a minimal impact on the cloth GDL. Experimental inputs to the 2-D model include: absolute permeability, liquid water relative permeability, the slope of the capillary pressure function with saturation, total porosity, GDL thickness, high frequency resistance, and appropriate Tafel parameters. Computational polarization curve results are compared to experimental polarization behavior and good agreement is achieved. / Ph. D.

Les piles à combustible à membrane échangeuse de protons (PEMFC) permettent de convertir efficacement de l'énergie chimique en électricité. Pour cela l'hydrogène s'oxyde sur une des électrodes de la pile, les protons ainsi créés traversent l'électrolyte (membrane) tandis que les électrons parcourant le circuit extérieur fournissent l'énergie électrique. Tous ces éléments se recombinent à la seconde électrode qui, à l'aide de la réduction de l'oxygène, va former de l'eau. Le rendement n'étant pas parfait, une partie de l'énergie des réactifs est aussi dégradée sous forme de chaleur. Malgré de récents progrès, la commercialisation à grande échelle des piles à combustible est toujours entravée par des problèmes de durabilité, liés notamment à la gestion de l'eau et de la température au sein de ce système. Afin de quantifier le comportement thermique et son effet sur le transport de l'eau, une pile à combustible a été instrumentée, permettant la mesure de la température aux électrodes, des flux de chaleur et d'eau. Les résultats montrent que de forts gradients de température (jusqu'à environ 30 K/mm) peuvent exister pour une pile fonctionnant dans des conditions standard. Il a été observé une nette influence du champ de température dans le coeur de pile sur le transport de l'eau qui se fait vers la partie la plus froide de la pile (généralement les canaux d'alimentation), l'eau traversant les couches de diffusion poreuses sous forme vapeur dans nos conditions expérimentales / Proton exchange membrane fuel cells (PEMFC) make it possible to convert efficiently chemical energy into electricity. For this, hydrogen is oxidized at one of the electrodes of the cell, created protons pass through the electrolyte (membrane) while electrons flow across the external circuit provide the electrical energy. All these elements recombine at the second electrode, with oxygen, to produce water. Performance is not perfect within a cell and a part of the reactants energy is also degraded as heat. Despite recent advances, the large scale commercialization of PEMFC is still hampered by durability issues, some of them being related to water and thermal management. In order to quantify the thermal behavior and its effect on the water transport, a fuel cell has been instrumented for the electrodes temperature, water and heat fluxes measurement. The results show that high temperature gradients (up to about 30 K/mm) can exist in a cell operating under standard conditions. It was observed a clear influence of the temperature field in the cell on the water transport. Water flows towards the coldest part of the cell (usually the channels), passing through the porous layers in vapor phase in our experimental conditions

Im Fokus dieser Arbeit steht die physiologische Reaktion von Einzelbäumen gegenüber Trockenheit. Das angewandte hydrodynamische Xylemwasserfluss (XWF) Model liefert eine hydrologische Abbildung der Einzelbäume. Aufgrund des funktionalen Zusammenhanges zwischen dem Blattwasserpotential und der stomatären Leitfähigkeit erlaubt das XWF Modell eine öko-physiologische Simulation der stomatären Reaktion auf Blattebene. Hieraus ergeben sich auch Rückschlüsse auf die Assimilationsleistung. Als integratives Maß des Verhältnisses zwischen der Kohlenstoffaufnahme und dem Wasserverbrauch werden die stabilen (Jahrring-) Isotope des Kohlen- und des Sauerstoffs analysiert. Des Weiteren werden Messungen des jährlichen Dickenwachstums sowie des Tagesganges der Xylem-Saftflussdichte untersucht. Die XWF Simulationen zeigen eine gute Übereinstimmung mit den Saftflussdichtemessungen an Buchen (Fagus sylvatica L.). Eine effektive stomatäre Regulation der Transpiration während der extreme Trockenheit des Jahres 2003 schütze die untersuchten Buchen vor einer Fehlfunktion des Wassertransportes. Gleichfalls konnte das Wachstum aufrechterhalten werden, was eine Remobilisierung von gespeichertem Kohlenstoff während Zeiten eingeschränkten Gasaustausches nahe legt. Des Weiteren zeigte sich Unterschiede in den (Wasser-) Nutzungsstrategien von Fichten (Picea abies L. Karst.), was auf eine physiologische Prädisposition der Gefährdung einzelner Bäume gegenüber Trockenstress hinweist. Die gemeinsame Betrachtung von hydrodynamischen Simulationen und öko-physiologischen Messungen kann dazu beitragen die komplexen physiologischen Prozesse auf Blattebene abzubilden und diese auf Baumebene zu projizieren. Weiterführend können somit die Vorhersagen des Wasserhaushaltes auf Bestandesebene angepasst und Auswirkungen des Klimawandels besser abgeschätzt werden. / This study focuses on the physiological response of individual trees towards drought. The hydrodynamic model of xylem water flow (XWF) applied provides a hydraulic map of the individual trees. Due to the functional linkage between the leaf water status and the stomatal conductance, the XWF model enables an eco-physiological representation of the stomatal response at the leaf level. As an integrative record of the ratio between water loss and carbon gain, the tree ring carbon and oxygen stable isotopes have been analyzed. Furthermore, measurements of seasonal growth and diurnal sap flow densities include in my study. The hydrodynamic XWF simulation shows good agreement with sap flow density measurements of beech trees (Fagus sylvatica L.). It demonstrates that the study trees were able to cope with the extreme drought events of the years 2003 due to a strong limitation of water loss by stomatal closure. The assessment of growth data and stable isotope measurements suggest an increased remobilization of stored carbohydrates during periods of limited gas exchange. Furthermore, differences in the resource use strategies of Norway spruce trees (Picea abies L. Karst.) suggest a physiological predisposition of individual trees toward drought stress. The combined investigation of hydrodynamic modeling and eco-physiological approaches helps to bridge the gap between the detailed examinations of physiological processes at the leaf level to the forecast of water use at the tree level. Thus, predictions of the water balance at the stand level may be adjusted for a better representation of the impact of climate change.

Swedish hardwood is today used in the energy, pulp and mechanical hardwood industries. Only very small volumes of Swedish hardwood are, however, consumed by the mechanical industry that normally pays the highest timber price. The smallness of the volumes used for mechanical refinement is a result both of forestry not focusing on the production of hardwood for these uses, and of the fact that the mechanical hardwood industry, particularly the sawing industry, is not designed to process the existing raw material in an optimal manner. This thesis discusses the possibilities of improving the conditions for the mechanical refinement of hardwood. The aim of the work has been to investigate the possibilities of developing products and methods for processing of Swedish hardwood. The thesis proposes a new manufacturing system for Swedish hardwood to better utilize the inherent properties of the wood material. The system is based on the so-called PrimWood Method and the star-sawing concept. Compared to normally sawn wood, the sawing concept utilizes the raw material more efficiently with regard to volume yield, and increases the distance between knots in the sawn wood. The material produced has vertical annual rings which give the wood smaller movements as a result of moisture variations and a different textural appearance. Using the PrimWood Method for hardwood would make it possible to more closely match customer requirements regarding hardwood products. Since Swedish hardwood is nowadays mainly used indoors, a possible way of expanding the market would be to increase the outdoor use of the material. Here the durability is of great importance, and one important factor is then the capillary characteristics of the material. The thesis therefore focuses on the characterisation of the capillarity in wood for the future improvement of its durability. It is shown that with the material produced by the proposed manufacturing system, i.e. wood with vertical annual rings, the possibility of using hardwood outdoors increases, because the susceptibility to cracking decreases.

Polymer electrolyte fuel cells (PEFC) convert the chemically bound energy in a fuel, e.g. hydrogen, directly into electricity by an electrochemical process. Examples of future applications are energy conversion such as combined heat and power generation (CHP), zero emission vehicles (ZEV) and consumer electronics. One of the key components in the PEFC is the membrane / electrode assembly (MEA). Both the membrane and the electrodes consist of proton conducting polymers (ionomers). In the membrane, properties such as gas permeability, high proton conductivity and sufficient mechanical and chemical stability are of crucial importance. In the electrodes, the morphology and electrochemical characteristics are strongly affected by the ionomer content. The primary purpose of the present thesis was to develop experimental techniques and to use them to characterise proton conducting polymers and membranes for PEFC applications electrochemically at, or close to, fuel cell operating conditions. The work presented ranges from polymer synthesis to electrochemical characterisation of the MEA performance. The use of a sulfonated dendritic polymer as the acidic component in proton conducting membranes was demonstrated. Proton conducting membranes were prepared by chemical cross-linking or in conjunction with a basic functionalised polymer, PSU-pyridine, to produce acid-base blend membranes. In order to study gas permeability a new in-situ method based on cylindrical microelectrodes was developed. An advantage of this method is that the measurements can be carried out at close to real fuel cell operating conditions, at elevated temperature and a wide range of relative humidities. The durability testing of membranes for use in a polymer electrolyte fuel cell (PEFC) has been studied in situ by a combination of galvanostatic steady-state and electrochemical impedance measurements (EIS). Long-term experiments have been compared to fast ex situ testing in 3 % H2O2 solution. For the direct assessment of membrane degradation, micro-Raman spectroscopy and determination of ion exchange capacity (IEC) have been used. PVDF-based membranes, radiation grafted with styrene and sulfonated, were used as model membranes. The influence of ionomer content on the structure and electrochemical characteristics of Nafion-based PEFC cathodes was also demonstrated. The electrodes were thoroughly investigated using various materials and electrochemical characterisation techniques. Electrodes having medium Nafion contents (35<x<45 wt %) showed the best performance. The mass-transport limitation was essentially due to O2 diffusion in the agglomerates. The performance of cathodes with low Nafion content (<30 wt %) is limited by poor kinetics owing to incomplete wetting of platinum (Pt) by Nafion, by proton migration throughout the cathode as well as by O2 diffusion in the agglomerates. At large Nafion content (>45 wt %), the cathode becomes limited by diffusion of O2 both in the agglomerates and throughout the cathode. Furthermore, models for the membrane coupled with kinetics for the hydrogen electrode, including water concentration dependence, were developed. The models were experimentally validated using a new reference electrode approach. The membrane, as well as the hydrogen anode and cathode characteristics, was studied experimentally using steady-state measurements, current interrupt and EIS. Data obtained with the experiments were in good agreement with the modelled results. / QC 20101014

<p>Polymer electrolyte fuel cells (PEFC) convert the chemically bound energy in a fuel, e.g. hydrogen, directly into electricity by an electrochemical process. Examples of future applications are energy conversion such as combined heat and power generation (CHP), zero emission vehicles (ZEV) and consumer electronics. One of the key components in the PEFC is the membrane / electrode assembly (MEA). Both the membrane and the electrodes consist of proton conducting polymers (ionomers). In the membrane, properties such as gas permeability, high proton conductivity and sufficient mechanical and chemical stability are of crucial importance. In the electrodes, the morphology and electrochemical characteristics are strongly affected by the ionomer content. The primary purpose of the present thesis was to develop experimental techniques and to use them to characterise proton conducting polymers and membranes for PEFC applications electrochemically at, or close to, fuel cell operating conditions. The work presented ranges from polymer synthesis to electrochemical characterisation of the MEA performance.</p><p>The use of a sulfonated dendritic polymer as the acidic component in proton conducting membranes was demonstrated. Proton conducting membranes were prepared by chemical cross-linking or in conjunction with a basic functionalised polymer, PSU-pyridine, to produce acid-base blend membranes. In order to study gas permeability a new in-situ method based on cylindrical microelectrodes was developed. An advantage of this method is that the measurements can be carried out at close to real fuel cell operating conditions, at elevated temperature and a wide range of relative humidities. The durability testing of membranes for use in a polymer electrolyte fuel cell (PEFC) has been studied in situ by a combination of galvanostatic steady-state and electrochemical impedance measurements (EIS). Long-term experiments have been compared to fast ex situ testing in 3 % H2O2 solution. For the direct assessment of membrane degradation, micro-Raman spectroscopy and determination of ion exchange capacity (IEC) have been used. PVDF-based membranes, radiation grafted with styrene and sulfonated, were used as model membranes. The influence of ionomer content on the structure and electrochemical characteristics of Nafion-based PEFC cathodes was also demonstrated. The electrodes were thoroughly investigated using various materials and electrochemical characterisation techniques. Electrodes having medium Nafion contents (35<x<45 wt %) showed the best performance. The mass-transport limitation was essentially due to O2 diffusion in the agglomerates. The performance of cathodes with low Nafion content (<30 wt %) is limited by poor kinetics owing to incomplete wetting of platinum (Pt) by Nafion, by proton migration throughout the cathode as well as by O2 diffusion in the agglomerates. At large Nafion content (>45 wt %), the cathode becomes limited by diffusion of O2 both in the agglomerates and throughout the cathode. Furthermore, models for the membrane coupled with kinetics for the hydrogen electrode, including water concentration dependence, were developed. The models were experimentally validated using a new reference electrode approach. The membrane, as well as the hydrogen anode and cathode characteristics, was studied experimentally using steady-state measurements, current interrupt and EIS. Data obtained with the experiments were in good agreement with the modelled results. Keywords: polymer electrolyte fuel cell, proton conducting membrane, porous electrode, gas permeability, degradation, water transport</p>

KBS-3 and very deep borehole (VDH) concepts are two major types of long-term geologicaldisposal methods for high-level radioactive waste (HLW) isolating from the biosphere. TheKBS-3V concept for isolating the HLW at the depth of 400-500 m, is the officially proposedoption in Sweden and has been the subject of considerable research in the past few decades,while the VDH concept was considered as an option in the 1950s but later became discouragedbecause of insufficient experience in drilling technology. The greatest merit of the VDHconcept is that the almost stagnant groundwater in the deep boreholes prevents the transport ofthe possible release of radionuclides into the rock or up to the ground level. Since variousdisadvantages of the KBS-3V concept were found in previous research, the superiority of VDHconcept attracted the researchers to continue studying it into the late 1980s.The geological repositories of both of KBS-3V and VDH types primarily consist of a naturalbarrier (host rock) and of an engineering barrier (also known as a buffer/backfill barrier).According to the principle of IAEA and national relative research organizations, thebuffer/backfill material should have low permeability and good expandability, as well assuitable physical and sealing properties.The thesis concerns the VDH concept and is focused on the construction and performance ofthose parts of the sealed repository that are not affected by high temperature or gamma radiation.In the lower part of a VDH repository, the clay packages containing HLW will be exposed tohigh temperature (100-150 􀄇 ) in the borehole and to highly saline groundwater. In theinstallation phase of HLW, the groundwater will be pumped out and replaced by medium-softsmectite clay mud in which the HLW packages are installed vertically. During the hydrationand maturation of the clay components, the microstructural reorganization, water transport,migration of clay particles and redistribution of the density of the components take place. Thematuration determines the transient evolution of the clay seals and influences the rheologicaland soil mechanical behavior in the installation phase. The maturation of clay system alsodetermines their ultimate sealing potential of VDH repositories.This study presents the work carried out for investigating the maturation of the buffer-backfillclay in the HLW deep borehole. Initially in the study three types of clays, the Namontmorillonite,magnesium-rich and illite-smectite mixed layer clays, were examined for estimating their performance as the barrier candidate material. This is mainly presented in theliterature review. The experimental study was conducted on montmorillonite GMZ clays andI/S mixed-layer Holmehus clay. The expandability and permeability tests were carried out forinterpretation of the recorded swelling development and assessment of the effect of the salineconditions, with the goal of deriving a relationship between swelling pressure and hydraulicconductivity for different dry densities. The maturation tests of initially fully-saturatedHolmehus clay and partly saturated GMZ clay were performed. During the tests, the shearstrength mobilised by the relative movement of densified mud and migrated dense clay -contained in a perforated central tube - were determined. According to the results of shearstrength tests, the maximum operation time or the number of clay packages to be placed in asingle operation was evaluated, whilst the suitable saturation degree of the dense clay wasdiscussed as well.A model of the maturation of initially water-saturated clay seals based on Darcy’s law wasworked out and the evolution of the clay components in a lab-scale borehole using Holmehusclay were performed and compared with the experimental recordings. Good agreementsbetween the physical behaviors of the theoretical simulations and the measurements wasachieved by which the validity of the model was verified. Using the results, the hydration andsoil migration in the entire maturation process were presented in diagram. The model was alsoused for preliminary evaluation of the maturation products in real boreholes by assuming thesame Holmehus clay as used in the tests. Two constellation of borehole and dense clay withdifferent diameters, 80 cm borehole /60 cm clay and 80cm/50cm, were assumed. The resultsrespecting dry density and hydraulic conductivity of the ultimate maturation products, and thedegree of homogeneous of the buffer and backfill clay system in the assumed boreholes, arepresented and discussed. The options of different mineral types and initial physical propertiesof the candidate buffer clays provide a reference for engineering barrier design of HLW disposalin VDH.