A demanda alimentar vem aumentando de acordo com o crescimento populacional e com isso há uma necessidade de que as práticas agrícolas tornem-se cada vez mais intensas e tecnificadas, mediante o incremento, entre outros, da utilização de insumos químicos. Porém, uma vez aplicados de maneira desorganizada, sem a devida preocupação com os possíveis impactos aos recursos naturais, tais produtos podem vir a provocar danos ao solo, contaminação de águas subterrâneas (mediante sua lixiviação) e em alguns casos, podem ser responsáveis pelo aumento da salinidade em alguns solos da região do semiárido do nordeste brasileiro. Nesse sentido, devido ao fato de envolverem processos físicos na natureza, o estudo da dinâmica desses produtos químicos têm motivado diversos pesquisadores a aplicarem ferramentas matemáticas (modelos matemáticos) na área de engenharia de água e solo, buscando entender a correlação entre a dinâmica da água e o movimento de solutos no perfil do solo. Portanto, a presente pesquisa tem como objetivo a aplicação do modelo matemático HYDRUS-1D para a simulação do movimento da água e do íon potássio, em condições de laboratório, utilizando-se colunas preenchidas com dois tipos de material de solos salinos e não saturados: Argissolo Amarelo (S1) e Latossolo Vermelho Amarelo (S2). Além disso, buscou-se também avaliar tanto o desempenho do referido modelo, em condições salinas, quanto proceder a uma análise de sensibilidade. Para alcançar tais objetivos, foram conduzidas as seguintes etapas: 1) elaboração de curvas de distribuição de efluentes (Breakthrough Curves - BTC) para obtenção dos parâmetros de transporte do íon potássio, com a aplicação de soluções de 1000 ppm, 2000 ppm e 3000 ppm de concentração de potássio, nos dois tipos de solos salinos, 2) Aplicação dessas soluções de potássio na coluna preenchida com o mesmo material de solo salino não saturado, 3) Simulação dos perfis de água e potássio para os diferentes materiais de solo salino pelo modelo HYDRUS-1D e 4) Avaliação de desempenho e análise de sensibilidade do modelo HYDRUS-1D. A avaliação de desempenho foi feita levando-se em conta os seguintes índices estatísticos: erro máximo, erro absoluto médio, raiz quadrada do erro médio normalizado, coeficiente de massa residual, coeficiente de determinação, eficiência e índice de concordância de Willmott e a análise de sensibilidade foi feita mediante a determinação do erro padrão, por meio de variações positivas (+ 10%, + 20%, + 30%, + 40%, + 50%) e negativas (- 10%, - 20%, - 10%, - 40%, - 50%), dos valores de: umidade volumétrica do solo saturado, condutividade hidráulica e os parâmetros n e ? do modelo de van Genuchten (1980). Diante dos resultados obtidos, pôde-se perceber que os procedimentos experimentais (BTC\'s) para a estimativa dos parâmetros de transporte do íon potássio em condições de solo salino, foram suficientes para descrever a movimentação do íon potássio no solo, gerando informações de entrada precisas para os modelos de simulação. Em termos do modelo HYDRUS-1D, observou-se que o deslocamento do íon potássio acompanhou a frente de molhamento e que o modelo foi eficiente nas simulações de deslocamento do íon potássio e da água para ambos os solos, em condições salinas. A análise de sensibilidade evidenciou que o modelo apresentou-se sensível, às variações negativas dos dados de entrada: umidade volumétrica do solo saturado, condutividade hidráulica do solo saturado e parâmetros \"n\" e \"?\" do modelo de van Genuchten (1980). / The increased demand for food due to population growth requires that agricultural practices become increasingly intensive and very technical, including the increased use of agricultural chemicals (fertilizers). If improperly applied without considering possible impacts on natural resources, agricultural chemicals may lead to soil and groundwater contamination through their leaching from the soil root zone. They may be responsible also for increased salinity in some soils of semiarid regions in northeastern Brazil. Since many transient physical and chemical processes affect their transport in the subsurface, mathematical models have become popular tools in soil and water engineering and management in order to understand the correlation between water dynamics and solute movement in soils. Thus, this research aimed at using the HYDRUS-1D software package to simulate water and potassium movement, under laboratory conditions, in unsaturated saline soil columns filled with two soil types: an Ultisol (S1) and an Oxisol (S2). Comparisons were made with experimental data while also a sensitivity analysis was carried out to evaluate the effect of various parameters on solute transport under saline conditions. For this purpose the following studies were performed: 1) Measurement of solute breakthrough curves (BTCs) to estimate the transport parameters of the potassium ion by applying potassium solutions of 1,000 ppm, 2,000 ppm and 3,000 ppm to both soil types, 2) Application of similar potassium solutions to columns containing the same saline unsaturated soils, 3) Simulation of water and potassium distributions for different saline soil materials using HYDRUS-1D, and 4) Performance evaluation and sensitivity analyses of the HYDRUS-1D numerical model. The performance evaluation was conducted using the following statistical indices: maximum error, mean absolute error, normalized root mean square error, coefficient of residual mass, coefficient of determination, efficiency and Willmott\'s concordance index. The sensitivity analyses considered standard deviations resulting from positive and negative changes (+ 10% + 20% + 30% + 40% + 50%) (-10%, -20%, -10%, -40%, -50%) in the values of the saturated volumetric soil moisture content, the saturated hydraulic conductivity, and the parameters n and ? of van Genuchten\'s (1980) model for the unsaturated soil hydraulic functions. Results indicate that the experimental procedures (BTCs) for estimating the transport parameters of potassium for saline soil conditions were sufficient to describe potassium ion transport in the soils by generating the required input information for the simulation models. Relative to HYDRUS-1D model, the displacement of potassium was found to follow closely the wetting front, with the model providing a very efficient means for simulating the movement of both water and potassium in the two soils during saline conditions. The sensitivity analysis showed that the model was relatively sensitive to negative variations of the input data, notably the saturated water content, the saturated hydraulic conductivity, and the n and ? soil hydraulic parameters.

As características hidráulicas do solo têm uma importância fundamental relacionada à disponibilidade de água para as plantas e ao transporte de solutos no solo. O modelo bifásico ou "móvel-imóvel" presume que o teor de água no solo (θ) pode ser dividido em duas frações: uma fração móvel (θm) e uma outra imóvel (θim). Define-se mobilidade μ da água no solo como a razão θm/θ. Correlações entre as funções θ(h), K(h) e μ(h) são esperadas, uma vez que essas três propriedades são relacionadas com a mesma estrutura do sistema poroso do solo. O objetivo do presente trabalho foi apresentar uma hipótese correlacionando a função mobilidade com a de condutividade, e testá-la através de dados obtidos segundo uma metodologia de laboratório desenvolvida. O experimento foi realizado em Piracicaba, SP e em Braunschweig, Alemanha. Amostras indeformadas de cinco solos (Latossolo Vermelho-Amarelo, no Brasil e Orthic Luvisol, Stagno-gleyic Luvisol, Dystric Podzoluvisol e Gleyic Podzoluvisol, na Alemanha) foram coletadas para a determinação das propriedades hidráulicas de retenção e mobilidade da água no solo. O método utilizado para a determinação da mobilidade da água consistiu na aplicação de um volume de água contendo o íon Cl- como traçador (um "pulso hidráulico") à amostra de solo sob sucção com o objetivo de simular eventos de chuva ou irrigação, que promovem uma alteração hidráulica rápida no solo. A difusão do íon entre as frações móvel e imóvel foi considerada desprezível, uma vez que o pulso hidráulico foi aplicado em uma única parcela e diretamente no solo, tornando o processo relativamente rápido. Resultados obtidos nos cinco solos avaliados indicam a existência de uma correlação linear entre μ e o valor de K/(dK/dθ), conforme hipotetizado. Utilizando o sistema de equações de Van Genuchten – Mualem, μ(h) pode portanto ser estimado por parâmetros da curva de retenção. A metodologia proposta permitiu a determinação da mobilidade da água em amostras de solo sob condições laboratoriais. A mobilidade da água mostrou ser uma função do volume relativo (v) aplicado podendo a relação μ – v ser parametrizada pelo ajuste de uma equação simples, com apenas um parâmetro. Não foi possível averiguar a existência de uma relação empírica entre esse parâmetro e os parâmetros da equação de Van Genuchten, possivelmente em função do número pequeno de dados disponíveis. / Soil hydraulic properties are essential for the determination of plant water availability and solute transport into the soil. The biphasic or mobile-immobile model concept assumes the soil water content (θ) to be divided in two fractions: a mobile fraction (θm) and an immobile fraction (θim). Soil water mobility, μ is defined as the ratio θm/&#952. Relationships between θ (h), K(h) e μ (h) are probable since these properties are related to the same soil pore structure. The objective of this study was to test a hypothesis regarding a correlation between the mobility function and the hydraulic conductivity function, using a new developed laboratory method to determine soil water mobility. The experiments were conducted in Piracicaba, Brazil and in Braunschweig, Germany. Undisturbed soil samples were collected in five soils (Oxisol, in Brazil, Orthic Luvisol, Stagno-gleyic Luvisol, Dystric Podzoluvisol e Gleyic Podzoluvisol, in Germany) to determine hydraulic properties and soil water mobility. The method used to determine water mobility consists in a water volume with Cl- ion as a tracer ("hydraulic pulse") applied to a soil sample under suction, simulating a rainfall or irrigation event leading to abrupt hydraulic changes. The ion diffusion between the mobile and immobile water fractions was negligible as the hydraulic pulse was applied directly to the soil in a relatively short process. Results of five evaluated soils indicate the existence of a linear correlation between μ and K/(dK/d θ), confirming the hypothesis. Using the Van Genuchten – Mualem equation system, μ(h) can therefore be estimated by retention curve parameters. The proposed laboratory method allowed determining soil water mobility in soil samples under laboratory. Soil water mobility showed to be a function of the applied relative volume (v), while the relationship μ – v could be modeled by a simple, one-parameter equation, however, it was not possible to verify the existence of an empirical relation between this parameter and parameters from the Van Genuchten equation, possibly due to small number of available data.

Em vacas de corte, folículos pré-ovulatórios (FPO) maiores, maiores concentrações de estradiol (E2) no proestro/estro e progesterona (P4) no diestro favorecem o crescimento do concepto e a fertilidade. Porém, os mecanismos mediados pelos esteroides femininos que influenciam a receptividade uterina ao embrião precisam ser esclarecidos. Os aminoácidos (AA) são componentes das secreções uterinas que são cruciais para a sobrevivência do embrião antes da implantação. A hipótese deste trabalho é que o tamanho do FPO e as concentrações de E2 e P4 modulam a abundância de transcritos relacionados ao transporte e metabolismo de AA no endométrio e afetam a concentração luminal de AA. Para isso, o crescimento folicular de vacas Nelore foi manipulado com o objetivo de formar dois grupos: FPO grande e CL grande (FG-CLG) e FPO pequeno e CL pequeno (FP-CLP). No Dia 4 (D4; Exp 1) e Dia 7 (D7; Exp 2) após a injeção de GnRH para indução da ovulação, foram coletados tecido endometrial e lavado uterino post-mortem. A abundância de transcritos foi avaliada por qRT-PCR e as concentrações de AA nos lavados foram quantificadas por HPLC. No Exp 1, o tamanho do FPO, concentrações plasmáticas de E2 no D-1 e de P4 no D4 foram 15,70mm±0,43 vs. 11,31mm±0,23 (p<0,01), 2,44pg/ml±0,19 vs. 0,65pg/ml (p<0,01) e 1,40ng/ml±0,23 vs. 0,80ng/ml±0,10 (p<0,01) para os grupos FG-CLG vs. FP-CLP, respectivamente. No Exp 2, o tamanho do FPO, concentrações plasmáticas de E2 no D-1 e de P4 no D7 foram 13,18mm±0,44 vs. 10,63mm±0,30 (p<0,01), 2,30pg/ml±0,57 vs. 0,50pg/ml±0,13 (p<0,01) e 3,68ng/ml±0,38 vs. 2,49ng/ml±0,43 (p=0,04) para os grupos FG-CLG vs. FP-CLP, respectivamente. No D4 a abundância de SLC1A4, SLC38A1, SLC6A6, SLC7A4 e SLCY e no D7, SLC1A4, SLC6A1, SLC6A14, SLC7A4, SLC7A8, SLC38A1, SLC38A7, SLC43A2 e DDO foi maior no endométrio dos animais do grupo FG-CLG (p<0,05). No D4, maiores concentrações de taurina, alanina e ácido α-aminobutírico foram observadas no grupo FP-CLP (p<0,05). Em contraste, menores concentrações de valina e cistationina foram encontradas nos lavados uterinos do D7 dos animais do grupo FP-CLP (p<0,05). No D4, os animais do grupo FG-CLG, associado a maior fertilidade, apresentaram menor quantidade de AA nas secreções uterinas, porém, a abundância dos transportadores de AA foi compatível com maior transporte em comparação aos animais do grupo FP-CLP. Esses resultados sugerem que antes do embrião se mover do oviduto ao útero, o transporte e metabolismo dos AA prioriza a preparação das células endometriais para receber o embrião e não o acúmulo nas secreções uterinas. Porém, no D7, quando o embrião está em contato direto com as secreções uterinas, os genes relacionados ao transporte de AA no endométrio e a concentração de AA no histotrofo são estimulados nas vacas do grupo FG-CLG. Portanto o metabolismo e transporte de AA no sentido das células endometriais ou das secreções uterinas pode ser um mecanismo importante para a receptividade materna. / In beef cattle, a large size of the pre-ovulatory follicle (POF) and resulting elevated proestrus/estrus estradiol (E2) and diestrus progesterone (P4) concentrations positively affect conceptus growth and fertility. However, sex-steroid-mediated mechanisms that influence uterine receptivity to the embryo need to be elucidated. Amino acids are important components of maternally-derived secretions that are crucial for embryo survival before implantation. The hypothesis is that the size of the POF, E2 and P4 concentrations modulate endometrial abundance of solute carrier proteins (SLC) transcripts related to AA transport and metabolism and subsequently affect lumenal amino acids concentrations. Therefore, follicle growth of Nelore cows was manipulated to produce two experimental groups: large POF and CL (LF-LCL group) and small POF and CL (SF-SCL group). On Day 4 (D4; Experiment 1) and Day 7 (D7; Experiment 2) post GnRH injection to induce ovulation, endometrial tissue and uterine washings were collected post-mortem. Transcript abundance was evaluated by qRT-PCR and amino acid concentrations were quantified in washings by HPLC. On Experiment 1, POF size, plasma E2 concentration on D-1, and plasma concentration of P4 on D4 were 15.70mm±0.43 vs. 11.31mm±0.23 (p<0.01), 2.44pg/ml±0.19 vs. 0.65pg/ml (p<0.01) and 1.40ng/ml±0.23 vs. 0.80ng/ml±0.10 (p<0.01) for the LF-LCL vs. SF-SCL groups, respectively. For Experiment 2, POF size, plasma E2 concentration on D-1 and plasma P4 concentration on D7 were 13.18mm±0.44 vs. 10.63mm±0.30 (p<0.01), 2.30pg/ml±0.57 vs. 0.50pg/ml±0.13 (p<0.01) and 3.68ng/ml±0.38 vs. 2.49ng/ml±0.43 (p=0.04) for the LF-LCL vs. SF-SCL groups, respectively. On D4, abundance of SLC6A6, SLC7A4, SLC17A5, SLC38A1, SLC38A7 and SLCY and on D7, SLC1A4, SLC6A1, SLC6A14, SLC7A4, SLC7A7, SLC7A8, SLC17A5, SLC38A1, SLC38A7, SLC43A2 and DDO was greater in the endometrium of cows from the LF-LCL group (p<0.05). On D4, higher concentrations of taurine, alanine and α-aminobutiric acid were observed in SF-SCL (p<0.05). In contrast, lower concentrations of valine and cystathionine were quantified in D7 uterine washings from SF-SCL cows (p<0.05). On D4, animals from LF-LCL group, associated with greater fertility, presented less amino acid content in uterine secretion but abundance of transporters was compatible to greater transport in comparison to animals from SF-SCL group. This suggests that before embryo moves from oviduct to uterus, amino acids transport and metabolism pathways prioritizes endometrium cells preparation for receiving the embryo but not accumulation in uterine secretions. However, on D7, when the embryo is in direct contact with uterine secretions, genes related to amino acids transport in endometrium and amino acids concentration in histotroph are up-regulated in LF-LCL cows. The latter insights indicate that amino acids metabolism and transport, towards endometrial cells or uterine secretions, might be mechanisms contributing to maternal receptivity.

Com o avanço do poder computacional nas últimas décadas, a modelagem molecular de problemas em diversas áreas se tornou mais acessível, sendo hoje uma ferramenta fundamental para o entendimento de diversos processos. Em especial, simulações moleculares com campos de força clássicos vem sendo importante para a amostragem de propriedades termodinâmicas, para a determinação de estruturas e população de confôrmeros, e seleção de configurações para utilização com métodos que combinam mecânica quântica com mecânica molecular. Os principais métodos de simulação atualmente utilizados são a dinâmica molecular (MD, do inglês molecular dynamics) e o Monte Carlo (MC). Ambos os métodos são a princípio equivalentes quando o objetivo é a amostragem configuracional, tendo a MD a vantagem de permitir a análise da dinâmica e evolução temporal, e o MC a vantagem de poder gerar configurações de forma probabilística, sem a necessidade de seguir um caminho sobre a superfície de energia potencial, o que pode resultar em uma amostragem mais eficiente. Contudo, não há ainda uma metodologia de MC que possa ser considerada eficiente e bem estabelecida para a amostragem dos graus de liberdade internos de moléculas com complexidade arbitrária. Visando avançar no desenvolvimento de métodos que trabalham nesse sentido, neste trabalho o método apresentado por Shah e Maginn [1] foi implementado e aprimorado. No método, a molécula é fragmentada em partes menores, formadas de graus de liberdade rígidos, que não variam drasticamente durante a simulação. Esses fragmentos por sua vez são conectadas por graus de liberdade maleáveis, os diedros e termos não ligados da energia. Durante a simulação a molécula tem fragmentos apagados, e então é reconstruída utilizando um esquema de Configurational Bias Monte Carlo (CBMC). A contribuição deste trabalho para a metodologia consiste em generalizar os tipos de fragmentos possíveis dentro do método, a simplificação do critério de aceitação e extensões com vieses adicionais, como é o caso do viés no potencial eletrostático e no critério de aceitação da amostragem preferencial com o CBMC. A validade da implementação do método foi avaliada através de simulações em dois sistemas simples: o octano e o 1,2-dicloroetano. Comparando a amostragem e os resultados obtidos para as populações de confôrmeros com resultados de MD e experimentais ou obtidos com outros métodos de MC da literatura foi possível verificar que a implementação reproduz os resultados esperados. Além disso, o equilíbrio conformacional da molécula de óxido mesityl (MOx) que possui duas conformações: syn e anti, foi estudado. Graças a barreira de potencial entre as duas conformações de cerca de 10 kcal/mol, a MD não é capaz de realizar uma amostragem ergódica, enquanto o CBMC realiza a amostragem sem problemas. Na simulação CBMC, a inversão da população dominante em fase gasosa e em água foi observada. Simulações do MOx em acetonitrila e metanol mostraram que a população de confôrmeros anti de fato aumenta conforme a polaridade do solvente. Entretanto, devido ao estiramento da ligação C = O do MOx em metanol devido as ligações de hidrogênio, a contribuição conformacional à posição do máximo da banda de absorção não segue a tendência da polaridade, tendo um deslocamento para o azul maior na acetonitrila do que em metanol. O estiramento da ligação C = O só pode ser observado graças a introdução da amostragem de fragmentos com deslocamentos Cartesianos e algoritmo de Metropolis ao método CBMC original. Esse efeito devido ao estiramento é compensado pelo efeito solvente, de modo que a contribuição total à energia de transição segue a polaridade do solvente. De uma maneira geral, concluímos que o desempenho do método CBMC utilizado é excelente para os casos estudados, e é inclusive superior ao da MD em alguns casos. A implementação no software DICE deixa um legado importante para diversos grupos de pesquisa, não somente por introduzir o CBMC, mas também por melhorias gerais como paralelização, lista de vizinhos e modernização do código, que foram introduzidas ao decorrer do projeto. / With the increase of computational power in the last decades, the molecular modeling of problems in several areas has become more accessible, being today a fundamental tool used to understand several processes. In particular, molecular simulations with classical force fields have been important for the sampling of thermodynamic properties, for the determination of structures and population of conformers, and for the selection of configurations to be used with methods that combine quantum mechanics with molecular mechanics. The most common simulation methods used nowadays are molecular dynamics (MD) and Monte Carlo (MC). Both methods are in principle equivalent when the goal is configurational sampling, with MD having the advantage of allowing the analysis of the dynamics and temporal evolution, while MC has the advantage of generating the configurations in a probabilistic manner, not necessarily following a path in the potential energy surface, possibly resulting in a more efficient sampling. However, there is no MC methodology that can be considered efficient and established to sample the internal degrees of freedom of molecules with arbitrary complexity. In order to advance in the development of methods that want to achieve this goal, in this work the method presented by Shah e Maginn [1] has been implemented and improved. In the method, the molecule is fragmented into smaller parts, each one composed by the hard degrees of freedom, which do not vary dramatically during the simulation. Those fragments are then connected by soft degrees of freedom, the dihedral and non-bonded terms of the energy. During the simulation the molecule has some of its fragments deleted, and is reconstructed using a Configurational Bias Monte Carlo (CBMC) approach. The contribution of this work to the methodology is generalizing the fragment types within the method, the simplification of the acceptance criteria and some extensions with additional biases, such as electrostatic potential bias and the acceptance criterion of the preferential sampling with the CBMC. The implementation was evaluated through simulations in two simple systems: octane and 1,2-dichloroethane. Comparing the sampling and results obtained for the populations of conformers with MD results, experimental data or values obtained with different MC methods present in the literature, we verified that the implementation reproduces the expected results. Beyond that, the conformational equilibrium of the mesityl oxide (MOx) molecule which has two conformers: syn and anti, was investigated. Due to the potential energy barrier between the two conformers of about 10 kcal/mol, the MD does not perform an ergodic simulation, while the CBMC does the same sampling accordingly. In the CBMC simulation, the inversion of the dominant conformer in gas phase and water was observed. The MOx simulation in acetonitrile and methanol showed that the frequency of the anti conformer indeed increases with the solvent polarity. Nonetheless, due to the stretch of the C = O bond of MOx in methanol, attributed to the hydrogen bonds formed with the solvent, the conformational contribution to the maximum of the absorption band does not follow the polarity tendency, having a larger blue shift in acetonitrile than in methanol. The C = O bond stretch can only be seen because the Cartesian displacement sampling with the Metropolis method was introduced to the original CBMC method. This effect attributed to the stretch is compensated by the solvent, in a way that the total contribution to the transition energy follows the solvent polarity. In general, we conclude that the performance of the developed CBMC method is excellent to the studied cases, being even superior to MD in some cases. The implementation in DICE leaves an important legacy to several research groups, not only for introducing the CBMC method, but also due to general improvements such as parallelization, neighbor list and code modernization, which were introduced during the project.

This thesis concerns computer simulation of diffusional processes in alloys. The main focus is on the development of simulation techniques for diffusion in single-phase domains, but also diffusion controlled phase-transformations and interfacial processes are discussed. Different one-dimensional simulation techniques for studying the Kirkendall effect are developed and analyzed. Comparisons with experimentally observed marker migration show good agreement for small shifts and comparisons with observed Kirkendall porosity show reasonable agreement under the assumption that a certain supersaturation is needed before the vacancies coalesce into pores. A convenient approach in simulations of kinetics is to use thermodynamic software, e.g. Thermo-Calc, to calculate thermodynamic quantities, e.g. chemical potentials, required in the simulation. The main drawback with such an approach is that it will generate a large amount of additional computational work. To overcome this problem a method that decreases the amount of computational work has been developed. The new method is based on artificial neural networks (ANN). By training the ANN to estimate thermodynamic quantities a significant increase in computational speed was obtained. By calculating the dissipation of available driving force due to diffusion inside migrating interfaces an approach for including the effect of solute drag in computer simulations of grain growth and phase transformations has been developed. The new method is based on an effective interfacial mobility and simulations of grain growth have been performed in binary and ternary systems using experimentally assessed model parameters. / QC 20100930

Geochemical processes associated with gas hydrate formation lead to the growth of iron sulphides which have a geophysically-measurable magnetic signature. Detailed magnetic investigation, complemented by petrological observations, were undertaken on cores from a permafrost setting, the Mackenzie Delta (Canadian Northwest Territories) Mallik region, and two marine settings, IODP Expedition 311 cores from the Cascadia margin off Vancouver Island and the Indian National Gas Hydrate Program Expedition 1 from the Bengal Fan. Stratigraphic profiles of the fine scale variations in bulk magnetic measurements correspond to changes in lithology, grain size and pore fluid geochemistry which can be correlated on local to regional scales. The lowest values of magnetic susceptibility are observed where iron has been reduced to paramagnetic pyrite, formed in settings with high methane and sulphate or sulphide flux, such as at methane vents. High magnetic susceptibility values are observed in sediments which contain detrital magnetite, for example from glacial deposits, which has survived diagenesis. Other high magnetic susceptibility values are observed in sediments in which the ferrimagnetic iron-sulphide minerals greigite or smythite have been diagenetically introduced. These minerals are mostly found outside the sediments which host gas hydrate. The mineral textures and compositions indicate rapid disequilibrium crystallization. The unique physical and geochemical properties of the environments where gas hydrates form, including the availability of methane to fuel microbiological activity and the concentration of pore water solutes during gas hydrate formation, lead to iron sulphide precipitation from solute-rich brines. Magnetic surveying techniques help delineate anomalies related to gas hydrate deposits and the diagenesis of magnetic iron minerals related to their formation. Detailed core logging measurements and laboratory analyses of magnetic properties provide direct ties to original lithology, petrophysical properties and diagenesis caused by gas hydrate formation.

Die Modellierung von komplexen Systemen, wie dem Untergrund, ist ein Hilfsmittel zur Beschreibung der in der Realität ablaufenden Prozesse. Die Durchführung von Experimenten an einem Modell, um qualitative Aussagen über ein reales System zu erhalten, wird als Simulation bezeichnet. Dabei können vielfältige Modelle, wie z.B. physikalische und mathematische, zum Einsatz kommen. Die ungesättigte Bodenzone (vadose Zone) bezeichnet den Bereich zwischen der Landoberfläche und dem Grundwasserspiegel, innerhalb dessen der Wassergehalt geringer als bei Vollsättigung, und der Druck geringer als der Atmosphärendruck ist. Dieser Bodenbereich hat für die Landwirtschaft, Geobiologie, aerobe Abbauprozesse und Grundwasserneubildung eine große Bedeutung. Für die Nachbildung von Strömungs- und Stofftransportprozessen der ungesättigten Bodenzone existieren numerische Simulationsprogramme. Ziel der vorliegenden Arbeit ist eine umfangreiche Validierung des Programms PCSiWaPro® (entwickelt an der TU-Dresden, Institut für Abfallwirtschaft und Altlasten) für unterschiedliche Anwendungsfälle. Ein weiteres Ziel der Arbeit besteht in der Untersuchung der Anwendbarkeit des aktuellen Stands des Simulationsprogramms PCSiWaPro® auf unterschiedliche Praxisfälle bei Kombination der ungesättigten Bodenzone mit technischen Anlagen. Vier Anwendungsfälle mit unterschiedlichen Zielen wurden dafür im Rahmen dieser Arbeit untersucht: die Simulation von dezentraler Abwasserversickerung (Kleinkläranlage - KKA) anhand entsprechender Säulen- und Feldversuche, die Berechnung der Grundwasserneubildung am Beispiel von Lysimetern, der Wasserhaushalt von Erddämmen und die Modellierung von Deponieabdeckungssystemen. Die Anwendungsfälle unterscheiden sich durch den Zweck der Simulation, die Geometrie, die Größe, die festgelegten Anfangs- und Randbedingungen, die Simulationszeit, die Materialien, das Koordinatensystem sowie die Ein- und Ausgabewerte. Die Simulationsergebnisse konnten eindeutig zeigen, dass das Programm PCSiWaPro® für alle im Rahmen der vorliegenden Arbeit untersuchten Fälle, mit unterschiedlichen Strömungsregimen, Stofftransport-Parametern, Randbedingungen, Koordinatensystemen sowie Raum- und Zeitdiskretisierungen anwendbar ist. Die Simulationsergebnisse der Säulenversuche am Beispiel dezentraler Abwasserversickerung zeigten eine sehr gute Übereinstimmung zwischen gemessenen und mittels PCSiWa-Pro® berechneten Werten des Wasser- und Stoffhaushaltes (Druckhöhe, Abfluss und Stoff-konzentration) der untersuchten Bodentypen B3 (schwachschluffiger Sand), B4 (Grobsand) und B5 (mittelschluffiger Sand). Die Wurzel des mittleren quadratischen Fehlers (RMSE) betrug für die Berechnung der Druckhöhe 1,84 cm bei B5, 3,61 cm bei B3 und 1,27 cm bei B4. Die relative Abweichung betrug für die Berechnung der Druckhöhe 2,19 % bei B5, 1,3 % bei B3 und ca. 5,3 % bei B4. Die Durchführung der Sensitivitätsanalyse der für die Modellierung relevanten Parameter zeigte eine sehr hohe Sensitivität der VAN GENUCHTEN-Parameter und der gesättigten hydraulischen Leitfähigkeit des Bodens. Darüber hinaus führten die Parameter nach DIN 4220 und die mithilfe von Pedotransferfunktionen aus Siebanalysen genommenen Parameter zu unterschiedlichen Ergebnissen. Im Rahmen des am Institut für Abfallwirtschaft und Altlasten durchgeführten Projektes EGSIM wurden die Programme SENSIT und ISSOP (in Zusammenarbeit mit DUALIS GmbH IT Solution) entwickelt und zur Parameteridentifikation/-kalibrierung benutzt. Die im Rahmen dieser Arbeit erzielten Ergebnisse konnten nachweisen, unter welchen Bedingungen eine Nachklärung des vollbiologisch gereinigten Abwassers innerhalb der Bodenzone möglich ist, so dass am Ort der Beurteilung (Grundwasseroberfläche) kein unzulässiger Schadstoffeintrag erfolgt. In Bezug auf die KKA-Feldmodelle ist die Anwendung des rotationssymmetrischen Koordinatensystems als Voraussetzung der Realität besser zu entsprechen und nicht als Option zu betrachten. Darüber hinaus wurden anhand der Feldmodelle verschiedene Szenarien mit kontinuierlicher und diskontinuierlicher Versickerung sowie zwei unterschiedlich großen Einleitflächen durchgeführt. Das Programm PCSiWaPro® ist sowohl für ungesättigte als auch für variabel-gesättigte porösen Medien anwendbar. Dies wurde im Rahmen der Simulation des Wasserhaushaltes eines Erddamms nachgewiesen. Die durchschnittliche relative Abweichung zwischen gemessenen und mittels PCSiWaPro® berechneten Wasserständen des entsprechenden Beobachtungspunkts im untersuchten Dammkörper lag bei 0,08 % (entspricht 5,8 cm bei einer Müchtigkeit von ca. 70 m) und das Bestimmtheitsmaß (R2) betrug 0,987. Die Simulation des Wasserhaushaltes unterschiedlicher Deponieabdichtungssystemen mittels PCSiWaPro® zeigte im Allgemeinen ein funktionierendes Ableiten des auf Deponien anfallenden Regenwassers (auch bei Starkregenereignissen). Darüber hinaus haben die durchgeführten Bewuchs-Modelle nachweisen können, dass die Vegetation der Deponieoberflächen den Wassergehalt, durch Pflanzenwurzelentzug bzw. Evapotranspiration, reduzieren können. Die Simulationsergebnisse der durchgeführten Szenarien des Wasserhaushaltes von Lysimetern zur prognostischen Berechnung der Grundwasserneubildung mittels PCSiWaPro® konnten nachweisen, dass das Programm für die Berechnung der Grundwasserneubildungsrate für diesen Zweck anwendbar ist. Die relativen Abweichungen der be-rechneten von den gemessenen Grundwasserneubildungsraten sind auf die verwendeten Materialparameter sowie auf Vernachlässigung der möglicherweise in Lysimetern sich befin-denden Makroporen (duale Porosität) zurückzuführen. / The modelling of complex systems such as the underground is a means to describe the processes occurring in the reality. The conducting of experiments on a model to obtain qualitative evidence about a real system is referred to as a simulation. Thereby, various models (e.g. physical and mathematical models) can be used. The unsaturated zone (vadose zone) is the region between the land surface and the water table, in which the water content is less than full saturation, and the pressure is lower than the atmospheric pressure. The unsaturated zone is very significant for agriculture, geobiology, aerobic degradation processes and groundwater recharge. The processes of water flow and solute transport in the unsaturated zone can be described by means of numerical simulation programs. The aim of the present work is a comprehensive validation of the simulation program PCSiWaPro® (developed at the TU-Dresden, Institute of Waste Management and Contaminated Site Treatment) for different applications. Another aim of this work is to investigate the applicability of the current version of PCSiWaPro® for different cases of a combination between the unsaturated zone and technical facilities. Four application cases with different objectives were investigated within the present work, which are: the simulation of decentralized wastewater infiltration with corresponding column and field experiments, the computation of groundwater recharge by means of lysimeters, the water balance of earth dams and the modelling of landfill covering systems. The application cases differ from each other by the objective of the simulation, the geometry, the size, the specified initial and boundary conditions, the simulation time, the applied materials, the coordinate system, the input and output data. The simulation results clearly showed that PCSiWaPro® is applicable for all investigated cases under consideration of different flow and solute transport regimes, parameters, boundary conditions, spatial and temporal discretization, and coordinate systems. The simulation results of the experimental soil columns for the decentralized treated wastewater infiltration case showed a very good agreement between measured and computed values of water and solute balance (pressure head, flow and solute concentration) of the investigated soil types B3 (slightly silty sand), B4 (coarse sand / gravel) and B5 (medium silty sand). The root of the mean squared error (RMSE) for the computation of the pressure head was 1,84 cm at B5, 3,61 cm at B3 and 1,27 cm at B4. The relative deviation in case of pressure head computation was 2,19 % at B5, 1,3 % at B3 and 5,3 % at B4. The implementation of the sensitivity analysis of the relevant parameters for the modelling showed a very high sensitivity of the VAN GENUCHTEN parameters and the saturated hydraulic conductivity of the soil. Moreover, the parameters according to DIN 4220 led to different results than the estimated ones according to pedotransfer methods based on sieve analysis. Within the project EGSIM, which was carried out at the Institute for waste management and contaminated sites treatment in collaboration with DUALIS GmbH IT Solution, the programs SENSIT and ISSOP were developed and used for parameter identification/ calibration. The results obtained in this Work showed under which conditions is a secondary treatment of full biologically treated wastewater in the soil possible, so that no unallowable pollutants entry in the groundwater occurs. With regard to the field models of this application the implementation of the rotationally symmetric coordinate system should be considered as a condition and not as an option for a better corresponding to the reality. Furthermore, different scenarios of the field models were carried out with continuous and discontinuous infiltration, as well as under different initiation areas. PCSiWaPro® could be applied for both unsaturated and variably-saturated porous media. This could be proven by the simulation of the water balance in an earth dam. The average relative deviation between measured and simulated water levels of the corresponding observation point in the investigated dam embankment was 0,08 % (corresponding to 5,8 cm at 70 m thickness) and the coefficient of determination (R2) was 0,987. In general, the simulation of the water balance using PCSiWaPro® of different landfill covering systems showed a successful draining of the falling rainwater (even under heavy rainfall). In addition, the implemented vegetation models have proven that the vegetation of the landfill surface can reduce the water content in the landfill by evapotranspiration and water uptake by roots. The water balance simulation results of the scenarios for the computation of groundwater recharge by means of lysimeters showed that the program is applicable for this case. The relative deviation of the simulated from the measured groundwater recharge rates occur due to the implemented material parameters as well as to the neglect of macro pores effects (dual porosity).

The modelling of the processes of advection and dispersion-diffusion is the most crucial factor in solute transport simulations. It is generally appreciated that the first order upwind difference scheme gives rise to excessive numerical diffusion, whereas the conventional second order central difference scheme exhibits severe oscillations for advection dominated transport, especially in regions of high solute gradients or discontinuities. Higher order schemes have therefore become increasingly used for improved accuracy and for reducing grid scale oscillations. Two such schemes are the QUICK (Quadratic Upwind Interpolation for Convective Kinematics) and TOASOD (Third Order Advection Second Order Diffusion) schemes, which are similar in formulation but different in accuracy, with the two schemes being second and third order accurate in space respectively for finite difference models. These two schemes can be written in various finite difference forms for transient solute transport models, with the different representations having different numerical properties and computational efficiencies. Although these two schemes are advectively (or convectively) stable, it has been shown that the originally proposed explicit QUICK and TOASOD schemes become numerically unstable for the case of pure advection. The stability constraints have been established for each scheme representation based upon the von Neumann stability analysis. All the derived schemes have been tested for various initial solute distributions and for a number of continuous discharge cases, with both constant and time varying velocity fields. The 1-D QUICKEST (QUICK with Estimated Streaming Term) scheme is third order accurate both in time and space. It has been shown analytically and numerically that a previously derived quasi 2-D explicit QUICKEST scheme, with a reduced accuracy in time, is unstable for the case of pure advection. The modified 2-D explicit QUICKEST, ADI-TOASOD and ADI-QUICK schemes have been developed herein and proved to be numerically stable, with the bility sta- region of each derived 2-D scheme having also been established. All these derived 2-D schemesh ave been tested in a 2-D domain for various initial solute distributions with both uniform and rotational flow fields. They were further tested for a number of 2-D continuous discharge cases, with the corresponding exact solutions having also been derived herein. All the numerical tests in both the 1-D and 2-D cases were compared with the corresponding exact solutions and the results obtained using various other difference schemes, with the higher order schemes generally producing more accurate predictions, except for the characteristic based schemes which failed to conserve mass for the 2-D rotational flow tests. The ADI-TOASOD scheme has also been applied to two water quality studies in the U. K., simulating nitrate and faecal coliform distributions respectively, with the results showing a marked improvement in comparison with the results obtained by the second order central difference scheme. Details are also given of a refined numerical representation of flooding and drying of tidal flood plains for hydrodynamic modelling, with the results showing considerable improvements in comparison with a number of existing models and in good agreement with the field measured data in a natural harbour study.

L'électrodialyse peut être utilisée pour traiter des effluents salins contenant de la matière organique. La compréhension des mécanismes de transfert (eau, ions, espèces organiques) à travers les membranes échangeuses d'ions et particulièrement l'influence de la composition ionique est un point clé vis-à-vis des performances du procédé. L'objectif de cette thèse est l'étude du transfert et la relation avec les performances de dessalement. Les nombres d'hydratation des ions sont tout d'abord calculés à partir des mesures du transfert des ions et de l'eau. Ils sont indépendants du courant et de la composition saline. La comparaison avec des valeurs de la littérature montre que les membranes ont peu d'effet sur l'hydratation des ions. Le transfert d'espèces organiques est ensuite étudié pour différentes compositions salines. Outre la diffusion, une contribution additionnelle est mise en évidence (convection pour les espèces neutres, migration pour les espèces chargées). Pour les espèces neutres, diffusion et convection sont du même ordre de grandeur et fixées par l'effet stérique. Des tendances inverses sont obtenues concernant l'hydratation des ions, la diffusion étant limitée par les modifications des membranes, la convection étant limitée par l'hydratation des espèces organiques en solution. Pour les espèces chargées, la migration domine la diffusion, les deux contributions étant influencées par la présence de sel. Les performances de dessalement sont enfin discutées sur la base d'un modèle phénoménologique à 4 paramètres liés au transfert de l'eau, des ions et des espèces organiques. La robustesse du modèle est validée pour différentes conditions. Ce travail montre que l'électrodialyse est une technologie très prometteuse pour le dessalement d'effluents contenant de la matière organique. / Electrodialysis can be used to treat saline water containing organic solute, separating organic solutes from salt. The understanding of salt, water and organic solute transfer through ion- exchange membranes and especially the influence of salt composition is a key factor regarding the process performances. The aim of the Thesis is to investigate the mass transfer and the relationship with the desalination performance. Firstly, hydration numbers of individual ion transferring through the membranes are computed based on experimental measurements of ion- water flux. They are independent from the salt compositions and current. Comparison with literatures values shows that the membranes have a weak influence on the ion hydration. Secondly, the transfer of different organic solutes is investigated with different salt compositions. Two contributions are pointed out, diffusion and additional one (convection for neutral solute, migration for charged one). For neutral solutes, diffusion and convection are comparable and both fixed by steric effect. Ion hydration leads to reversed trend for diffusion due to membrane swelling and convection due to solute dehydration. For charged solute, migration is more important than diffusion, both being influenced by the presence of salt. Then, desalination performance is discussed based on a phenomenological model, consisting of 4 parameters, related to ion, water and organic solute transfer respectively. The robustness of the model is demonstrated for different conditions. This work shows that electrodialysis can be a very promising process for the desalination of saline water containing organic solutes.

Esta dissertação apresentou um estudo dos mecanismos de transporte de sódio, fosfato e amônio em colunas indeformadas de material inconsolidado residual de arenitos da Formação Adamantina. Em campo foi realizada caracterização táctil visual do material, alem de ensaios de condutividade hidráulica. Em laboratório, realizou-se ensaio de coluna em material indeformado, para que fossem obtidos os parâmetros de fluxo de água: velocidade linear media, velocidade de Darcy, vazão e condutividade hidráulica. Também foram obtidos os coeficientes de dispersão hidrodinâmica dos três íons estudados por meio de quatro métodos. Os fatores de retardamento dos íons foram obtidos por meio de três métodos. Para auxiliar nas analises, o solo foi caracterizado mineralógica, química, física e físico-quimicamente. Adicionalmente foram feitas analises da poro simetria e estudo das trajetórias de transporte. As informações foram integradas para que fosse possível analisar os parâmetros de transporte de solutos no solo. Com esta pesquisa percebeu-se que o uso dos parâmetros de transporte em modelagem do transporte de contaminantes deve ser feito com cautela, observando tanto as características do solo (mineralógicas, físicas, físico-químicas) quanto os modelos conceituais e as limitações dos métodos utilizados. / This research aimed to study the transport mechanisms of sodium, phosphate and ammonium in undisturbed columns of unconsolidated residual material of the sandstones from the Adamantina Formation. At field, visual and tactile characterization of the material were performed as well as hydraulic conductivity tests . At laboratory, there were made column tests in undisturbed samples to obtain the parameters of water flow, i.e., average linear velocity, Darcy velocity, flow rate and hydraulic conductivity. Hydrodynamic dispersion coefficients of every studied ion were determined using four methods. The retardation factors of the three ions were obtained using three methods. To assist the analysis, the soil was mineralogical, chemistry, physically and physic-chemically characterized. We also analyzed the water retention curve, mercury intrusion porosimetry and solute transport trajectories. All available data were integrated for analyzing the parameters of solute transport in soil. The results showed that the use of transport parameters in modeling of contaminant transport should be done with caution, observing soil characteristics, the conceptual models and the limitations of the methods used.