The decline of tree islands in the freshwater-Everglades wetland because of hydrologic manipulation, has compromised valuable ecosystem services. Although the role of tree islands in maintaining freshwater quality stems largely from evapotranspiration processes, fundamental questions remain about the effects of different geologic materials on their hydrogeochemical functioning. To reduce this uncertainty, the lithological composition of a set of man-made tree islands was investigated coupled with long-term hydrologic and hydrochemical data. Key results indicate that limestone substrates and peat substrates with elevated proportions of sand, facilitated surface water-groundwater interactions and mineral dissolution. However, limestone-based islands were more effective in lowering the water table and concentrating solutes in response to evapotranspiration during low surface water stages. Additionally, the peat substrate of an island with low sand content favored the thermodynamic conditions for calcite accumulation in the phreatic zone, while phosphorus concentrations in the groundwater were associated with the breakdown of organic matter.

abstract: The hydrous alteration of ultramafic rocks, known as serpentinization, produces some of the most reduced (H2 >1 mmolal) and alkaline (pH >11) fluids on Earth. Serpentinization can proceed even at the low-temperature conditions (<50°C) characteristic of most of Earth’s continental aquifers, raising questions on the limits of life deep in the subsurface and the magnitude in the flux of reduced volatiles to the surface. In this work, I explored the compositions and consequences of fluids and volatiles found in three low-temperature serpentinizing environments: (1) active hyperalkaline springs in ophiolites, (2) modern shallow and deep peridotite aquifers, and (3) komatiitic aquifers during the Archean. Around 140 fluids were sampled from the Oman ophiolite and analyzed for their compositions. Fluid compositions can be accounted for by thermodynamic simulations of reactions accompanying incipient to advanced stages of serpentinization, as well as by simulations of mass transport processes such as fluid mixing and mineral leaching. Thermodynamic calculations were also used to predict compositions of end-member fluids representative of the shallow and deep peridotite aquifers that were ultimately used to quantify energy available to various subsurface chemolithotrophs. Calculations showed that sufficient energy and power supply can be available to support deep-seated methanogens. An additional and a more diverse energy supply can be available when surfacing deep-seated fluids mix with shallow groundwater in discharge zones of the subsurface fluid pathway. Finally, the consequence of the evolving continental composition during the Archean for the global supply of H2 generated through komatiite serpentinization was quantified. Results show that the flux of serpentinization-generated H2 could have been a significant sink for O2 during most of the Archean. This O2 sink diminished greatly towards the end of the Archean as komatiites became less common and helped set the stage for the Great Oxidation Event. Overall, this study provides a framework for exploring the origins of fluid and volatile compositions, including their redox state, that can result from various low-temperature serpentinizing environments in the present and past Earth and in other rocky bodies in the solar system. / Dissertation/Thesis / Doctoral Dissertation Geological Sciences 2020

Pressure solution creep is a fundamental deformation mechanism in the upper crust. Overburden pressure that acts upon layers of sediment leaves grains densely packed. Nonhydrostatic stress distributed over the contacts between grains brings an enhancement effect on surface dissolution. As surface retreat over the contacts and hence grain repacking squeeze out pore water in the voids, the layers of sediment are deformed to become denser and denser. This work aims to identify what process slows down pressure solution creep over time. For this purpose, a new mechanistic model of pressure solution creep is developed, derived from the reaction rate law for nonhydrostatic dissolution kinetics under the hypothesis of a closed system. The present mechanistic model shows that (1) the creep rate goes down as a combined consequence of stress transfer across expanding contacts and concentration build-up in the interlayer of absorbed water; and (2) solute migration process acts as the primary rate-limiting process of pressure solution creep in the long run. This work then focuses on hydraulic evolution of channelling flow through a single deformable fracture which is simultaneously subjected to pressure solution creep. The developed 1-D reactive transport model is allowed to capture the strong interaction between channelling flow and pressure solution creep under crustal conditions. This numerical investigation provides a justified interpretation for the unusual experimental observation that fracture permeability reduction does not necessarily cause concentration enrichment. Temperature elevation contributes to accelerating the progression of pressure solution creep.

La Nouvelle-Calédonie détient d’importantes réserves de nickel latéritique et est devenue, en 2017, le cinquième producteur mondial de Ni. Ces dépôts sont habituellement considérés comme résultant d’altération latéritique intense de la péridotite, qui constitue la principale source de nickel. Ainsi, le principal modèle conceptuel de la formation des minerais de nickel latéritique en Nouvelle-Calédonie est un modèle per descensum où la plupart des éléments (Mg, Ni et Si) ont été lessivés depuis la surface, en particulier lors du développement du sol latéritique. Le nickel est ensuite reprécipité, soit dans la goethite de la latérite fine, soit au niveau de la saprolite, sous forme de goethite et de silicates Mg-Ni, dont des talc-like ou kérolite. Les observations minéralogiques et structurales récentes ainsi que les données minières ont cependant mis en évidence de nombreux types d’hétérogénéités dans les concentrations, et la distribution des porteurs de Ni. Comprendre les facteurs la mobilité de cet élément, ses mécanismes de piégeage ainsi que les paramètres chimiques et hydrodynamiques à l’origine de ce piégeage, est essentiel afin de prévoir la distribution du nickel dans les profils latéritiques en Nouvelle-Calédonie, et constitue l’objectif de cette thèse. Ce travail est basé sur le développement (i) d’un modèle 1D s’intéressant en particulier au comportement géochimique du nickel lors de l’altération de l’ophiolite, sa comparaison avec les observations in situ et une compréhension détaillée de la mobilité des éléments traces pendant le processus, et (ii) d’un modèle 2D hydro-géochimique couplé avec l’hydrodynamique complexe des profils latéritiques, améliorant ainsi la connaissance du contrôle structural sur la redistribution et la minéralisation du nickel. Tandis que les simulations 1D permettent de mieux comprendre les aspects chimiques contrôlant les processus de rétention du nickel au sein d’un profil, le modèle 2D se révèle être un outil puissant pour la compréhension de la formation des dépôts locaux les plus riches en nickel. Les résultats du modèle 2D montrent une remobilisation du nickel depuis les horizons supérieurs puis sa reprécipitation sous forme de silicates dans la saprolite. Le nickel remobilisé provient principalement de la zone saprolitique à cause de la dissolution des silicates de nickel formés précédemment ainsi que de l’olivine résiduelle de cette zone. Ce modèle a également révélé que l’horizon latéritique (et en particulier les oxy- hydroxydes de nickel) avait un faible impact dans la remobilisation du nickel. L’infiltration latérale de l’eau contenant le nickel dissout issu des formations surincombantes est à l’origine de la formation des zones les plus riches dans les parties inférieures du profil. Cette redistribution est entièrement contrôlée par l’hydrodynamique locale, la topographie ainsi que l’orientation et la position des fractures. Les modèles présentés permettent d’expliquer les processus de formation des minerais de nickel latéritique saprolitique, améliorant ainsi la compréhension des paramètres contrôlant la mobilité des éléments traces dans un environnement ultramafique. Ceci donne une nouvelle clé de distribution du nickel dans les profils actuels, qui peut devenir un outil pour la prospection minière, et la recherche de nouvelles ressources exploitables / New Caledonia hosts significant lateritic nickel reserves, and presently became the fifth largest Ni producer in the world. These deposits are generally thought to be closely as- sociated with the intense chemical and mechanical weathering of peridotite bedrock that is a principal source of nickel. Thus, the main ore genesis model for Ni ores in New Caledonia is based on a single per descensum model where most elements (Mg, Ni, and Si) are leached from the surface, particularly, during lateritic soil development. Nickel is then concentrated either in the fine-grained laterite where goethite is the main Ni bearer, the so-called ’lateritic ore’, or below the laterites, in the saprolite level, where nickel occurs as goethite and several types of Mg-Ni silicates, in particular kerolite. Recent mineralogical and structural observations together with mining data have revealed a lot of different types of heterogeneities associated with the distribution and mineralogy of Ni bearing minerals. Therefore, in depth investigations of Ni mobility, its retardation processes along with its governing chemical and hydrodynamic parameters are of big importance for understanding and subsequent prediction of Ni distribution in profiles of New Caledonia. Such an investigation is an objective of the present work. The concept is based on the development of i) a powerful 1D model with particular emphasis on Ni geochemical behavior during ophiolite weathering, its comparison with in situ observations, and detailed understanding of trace elements mobility, and ii) 2D hydro-geochemical model coupled with complex hydrodynamics, that would additionally provide new insight into the structural control on Ni redistribution and mineralization. While the 1D simulations provide a remarkable result for understanding the chemical features that drive Ni retention processes in a profile, 2D model appears to be a powerful tool for understanding how local Ni-enrichments may form. The results of this model show the reactivation of Ni from upper horizons and its concentration in neo-formed silicates in bottom of the saprolite. The reactivated Ni comes mostly from the saprolite horizon due to the redissolution of previously formed Ni-bearing silicates and still persisting in this olivine zone. Modeling has revealed minor contribution of the laterite horizon (Ni-oxi-hydroxides) into the Ni remobilization. The lateral infiltration of water with remobilized Ni from areas such as topographic highs to downstream slope areas leads to the formation of richest deposits in this lower part of profile. The manner of redistribution is fully governed by the topographic slopes, orientation and position of the fractures. Presented models appear to be of importance in attempt of explanation of Ni mineralization processes, revealing the main keys to understanding the control of trace elements mobility in ultramafic environment. The latter gives new insights into the Ni distribution in present day profiles and, therefore, may greatly help in mineral prospecting and forecasting the distribution of future resources

Hydrothermal fluid circulation is an important process in the formation and evolution of ocean crust. A tectonic window located at Pit Deep (NE corner Easter Microplate) provides an ideal location to examine a 3-dimensional view of ocean crust formed at the fast-spreading East Pacific Rise. This study focuses on the base metal (Cu, Ni, Mn, Co, Zn, and Pb) content of the bulk rock and mineral components in the sheeted dike complex. There is no observable trend of metal mobility with depth, geographic location, or dominant alteration phase. Secondary mineral analyses (using LA-ICP-MS) show that metals are redistributed throughout the sheeted dikes, entering into secondary sulphides, chlorite, and amphibole. Temperature and mineral stability is a primary control of metal mobility in these rocks. Due to highly variable metal concentrations and observed temperatures of alterations, the hydrothermal cell is suggested to be a continuously evolving system, and can cause the large variability observed in the metal distribution in the sheeted dikes. / Graduate / 0996 / 0411 / 0372

Um software de modelagem de especiação geoquímica é responsável pelo cálculo da distribuição das espécies dissolvidas entre solutos e complexos aquosos, e também computar os índices de saturação para diferentes minerais. Neste trabalho nós apresentamos SHPECK, um software desenvolvido para modelar sistemas de equilíbrio geoquímico usando condições de balanço de massa baseadas no conceito da lei de fases (GARRELS; CHRIST, 1965). SHPECK gera um sistema de equações de ação de massa acopladas com restrições de equilíbrio e resolve com a utilização do método se Newton-Raphson. Nosso software aceita qualquer combinação de elementos, espécies e reações, permitindo ao usuário criar diferentes ambientes de simulação e, portanto, controlar qualquet aspecto e configuração do modelo. SHPECK contém uma interface de interação com o usuário e também um banco de dados estruturado que controla todo o gerenciamento dos dados termodinâmicos utilizados para a modelagem geoquímica. Aliado a isso, apresentamos também os conceitos básicos necessários para compreenção da modelagem geoquímica seguida por uma revisão de opções de software disponíveis para modelagem geoquímica. Para finalizar, fizemos uma validação do SHPECK através da modelagem de um sistema de reações diagenéticas observadas em um reservatório asiliclástico e realizamos um estudo comparativo dos resultados do SHPECK com outros software disponíveis. Também para validação, realizamos uma avaliação de tempo de acesso ao banco de dados e pode-se notar um aumento de performance considerável através do uso de um banco de dados relacional comparando-se aos approaches existentes. / A geochemical speciation modeling software is responsible for calculating the distribution of dissolved species between solutes and aqueous complexes, and also computes saturation indexes for different minerals. In this work we introduce SHPECK, a software program developed to model geochemical equilibrium systems using the mass-balance conditions based on the phase rule concept (GARRELS; CHRIST, 1965). SHPECK composes a system of mass-action equations coupled with equilibrium constraints and solve using Newton-Raphson method. Our software accepts any general combination of elements, species, and reactions, allowing the user to create different environments, simulations and, therefore, fully control any aspect and configuration of the model. It provides an interactive user interface as well as the support of a builtfrom- the-ground database structure that handles the management of the whole thermodynamic data used for the geochemical modeling. Also, we present the basic concepts for geochemical modeling followed by a computer science based review about the available geochemical modeling software. Finally, we validate SHPECK by modeling the diagenetic reactions observed in asiliciclastic reservoir and by performing a comparative study with other modelling software package. In addition to this, a database comparison was addressed and the results demonstrate a substantial improvement on the performance by the use of the SHPECK’s relational database comparing to the existent approaches.

Um software de modelagem de especiação geoquímica é responsável pelo cálculo da distribuição das espécies dissolvidas entre solutos e complexos aquosos, e também computar os índices de saturação para diferentes minerais. Neste trabalho nós apresentamos SHPECK, um software desenvolvido para modelar sistemas de equilíbrio geoquímico usando condições de balanço de massa baseadas no conceito da lei de fases (GARRELS; CHRIST, 1965). SHPECK gera um sistema de equações de ação de massa acopladas com restrições de equilíbrio e resolve com a utilização do método se Newton-Raphson. Nosso software aceita qualquer combinação de elementos, espécies e reações, permitindo ao usuário criar diferentes ambientes de simulação e, portanto, controlar qualquet aspecto e configuração do modelo. SHPECK contém uma interface de interação com o usuário e também um banco de dados estruturado que controla todo o gerenciamento dos dados termodinâmicos utilizados para a modelagem geoquímica. Aliado a isso, apresentamos também os conceitos básicos necessários para compreenção da modelagem geoquímica seguida por uma revisão de opções de software disponíveis para modelagem geoquímica. Para finalizar, fizemos uma validação do SHPECK através da modelagem de um sistema de reações diagenéticas observadas em um reservatório asiliclástico e realizamos um estudo comparativo dos resultados do SHPECK com outros software disponíveis. Também para validação, realizamos uma avaliação de tempo de acesso ao banco de dados e pode-se notar um aumento de performance considerável através do uso de um banco de dados relacional comparando-se aos approaches existentes. / A geochemical speciation modeling software is responsible for calculating the distribution of dissolved species between solutes and aqueous complexes, and also computes saturation indexes for different minerals. In this work we introduce SHPECK, a software program developed to model geochemical equilibrium systems using the mass-balance conditions based on the phase rule concept (GARRELS; CHRIST, 1965). SHPECK composes a system of mass-action equations coupled with equilibrium constraints and solve using Newton-Raphson method. Our software accepts any general combination of elements, species, and reactions, allowing the user to create different environments, simulations and, therefore, fully control any aspect and configuration of the model. It provides an interactive user interface as well as the support of a builtfrom- the-ground database structure that handles the management of the whole thermodynamic data used for the geochemical modeling. Also, we present the basic concepts for geochemical modeling followed by a computer science based review about the available geochemical modeling software. Finally, we validate SHPECK by modeling the diagenetic reactions observed in asiliciclastic reservoir and by performing a comparative study with other modelling software package. In addition to this, a database comparison was addressed and the results demonstrate a substantial improvement on the performance by the use of the SHPECK’s relational database comparing to the existent approaches.

Um software de modelagem de especiação geoquímica é responsável pelo cálculo da distribuição das espécies dissolvidas entre solutos e complexos aquosos, e também computar os índices de saturação para diferentes minerais. Neste trabalho nós apresentamos SHPECK, um software desenvolvido para modelar sistemas de equilíbrio geoquímico usando condições de balanço de massa baseadas no conceito da lei de fases (GARRELS; CHRIST, 1965). SHPECK gera um sistema de equações de ação de massa acopladas com restrições de equilíbrio e resolve com a utilização do método se Newton-Raphson. Nosso software aceita qualquer combinação de elementos, espécies e reações, permitindo ao usuário criar diferentes ambientes de simulação e, portanto, controlar qualquet aspecto e configuração do modelo. SHPECK contém uma interface de interação com o usuário e também um banco de dados estruturado que controla todo o gerenciamento dos dados termodinâmicos utilizados para a modelagem geoquímica. Aliado a isso, apresentamos também os conceitos básicos necessários para compreenção da modelagem geoquímica seguida por uma revisão de opções de software disponíveis para modelagem geoquímica. Para finalizar, fizemos uma validação do SHPECK através da modelagem de um sistema de reações diagenéticas observadas em um reservatório asiliclástico e realizamos um estudo comparativo dos resultados do SHPECK com outros software disponíveis. Também para validação, realizamos uma avaliação de tempo de acesso ao banco de dados e pode-se notar um aumento de performance considerável através do uso de um banco de dados relacional comparando-se aos approaches existentes. / A geochemical speciation modeling software is responsible for calculating the distribution of dissolved species between solutes and aqueous complexes, and also computes saturation indexes for different minerals. In this work we introduce SHPECK, a software program developed to model geochemical equilibrium systems using the mass-balance conditions based on the phase rule concept (GARRELS; CHRIST, 1965). SHPECK composes a system of mass-action equations coupled with equilibrium constraints and solve using Newton-Raphson method. Our software accepts any general combination of elements, species, and reactions, allowing the user to create different environments, simulations and, therefore, fully control any aspect and configuration of the model. It provides an interactive user interface as well as the support of a builtfrom- the-ground database structure that handles the management of the whole thermodynamic data used for the geochemical modeling. Also, we present the basic concepts for geochemical modeling followed by a computer science based review about the available geochemical modeling software. Finally, we validate SHPECK by modeling the diagenetic reactions observed in asiliciclastic reservoir and by performing a comparative study with other modelling software package. In addition to this, a database comparison was addressed and the results demonstrate a substantial improvement on the performance by the use of the SHPECK’s relational database comparing to the existent approaches.