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.

La composition chimique de la croûte continentale a significativement évolué à la transition Archéen-Protérozoïque (3000–2500 Ma), témoignant de changements géodynamiques majeurs à cette époque. Afin d’étudier l’expression et les origines de ces changements, qui sont encore mal contraints, j’ai étudié une diversité de granitoïdes qui se sont mis en place dans cette gamme d’âges à la marge Nord du craton du Kaapvaal, en Afrique du Sud. Ce travail a permis de préciser la typologie et l’origine des granitoïdes tardi-archéens ; ceux-ci peuvent être classés dans trois grands groupes : (1) Les sanukitoïdes, représentés en Afrique du Sud par le pluton de Bulai, sont des magmas dérivant de l’interaction entre une péridotite mantellique et un composant riche en éléments incompatibles (TTG, liquide issu de la fusion de sédiments, et, plus rarement, fluide aqueux). Les sanukitoïdes peuvent être classés en deux groupes distincts, selon les mécanismes de cette hybridation : les low-Ti sanukitoids proviennent d’une simple hybridation du liquide silicaté avec la péridotite, alors que les high-Ti sanukitoids sont issus de la fusion d’un assemblage métasomatique à amphibole et phlogopite, résultant de ces interactions. Enfin, les mécanismes de différenciation des suites sanukitoïdes au niveau de la croûte sont contrôlées par des mécanismes de cristallisation fractionnée ou (moins vraisemblablement) de fusion partielle. (2) Les sanukitoïdes « marginaux », représentés dans le craton du Kaapvaal par les plutons de Mashashane, Matlala, Matok et Moletsi, sont des granitoïdes résultant de l’interaction entre des sanukitoïdes et des magmas provenant de la fusion de croûte préexistante. Etant donné la large gamme de sources possibles (TTG, métasédiments, roches mafiques) d’un craton à l’autre, ce groupe est extrêmement diversifié. Leurs mécanismes de différenciation sont contrôlés par la cristallisation fractionnée. (3) Certains granites, tels que le batholite de Turfloop en Afrique du Sud, sont directement issus de la fusion de lithologies crustales (TTG, métasédiments et amphibolites). Au sein du craton du Kaapvaal, l’évolution spatio-temporelle du magmatisme tardi-archéen suit un schéma très caractéristique : les TTG se mettent en place entre ~3300 et ~2800 Ma, puis laissent la place à la genèse de l’ensemble des granitoïdes présentés ci-dessus, qui se déroule entre 2780 et 2590 Ma. Cette séquence d’évènements est reproduite au sein de tous les cratons du monde à la fin de l’Archéen. Elle témoigne de l’avènement des processus de recyclage crustal, puisque, par opposition aux TTG archéennes qui dérivent de métabasaltes juvéniles, les magmas tardi-archéens sont issus à la fois de la différenciation intracrustale et de l’interaction entre une péridotite et du matériel continental introduit dans le manteau. Cette dualité de processus pétrogénétiques est aussi très typique des épisodes magmatiques qui ont lieu à la fin des cycles de subduction-collision post-archéens. Ainsi, l’évolution de la composition des granitoïdes entre 3000 et 2500 Ma traduit vraisemblablement l’initiation d’une forme de tectonique des plaques proche du régime actuel. Celle-ci serait liée au refroidissement planétaire global, qui a probablement entraîné un « effet de seuil » dans l’évolution de l’épaisseur de la croûte océanique ainsi que la rhéologie et le volume de la croûte continentale, permettant ainsi à la subduction et à la collision de ne devenir thermo-mécaniquement stables qu’à partir de la fin de l’Archéen. / The chemical composition of continental crust significantly evolved though time, in particular at the Archaean-Proterozoic transition (3000–2500 Ma), which witnesses major geodynamic changes at that time. The nature and origin of these changes are poorly constrained so far. To better constrain them, I studied a range of granitoid emplaced at that time at the northern margin of the Kaapvaal Craton, in South Africa. In the light of my work, the typology and origin of this magmatism has been reappraised; in particular, the late-archaean granitoids can be split in three different groups : (1) Sanukitoids are represented in South Africa by the Bulai pluton. They are hybrid magmas derived from interaction between mantle peridotite and a component rich in incompatible elements (generally a melt derived from either metabasalts or metasediments). They can be separated in two groups, depending on the hybridation process: low-Ti sanukitoids derive from one-step interaction of silicate melt with peridotite, while high-Ti sanukitoids result from melting of a metasomatic, amphibole- and phlogopite-bearing assemblage equilibrated during the interactions. Finally, the differentiation mechanisms of sanukitoid suites at crustal levels are mainly controlled by fractional crystallization or, less likely, partial melting. (2) « Marginal » sanukitoids, as represented in the Kaapvaal craton by Mashashane, Matlala, Matok and Moletsi plutons, are produced by interactions between sanukitoids and crust-derived melts. Because the source of the latter can be very different from a craton to another, this group of granitoids is extremely diverse. Their magmatic evolution is mostly controlled by fractional crystallization, such as sanukitoids. (3) Some granites, such as those from the Turfloop batholith in South Africa, directly derive from melting of older crustallithologies (TTGs, metasediments, mafic rocks). The evolution of late-archaean magmatism in the Kaapvaal craton follows a very typical sequence: genesis of TTG took place between ~3300 and ~2800 Ma, and give way to the emplacement of all granitoid types presented above, which occurs in a short time span between 2780 and 2590 Ma. This succession of events is identical within every craton worldwide at the end of the Archaean. It witnesses the advent of crust recycling processes, as late-archaean magmas derive from both intracrustal differentiation and interactions between peridotite and continental material introduced within the mantle. This sharply contrasts with the genesis of TTG through melting of juvenile metabasalts only. This duality of petrogenetic processes is also typical of magmatic events in late- to post-orogenic settings, at the end of present-day subduction-collision cycles. As a result, the evolution of the crust composition between 3000 and 2500 Ma likely reflects the initiation of modernstyle plate tectonics. This would be the consequence of global cooling of Earth, which has induced a threshold effect in parameters such as (1) the thickness of oceanic crust and (2) the rheology and volume of continental crust. Indeed, these parameters exert a primary control on the thermo-mechanical stability of subduction and collision, and both became possible at the end of the Archaean only.

No description available.

Gold mining in the Witwatersrand Basin of South Africa has resulted in soil contamination due to the lack of sufficient environmental management plans for the tailings dumps and remnant footprints. Tailings reclamation as a strategy of reducing pollution in the Central Rand, for instance, has resulted in contamination of water systems by acid mine drainage (AMD). After removal of the tailings dumps, remnant material is left over on the tailings footprints and these contain significant amounts of pollutants that were initially in the tailings. Heavy rainfall during summer dissolves primary minerals and later in the dry season, secondary minerals are precipitated as efflorescent crusts on and nearby tailings dumps as well as footprints due to high evaporation. The efflorescent crusts can redissolve when it rains and form acidic, metal and sulphate-rich solutions due to their soluble characteristics. This study aimed to characterise tailings footprints in areas targeted for human settlements and office spaces to assess their potential to release left over toxic elements such arsenic (As), lead (Pb), copper (Cu) and zinc (Zn). The approach to the study involved characterisation of oxidised and unoxidised tailings material and secondary precipitates on both tailings dumps and footprints. This involved determining the mineralogical composition using Powder X-ray Diffraction (PXRD). Dissolution and leaching studies were also conducted on the material followed by determination of constituent elements using inductively coupled plasma optical emission spectroscopy (ICP-OES) and sulphates using ion chromatography (IC). The leaching solutions used included rainwater; dilute sulphuric acid at pH of 3.0 (a common leachate in such acidic soils); as well as plant exudates such as oxalic and citric acids. The leachate solutions were used to correlate the mineralogical composition of secondary precipitates and tailings footprints. Potential implications on humans following any accidental ingestion of the tailings or contaminated soils were assessed using gastric juices. The ecological risk factors and risk index together with the model to evaluate daily intake and different pathways to humans were used to assess the toxicity caused by exposure to contaminants in the materials. The experimental work was augmented by computer simulations based on geochemical modelling (using the PHREEQC geochemical modelling code) to determine the speciation of elements (and thus their potential lability and bioavailability), dissolution and formation of secondary mineral precipitates in the tailings dumps and footprints. The findings of the PXRD study showed that the mineralogy of the tailings and footprints was dominated by quartz (SiO2) and some minor minerals such as pyrite (FeS2), pyrophyllite (Al2Si4O10(OH)2), chlorite (Mg,Fe)3(Si,Al)4O10), mica (K(Mg,Fe)3 AlSi3O10(F,OH)2) while that of secondary precipitates was dominated by jarosite (KFe3+ 3(OH)6 (SO4)2), goethite (FeOOH), melanterite (FeSO4.7H2O) and gypsum (CaSO4.2H2O). Minerals obtained for the secondary precipitates were corroborated by geochemical modelling. Leaching results using rainwater with pH ranges from 3.5 to 3.9 showed that trace elements are released very slowly from tailings dumps and footprints and in small concentrations during rainy seasons as follows: As (1.5 mg/L-4.5 mg/L), Pb (3.5 mg/L-5.5 mg/L), Cu (4 mg/L-4.8 mg/L) and Zn (23 mg/L-44 mg/L). The release and mobility of Cu, Pb, Zn and As occurs quite markedly when secondary precipitates dissolve, making the immediate impacted environment unfavourable for plant growth and any habits in the vicinity. This was substantiated by simulated dissolutions and assessment of the resulting elemental speciation that pointed to the elements being distributed in bioavailable forms, implying potential uptake by plants (such as vegetables that may be cultivated on such impacted soils). The model was used to evaluate the daily intake and different exposure pathways and the results showed that children may daily intake 48.4 mg kg-1 day-1 and adults‟ 32.8 mg kg-1 day-1 . After 5 years (1825 days) of exposure more harm may be experienced and findings shows that kids are the most victims on these contaminated sites compared to adults. Both children and adults may absorb low levels of these toxic elements daily and after long time of exposure it may cause disease like cancer in their body which may lead to death. Pathways may be through inhalation and accidentally ingesting tailings soil that contain toxic elements. Drawing from the above findings, it will be important that tailings footprints that have been earmarked as land for development (residential or office space) be thoroughly assessed for potential release of toxic elements and high levels of acidity. Further reclamation aimed at reducing these hazards can then be implemented. / College of Agriculture and Environmental Sciences / M. Sc. (Environmental Science)

Le verre SON68 est dans un premier temps altéré en mode dynamique dans l’eau de COx riche en silicium (42mg/L) à pH 8, à fort S/V (14000 m⁻¹) et à 35, 50 et 90°C. Les résultats montrent que l’altération du verre semble être gouvernée par un mélange de processus de diffusion et de réaction de surface. La vitesse résiduelle à 90°C est de l’ordre de 10⁻⁴ g.m⁻².j⁻¹, l’énergie d’activation est de l’ordre de 70 kJ.mol⁻¹. Un mécanisme de dissolution/précipitation et d’hydrolyse/condensation sont responsables du développement de la couche d’altération. Les silicates de Mg et la calcite précipitent à 35 et 50°C, mais en plus la powellite et l’apatite ont été identifiées à90°C. Les résultats de la modélisation géochimique reproduisent les données expérimentales. Le verre est ensuite hydraté à des températures allant de 35 à 125°C et des valeurs d’humidité relative (HR) entre 92 et 99,9%. L’hydratation du verre augmente avec la température et l’HR. L’énergie d’hydratation est de l’ordre de 34,2 kJ.mol⁻¹. Les épaisseurs des couches d’altération varient entre 0,3μm à 35°C et 5μm à 125°C. La couche d’altération est appauvrie en (B, Li, Na) et enrichie en (Si, Al, Fe, Ca, Zn et Ni). Les principales phases secondaires formées sont la calcite, la powellite, l’apatite, la tobermorite et un gel hydraté.L’influence des matériaux en champ proche sur l’altération du verre SON68 dopé en ²⁹Si a été étudiée. La présence d’acier augmente le pH et diminue la concentration en Si et en Mo sans modifier la vitesse globale de corrosion du verre. Le Si est retenu sur les produits de corrosion d’acier, sa concentration en solution semble être contrôlée par la dissolution de l’argilite. La corrosion du verre en présence d’acier et d’argile à 90°C conduit à la formation de magnétite, sidérite, ferrosilicates, silice pure, sulfures de fer (pyrite, troïlite, pyrrhotite etmackinawite), calcite, apatite, powellite et silicates de Mg. Les résultats de modélisation sont en bon accord avec les données expérimentales. / The SON68 glass is initially altered in dynamic mode under silica rich COx water (42 mg/L) at pH8, high S/V ratio (14000 m⁻¹) and at 35, 50 and 90°C. The results showed that the glass alteration seems to be governed by both diffusion and surface reaction process. The residual rate at 90°C is around 10-4 g.m⁻².d⁻¹. The activation energy is about 70 kJ.mol⁻¹. The dissolution /precipitation and hydrolysis/condensation mechanisms are responsible for the development of the alteration layer. Mg silicates and calcites precipitate at 35 and 50°C, the same phases in addition to powellite and apatite precipitate at 90°C. The results predicted by the model reproduce well experimental data. The glass is then hydrated at temperatures ranging from 35 to 125°C and relative humidity values (RH) between 92 an 99.9%. The glass hydration increases with the temperature and RH, the hydration energy is about 34.2 kJ.mol⁻¹. The alteration layers thicknesses vary between 0.3μm at 35°C and 5μm at 125°C. The alteration layer is depleted in (B, Li, Na) and enriched in (Si, Al, Fe, Zn and Ni). The secondary phases are calcite, powellite, apatite and tobermorite in adition to a hydration gel. The effect of near field materials on the ²⁹Si doped SON68 glass alteration was studied. The presence of steel increases the pH and decreases the Si and Mo concentrations without changing the overall rate of glass corrosion. The Si is retained on the steel corrosion products, its concentration in solution seems to be controlled by the clay dissolution. The glass corrosion in the presence of steel and clay at 90°C leads to the formation of magnetite, siderite, ironsilicates, pure silica, iron sulphur (pyrite, troilite,pyrrhotite and mackinawite), calcite, apatite, powellite and Mg silicates. The modelling results agree well with the experimental data.

Une solution prometteuse pour diminuer les émissions anthropogéniques de gaz à effet de serre consiste à injecter une partie des rejets industriels de CO2 dans des formations souterraines. Celles-ci comportent un réservoir entouré de roches de couverture, qui constituent la première barrière à la migration des fluides. La caractérisation de leurs propriétés de confinement et de leur évolution en présence de CO2 est donc un élément clé de la sécurité d’un site de stockage. Le travail présenté propose une méthodologie, appliquée ici à des roches carbonatées du bassin parisien, permettant de mesurer les paramètres de transport de roches de couverture et les conséquences d’un vieillissement en conditions représentatives de celles d’un stockage en aquifère profond. La pression de percée, le coefficient de diffusion des produits de dissolution du CO2, et la perméabilité, paramètres contrôlant les principaux mécanismes de fuite, ont été mesurés avant et après altération des matériaux par réaction avec une saumure saturée en CO2 dans des conditions thermodynamiques typiques d’un réservoir (environ 80°C et 100 bar). Les résultats obtenus ont révélé un bon comportement global des roches, mais également une forte diminution du potentiel de confinement en présence de défauts structurels initiaux (fractures rebouchées, pores de grand diamètre...). Une simulation numérique décrivant les évolutions de la formation rocheuse non-fissurée sur une durée de 1000 ans a été réalisée en s’appuyant sur des paramètres mesurés directement ou obtenus par modélisation des essais d’altération. Elle a montré que les transformations engendrées par le stockage de CO2 sous une roche de couverture homogène restent très limitées spatialement / A promising solution to reduce anthropogenic emissions of greenhouse effect gases consists in the injection and long-term storage of a part of the industrial carbon dioxide discharges in underground formations. These formations must be composed of a reservoir surrounded by tight caprocks, which represent the first barrier preventing fluids migration. The characterization of their confining properties and of their evolution in presence of CO2 is thus a key element regarding a storage site security. This work presents a methodology allowing the measurement of caprocks transport parameters and the consequences of an alteration under representative conditions of deep aquifers storage. This methodology was applied to carbonate rocks from the Paris basin. The breakthrough pressure, the diffusion coefficient of CO2 dissolution products, and the permeability, controlling parameters of leakage mechanisms, were measured before and after alteration of the materials by reaction with a CO2-saturated brine under reservoir thermodynamic conditions (about 80°C and 100 bar). Results revealed a satisfactory global behaviour under these aggressive conditions, but also a strong diminution of the confinement potential in presence of initial structural faults (sealed fractures, large-diameter pores…) forming higher-permeability zones. A numeric simulation describing the evolution of a homogeneous rock formation during 1000 years was also realized based on parameters directly measured or obtained by modelling of the alteration experiments. It showed that the transformations brought by the CO2 storage under a rock formation with no initial faults remain very localized spatially

The Davle Volcanic Complex (DVC) situated in the Teplá-Barrandian unit (TBU) of the Bohemian Massif, is considered as a Neoproterozoic-Cambrian magmatic arc that developed on the northern active margin of Gondwana supercontinent during Cadomian accretionary orogeny. This study combines data obtained from fieldwork, petrography, rock-forming mineral microanalysis, major and trace element analysis, Sr-Nd-Pb isotopic systematics and U-Pb zircon geochronology in order to reveal the petrogenesis and evolution of the DVC. At least three-stage metamorphism including Cadomian seafloor alteration, Variscan regional metamorphism as well as contact metamorphism related to the emplacement of the Central Bohemian Plutonic Complex affected the DVC. The studied rocks follow calc-alkaline trend whereas tholeiitic trend previously reported is rather related to younger magmatic events. The northern part of the DVC is dominated by felsic subvolcanic (plagiogranite), volcanic (dacite- rhyolite) and pyroclastic (dacitic-rhyolitic tuffs and breccias) rocks with a few outcrops of basaltic andesite-andesite pillow lavas documenting the subaqueous activity of the DVC. These rocks are Na-rich, but K-poor, the plagiogranite contains albite most likely primary in origin, and exhibit highly radiogenic εNd values (~ +6 to +11),...

PhDENV / Department of Ecology and Resource Management / See the attached abstract below