<p>This thesis uses results of systematic numerical models to argue that externally inactive salt structures, which are potential targets for radioactive waste disposal, might be internally active due to the presence of dense layers or blocks within a salt layer.</p><p>The three papers that support this thesis use the Gorleben salt diapir (NW Germany), which was targeted as a future final repository for high-grade radioactive waste, as a general guideline.</p><p>The first two papers present systematic studies of the parameters that control the development of a salt diapir and how it entrains a dense anhydrite layer. Results from these numerical models show that the entrainment of a dense anhydrite layer within a salt diapir depends on four parameters: sedimentation rate, viscosity of salt, perturbation width and the stratigraphic location of the dense layer. The combined effect of these four parameters, which has a direct impact on the rate of salt supply (volume/area of the salt that is supplied to the diapir with time), shape a diapir and the mode of entrainment. Salt diapirs down-built with sedimentary units of high viscosity can potentially grow with an embedded anhydrite layer and deplete their source layer (salt supply ceases). However, when salt supply decreases dramatically or ceases entirely, the entrained anhydrite layer/segments start to sink within the diapir. In inactive diapirs, sinking of the entrained anhydrite layer is inevitable and strongly depends on the rheology of the salt, which is in direct contact with the anhydrite layer. During the post-depositional stage, if the effective viscosity of salt falls below the threshold value of around 10¹⁸-10¹⁹ Pa s, the mobility of anhydrite blocks might influence any repository within the diapir. However, the internal deformation of the salt diapir by the descending blocks decreases with increase in effective viscosity of salt.</p><p>The results presented in this thesis suggest that it is highly likely that salt structures where dense and viscous layer/blocks are present undergo an internal deformation processes when these dense blocks start sinking within the diapir. Depending on size and orientation of these blocks, deformation pattern is significantly different within the diapir. Furthermore, model results applied to the Gorleben diapir show that the rate of descent of the entrained anhydrite blocks differs on different sides of the diapir. This suggests that if the anhydrite blocks descent within the Gorleben diapir, they initiate an asymmetric internal flow within it.</p>

This thesis uses results of systematic numerical models to argue that externally inactive salt structures, which are potential targets for radioactive waste disposal, might be internally active due to the presence of dense layers or blocks within a salt layer. The three papers that support this thesis use the Gorleben salt diapir (NW Germany), which was targeted as a future final repository for high-grade radioactive waste, as a general guideline. The first two papers present systematic studies of the parameters that control the development of a salt diapir and how it entrains a dense anhydrite layer. Results from these numerical models show that the entrainment of a dense anhydrite layer within a salt diapir depends on four parameters: sedimentation rate, viscosity of salt, perturbation width and the stratigraphic location of the dense layer. The combined effect of these four parameters, which has a direct impact on the rate of salt supply (volume/area of the salt that is supplied to the diapir with time), shape a diapir and the mode of entrainment. Salt diapirs down-built with sedimentary units of high viscosity can potentially grow with an embedded anhydrite layer and deplete their source layer (salt supply ceases). However, when salt supply decreases dramatically or ceases entirely, the entrained anhydrite layer/segments start to sink within the diapir. In inactive diapirs, sinking of the entrained anhydrite layer is inevitable and strongly depends on the rheology of the salt, which is in direct contact with the anhydrite layer. During the post-depositional stage, if the effective viscosity of salt falls below the threshold value of around 1018-1019 Pa s, the mobility of anhydrite blocks might influence any repository within the diapir. However, the internal deformation of the salt diapir by the descending blocks decreases with increase in effective viscosity of salt. The results presented in this thesis suggest that it is highly likely that salt structures where dense and viscous layer/blocks are present undergo an internal deformation processes when these dense blocks start sinking within the diapir. Depending on size and orientation of these blocks, deformation pattern is significantly different within the diapir. Furthermore, model results applied to the Gorleben diapir show that the rate of descent of the entrained anhydrite blocks differs on different sides of the diapir. This suggests that if the anhydrite blocks descent within the Gorleben diapir, they initiate an asymmetric internal flow within it.

This research studies 6 eclogites from Qinglongshan Donghai in the Sulu ultrahigh-pressure (UHP) province, eastern China. Petrographic microscope, Ramam spectrometer, scanning electron microscope (SEM) and transmission electron microscope (TEM) are utilized to identify mineral compositions, microstructures and mineral precipitates. Optical observations show the eclogites with the following mineral assemblage: garnet + omphacite + amphibole + epidote + rutile ¡Ó quartz ¡Ó phengite ¡Ó kyanite ¡Ó coesite pseudomorph ¡Ó apatite ¡Ó talc. Oriented mineral precipitates are found within omphacite and within apatites. The parallel precipitates in omphacite are quartz rods confirmed by electron probe microanalysis (EPMA) and TEM diffraction patterns. The direction of the long axes of the quartz rods seem to have relation with the cleavage and with the parting of omphacite. The direction of the long axis of quartz is not necessarily the c axis direction of quartz. Pargasite is intergrown with quartz and the amounts of both minerals seem to have a positive relation. Pargasite contain element K which is not found in omphacite and there is no obvious crystallographic relation between quartz, pargasite, and omphacite. There is amphibole exsolved from the omphacite and the crystallographic axes of tht exsolved amphibole parallel to those of omphacite. The a and c parameters for the two phases are equal while the b parameter of the amphibole is almost twice that of omphacite. A two-stage growth mechanism for quartz and amphibole intergrown within omphacite is proposed: (1) very fine quartz rods exsolved (or aided with infilling fluids) from a supersilicic clinopyroxene during decompression, creating grain boundaries between quartz rods and host, (2) growth of amphibole and quartz along the grain boundaries with fluid participation and an expense of omphacite during retrograde metamorphism. There are two different precipitates within apatites in different eclogites. One of the precipitates is calcium sulfate (anhydrite or gypsum) and the other is ferrous sulfide (pyrrhotite?). There was no report about calcium sulfate within apatite in UHP rocks before. The formation of sulfide (reduced) or sulfate (oxidized) is controlled by the fugacity of oxygen. According to the previous reports and the discoveries of this research, there are many different kinds of precipitates containing silicate incompatible elements in apatites. It can¡¦t be ruled out that the precipitates exsolved from apapites but apatites are more likely to act as sinks of silicate incompatible elements and different minerals precipitated within apatites under different redox conditions rather than exsolution processes.

Seafloor hydrothermal systems have been intensively studied for the past few decades; however, the location of recharge zones and details of fluid circulation patterns are still largely uncertain. To better understand the effects of anhydrite precipitation on hydrothermal flow paths, we conduct 2-D numerical simulations of hydrothermal circulation at a mid-ocean ridge using a NaCl-H2O numerical code. The simulations focus on East Pacific Rise hydrothermal system at 950N due to availability of key observational data to constrain the models. Seismicity data that is available suggests that fluid flow is primarily along axis and that recharge is focused into a small zone near a 4th order discontinuity in the ridge axis. Simulations are carried out in an open-top square box 1500 m on a side maintained at a surface pressure of 25 MPa, and nominal seawater temperature of 10 C. The sides of the box are assumed to be impermeable and insulated. A constant temperature distribution is maintained along the bottom of the box consisting of a 1000 m long central-heated region maintained at 450 C to represent the axial magma chamber and ensure P-T conditions for phase separation; a linearly decreasing temperature profile from 450 to 300 C is maintained along the 250 m long segments adjacent to the heated region to delineate the recharge zone. We constructed a homogeneous model with a uniform cell size of 25 m with a permeability of 10-13 m2 and a similar model with a 200 m thick layer 2A region with a permeability of 10-12 m2. For the homogeneous model the simulations were run for 100 years to approximate steady state conditions and the model with layer 2A was run for 50 years. Assuming that anhydrite precipitation resulted from the decrease in solubility with increasing temperature as downwelling fluid gets heated, the rate of porosity decrease and sealing time was calculated at 50 and 100 years. The results showed that sealing occurred most rapidly at the bottom of the recharge areas near the base of the high-temperature plumes, where complete sealing occurred after ~55-625 years for an initial porosity of 0.1. The simulations also suggested that sealing would occur more slowly at the margins of the ascending plumes, with times ranging between ~ 80 and 5000 years. The sealing times in the deep recharge zone determined in these simulations are considerably greater than estimated from 1D analytical calculations, suggesting that with a 2D model, focused recharge at the EPR 950N site may occur, at least on a decadal time scale. More detailed analyses are needed to determine whether such focused recharge can be maintained for longer times. / Master of Science

This diploma thesis deals with the study of the binder mortar based on calcium sulphate. The theoretical part deals with the general theory of sulfate binders and anhydrite mortars. Further attention is paid to the standard requirements for these binders and mortars and the evaluation of the existing research at the THD Institute. The experimental part is devoted to research of anhydrite mortar for the production of self-leveling mixtures. The subject of the research was the design of a suitable activating agent, performing technological tests on designed anhydrite pastes and mortars and monitoring hydration.

L'objectif de ce travail a été d'apporter une meilleure compréhension des mécanismes réactionnels de l'hydratation de ciments appartenant à la famille de ciment BCSAF afin de développer des schémas réactionnels simplifiés permettant d'optimiser les ciments à base d'un clinker BCSAF et d'autres constituants pour des applications spécifiques. Les ciments étudiés ont été réalisés à partir d'un clinker contenant 52% de belite, 33% de ye'elimite and 14% de ferrite et diverses quantités d'anhydrite et de calcaire. A partir de l'étude détaillée de l'hydratation d'un ciment contenant 95% de clinker et 5% d'anhydrite, il a été démontré que le mécanisme de l'hydratation est constitué de deux périodes successives : le début de l'hydratation est contrôlé par l'hydratation de la ye'elimite réagissant avec l'anhydrite, tandis que la suite de l'hydratation est contrôlée par les hydratations de la belite et de la ferrite qui réagissent avec certains des hydrates formés lors de la première période. La vitesse de nucléation de la strätlingite contrôle le début de l'hydratation de la belite. Le principal paramètre qui contrôle cette dernière est la concentration en sulfate de la phase aqueuse qui doit être très faible. Ainsi C-S-H n'est pas formé au début de l'hydratation de la belite parce qu'elle n'est pas saturé à cause de faible concentration de calcium et silicon et sa formation est retardé plus tard à cause de l'inhibition de sa nucléation par de trop fortes quantités d'aluminate en solution. Par conséquence, c'est indirectement la concentration en sulfate de la solution qui contrôle le début de l'hydratation de la belite and ainsi les réactions conduisant à sa réduction à travers la précipitation de phase notamment lors de l'hydratation de la ye'elimite pour former de l'ettringite. Ainsi d'une façon générale, la strätlingite commence à nucléer quand la ye'elimite a complètement réagi. D'autre part, une synergie entre les hydratations de la belite et de la ferrite permet de former des hydrogrenats et des C-S-H à des temps longs au détriment de la strätlingite formée auparavant. Un mécanisme d'hydratation similaire a été trouvé pour les ciments contenant des quantités plus importantes d'anhydrite à l'exception de ceux qui contiennent une quantité d'anhydrite supérieure que la quantité théorique permettant de faire réagir toute la ye'elimite en ettringite. Toutefois pour le premier type de ciments, une augmentation de la quantité d'anhydrite allonge à la fois le temps d'apparition de la seconde période et la durée des différentes étapes de cette dernière. Donc l'hydratation est globalement plus lente. Pour le second type de ciment, contenant de fortes quantités d'anhydrite, le mécanisme d'hydratation est assez différent car l'hydratation de la belite commence dès le début de l'hydratation et conduit à la formation, soit d'ettringite contenant Si, soit de C-S-H. L'effet de 15% de calcaire a également été étudié pour le ciment contenant 95% de clinker et 5% d'anhydrite. Les résultats ont montré que le calcaire ne change pas la première période de l'hydratation mettant en jeu principalement la ye'elimite et l'anhydrite. Par contre la seconde période, durant laquelle la belite et la ferrite s'hydratent, est fortement retardée à son début. Ceci peut être dû à un retard de la nucléation de la strätlingite à cause de concentrations en sulfate de la solution restant plus longtemps élevées par le fait que l'ettringite est stabilisée en présence de carbonate par la formation de phases AFm carbonatées qui inhibent la formation de monosulfoaluminate de calcium hydraté. Pour finir, des perspectives sont données notamment afin de réduire la durée de la première période de l'hydratation et ainsi permettre un démarrage plus rapide de l'hydratation de la belite et de la ferrite.

Late Ordovician Red River strata of southeastern Saskatchewan were deposited in a broad epicontinental sea. In the lower part, the Yeoman and Herald formations comprise two cycles of carbonateevaporite sequences. Although these units possess an overall layer-cake aspect, thickness variations especially in the Herald Formation show that accumulation was affected by syndepositional flexure, differential subsidence and displacement of fault-bounded blocks. The mainly laminated dolomudstones and anhydrites of the Lake Alma and Coronach members of the Herald Formation were deposited under relatively tranquil conditions. These units host different kinds of synsedimentary deformation features, interpreted to have been induced by earthquakes generated because of movements along basement faults thought to have been oriented orthogonally NE−SW and NW−SE. The low-energy environmental setting was conducive to preserving these features, referred to as seismites.<p> The variety of seismites in the Herald Formation is related to the varying rheology of the carbonate or evaporite sediment, as well as shaking intensity. Brittle and quasi-brittle failure is represented by faults, microfaults, shear-vein arrays and pseudo-intraclastic breccias, mostly in dolomudstones which must have been stiff at the time of deformation. Plastic behaviour is recorded by soft-sediment deformation, comprising a family of features that includes loop bedding, folded laminae and convolute bedding. Indeed, these structures in enterolithic anhydrite are more reasonably interpreted as due to deformation than crystal growth, volume expansion and displacement, the more usual explanations. Sediment shrinkage and concomitant fluidization are recorded by dikelets containing injected carbonate mud or granular gypsum, the latter now preserved as anhydrite. Evidence for wholesale liquefaction, however, was not observed. These rheological differences were caused by the primary nature of the sediment plus modifications due to early diagenesis and burial confinement. Shaking intensity is difficult to gauge, but it is presumed that a minimum of VI on the modified Mercalli scale was required to produce these features. Consequently, shaking of lesser magnitude was probably not recorded.<p> The geographic distribution of seismites should reflect the location of basement faults presumed to have been active during deposition, and indeed there is a concentration adjacent to the known location of syndepositonal fault lineaments. In addition, the stratigraphic distribution of seismites records higher frequencies of activity of these same faults. These distributions show that earthquake-induced ground motion was common during deposition of the Lake Alma Member in southeastern Saskatchewan but less so during deposition of the Coronach Member.<p> Seismites serve as proxies for the activity of relatively nearby syndepositional faults making up the tectonic fabric of sedimentary basins. They also point to basement features that, if re-activated, can induce fracture porosity or influence subsurface fluid flow. Syndepositional tectonism undoubtedly had a much more profound influence on many successions than is presently accepted, and its effects are more widespread than currently appreciated.

Des solides ayant même analyse chimique, cristallisant dans le même système et possédant des textures identiques peuvent cependant avoir des comportements très différents. Il est maintenant couramment admis que les défauts des solides ont un rôle important sur leur réactivité. Il est donc nécessaire de caractériser ces défauts. Nous avons mis en évidence l'influence de divers facteurs sur la nature des gels d'alumine et sur les produits de déshydratation. On remarque en particulier que la nature des défauts de structure de l'alumine α est liée à celle des impuretés chimiques du gel ainsi qu'à la composition de l'atmosphère gazeuse au cours de la cuisson. Le nombre de ces défauts détectés par émission exoélectronique thermostimulée évolue avec la température d'obtention mais cette évolution dépend également de la nature des impuretés chimiques contenues dans le gel initial. On peut noter que le nombre des défauts diminue lors de traitements mécaniques. La température a aussi une grande influence sur le nombre des défauts superficiels de l'anhydrite. On constate en effet qu'il est maximum pour un traitement effectué à 800°C. Comme pour l'alumine, il diminue lors de la comminution. Quant aux défauts détectés sur le fluorure de lithium, ils ont un comportement très différent de ceux des deux autres solides étudiés. En effet dans les premiers instants du broyage, leur nombre augmente alors que dans les deux cas précédents on observe une diminution. Cette recherche a donc permis de mettre en évidence l'influence du mode de synthèse et des traitements thermiques et mécaniques sur les défauts de surface des solides. Ceux-ci sont détectés principalement au moyen d'une technique originale: l'émission exoélectronique thermostimulée. La recherche industrielle est très intéressée par ces résultats et envisage de s'équiper d'une telle technique pour contrôler d'une façon plus rigoureuse la qualité de certains produits.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / Este trabalho tem como objetivo o estudo da genÃtica e o paleoambiente do membro Ipubi da FormaÃÃo Santana, nas minas Pedra Branca e ConceiÃÃo Preta, no municÃpio de Santana do Cariri, situado na Chapada do Araripe, porÃÃo Sul do estado do CearÃ. A metodologia utilizada foi o levantamento de seÃÃes estratigrÃficas nas minas e a descriÃÃo faciÃlogica, com o uso de DescriÃÃo PetrogrÃfica, DifraÃÃo de Raios X e FluorescÃncia de Raios X. No trabalho, foram identificadas nas analises petrogrÃficas que a sequÃncia evaporÃtica sofre o processos de diagÃnese de anidrita para gipsita quase que completo, as anÃlise da DifraÃÃo de Raios X evidenciaram que os argilominerais presentes na unidade sÃo bem formados e constituÃdos por Nontronita e Saponita, jà analise das rochas evaporÃticas evidenciaram a predominÃncia de CaSO4.2H20 (gipsita). Para os ensaios de FluorescÃncia de Raios X, os argilominerais sÃo compostos por SiO2, F2O3, Al2O3 e CaO, preliminarmente. A unidade foi divida e dois conjuntos faciolÃgicos: de composiÃÃo pelÃtico e gipsitico intercalados, onde o fÃcies pelÃtico à composto por folhelhos, margas e calcÃrio, o fÃcies gipsitico por gipsita branca, cinza e marrom, com cristais em roseta, com hÃbito maciÃo e fibroso. Foram propostos para a unidade que o Paleoambiente formador do deposito seria o de lagunas evaporÃticas, com influÃncia ou nÃo de Ãguas marinhas e a gÃnese para um deposito como sendo do tipo sabkhas / This work aims to study the genetic and paleo Ipubi member of the Santana Formation, mines Pedra Branca and Preta Conception, in the municipality of Santana do Cariri, situated in the Araripe, the southern portion of the state of CearÃ. The methodology used was a survey of stratigraphic sections in mines and facies description, using Petrographic Description, X-ray Diffraction and X-Ray Fluorescence At work, were identified in petrographic analyzes the evaporite sequence undergoes the processes of diagenesis of anhydrite to gypsum almost complete, the analysis of X-ray diffraction showed that the clay minerals in the unit are well trained and consist of nontronite and saponite, already analysis of evaporitic rocks showed the predominance of CaSO4.2H20 (gypsum). For tests of X-ray Fluorescence, clay minerals are composed of SiO2, F2O3, Al2O3 and CaO, preliminarily. The unit was divided and two sets facies analysis: composition of pelitic and gipsitico interspersed, where the pelitic facies is composed of shale, marl and limestone, gypsum facies gipsitico by white, gray and brown, with crystals in rosettes, with mass and fibrous habit . Been proposed to drive the paleoenvironment of the deposit would be the trainer of evaporitic lagoons, with no influence or marine waters and the genesis for a deposit as type sabkhas.

Sulphate-rich wastewater is an increasing concern for industries as LKAB. The water chemistry of the LKAB Kiruna water system is characterized by high alkalinity, high pH (pH 7.5-9.0) and high concentrations of chemical species and soluble minerals. The sulphate content in the water system of Kiruna is associated with the dissolution of calcium sulphate as anhydrite (CaSO4) and gypsum (CaSO4 2H2O). However, the high concentrations of sulphate in the effluents from the LKAB Kiruna operation are unique for iron ore mining.    The aim of the thesis was to study and evaluate the behavior of sulphate in the process water system of the Kiruna concentrator plants. This was done by laboratory grinding (leaching tests), equilibrium calculations with the HSC software and mass balancing of the concentrator KA3 in Kiruna. The highest concentrations of sulphate have been detected in the process water of KA3, hence the focus has been on KA3 regarding sampling, evaluation and comparison. Water treatment technologies for sulphate and the effect of process water on ore processing have not been included in this project.   The laboratory grinding was done using process water and ore from the concentrator KA3. During the experimental work with laboratory grinding the parameters pH, temperature and operating times for primary- and secondary grinding, respectively, were varied. The observations from the experimental work were further confirmed by equilibrium calculations and mass balancing. The following conclusions were drawn.     Anhydrite/gypsum is not leached from the ore during ore processing with process water having concentrations of sulphate already close to the saturation point at approximately 1800 mg/L. If the process water is diluted with water with lower sulphate content, e.g. mine water or a diluted return water from the pond system (e.g. during spring flood), anhydrite/gypsum in ore will be dissolved until the sulphate concentration reaches the saturation point. The ionic strength of the process water controls the saturation point and thus the sulphate concentration. Leaching of anhydrite/gypsum in saturated process water, with respect to sulphate, is not affected by grinding time or adjusted conditions in the process water, such as temperature or pH value.    For further work, it is recommended to investigate the behavior of sulphate in the tailings pond system to increase knowledge of the overall behavior in the water system. In addition, a similar investigation of the behavior of uranium in the process water is recommended in order to face future environmental standards.