The timing of motion on thrust faults in the Idaho-Wyoming-Utah (IWU) thrust belt comes from synorogenic sediments, apatite thermochronology and direct dating of fault rocks coupled with good geometrical constraints of the subsurface structure. The thermal history comes from the analyses of apatite thermochronology, thermal maturation of hydrocarbon source rocks and isotope analysis of fluid inclusions from syntectonic veins. New information from zircon fission track and zircon (U-Th)/He analysis provide constraints on the thermal evolution of the IWU thrust belt over geological time. These analyses demonstrate that the time-temperature pathway of the rocks sampled never reached the required conditions to reset the thermochronometers necessary to provide new timing constraints. Previous thermal constraints for maximum temperatures of IWU thrust belt rocks, place the lower limit at ~110°C and the upper limit at ~328°C. New zircon fission track results suggest an upper limit at ~180°C for million year time scales. ID-TIMS and LA-ICPMS of syntectonic calcite veins suggest that new techniques for dating times of active deformation are viable given that radiogenic isotope concentrations occur at sufficient levels within the vein material.

Th. 3e cycle--Hydrogéol.--Montpellier 2, 1978.

Carbonatites are unique and enigmatic magmatic rocks of unclear origin, with very specific mineralogy and geochemical properties. They are predominantly composed of magmatic calcite or other carbonate minerals (Le Bas 1987) and have low content of SiO2 (Le Maitre 2002). Origin of these peculiar magmas is still not clear but they appear to represent an important "window" into processes in Earth's mantle. They are considered either as residual melts from a fractionated carbonated nephelinite or melilitite (Gittins 1989; Gittins and Jago 1998), as immiscible fractions of CO2-saturated silicate melts (Freestone and Hamilton 1980; Amundsen 1987; Kjarsgaard and Hamilton 1988, 1989; Brooker and Hamilton 1990; Kjarsgaard and Peterson 1991; Church and Jones 1995; Lee and Wyllie 1997; Dawson 1998; Halama et al. 2005; Brooker and Kjarsgaard 2011), or as primary melts which are were generated from CO2-bearing peridotite through partial melting (Wallace and Green 1988; Sweeney 1994; Harmer and Gittins 1998; Harmer et al. 1998; Ying et al. 2004). Abundances of rare earth elements (REE) are often high in carbonatites because carbonatitic magmas can dissolve these elements much easily than silicate magmas (Nelson et al. 1988). Carbonatitic magma can also dissolve large quantities of Sr, Ba, P and mainly Zr and Nb,...

Masters of Science / This study was conducted to investigate hydrogeochemical processes controlling the evolution of groundwater chemistry and their influence on water quality in the Heuningnes Catchment. The role or influence of hydrogeochemical processes in groundwater quality in aquifer systems remains poorly understood. One of the ways of improving such understanding is to employ different techniques to explore key processes that govern groundwater quality in aquifer systems. Therefore, the present study investigated hydrogeochemical processes of groundwater resources and identified key processes that explained its quality from a spatiotemporal perspective. The quantitative approach that provides the ability to assess relationships between variables both spatially and temporally was applied. Groundwater sampling was done on four occasions during July 2017, October 2017, March 2018, and July 2018. Identification of hydrogeochemical processes controlling the evolution of groundwater chemistry and quality was done using various complementary tools. These tools included classification of the main water types, evaluation of water-rock interaction by means of stoichiometry analysis and bivariate correlation plots, inverse geochemical modelling, and statistical analysis (hierarchical cluster analysis and factor analysis). Physical parameters were measured in situ, while water samples were collected from boreholes, piezometers, springs, and artesian boreholes for laboratory analysis for major ions analysis. Descriptive and bivariate statistical methods were used to summarise and evaluate the strength of the relationship between variables, while multivariate statistical methods were applied to group similar samples based on their chemical compositions. Tri linear Piper diagrams were generated to characterize water type based on double normalizing the proportions of cations and anions, while correlation and stoichiometric analysis were applied to identify hydrogeochemical processes influencing groundwater chemistry. The results generated from the trilinear Piper diagrams confirmed the dominance of sodium and chloride ions in waters of the Heuningnes Catchment. Groundwater of a Na/Cl type is typical for a coastal aquifer characterised by saline, deep ancient groundwater. The lower parts of the Catchment were characterised by saline groundwater. The results indicated that shallow groundwater samples within the study area were more mineralised as compared to deep groundwater with EC values ranging between 20.8 and 2990 mS/m, with waters within the Table Mountain Group region (TMG), recording the lowest values. Deep groundwater for boreholes and artesian boreholes located upstream in the Catchment was fresh and yielded some of the lowest EC values recorded with an EC value below 50 mS/m. Generally, EC values increased from the upper TMG region of the Catchment towards the Bokkeveld shale region downstream and were highest during the dry season of 2018. The results indicated strong geological influences on water chemistry. Bivariate correlation and stoichiometric analysis identified cation exchange, adsorption, evaporation, weathering of carbonates, sulphates and silicate minerals as processes influencing the chemistry of groundwater in the Heuningnes Catchment. The Saturation Index (SI) results showed a change of calcite, dolomite, aragonite, gypsum, anhydrite, halite, melantinterite, siderite and sylvite from being undersaturated to oversaturated at some areas for the different seasons along the flow path. The mass-balance modelling results indicated that ion exchange and reverse ion exchange processes were more dominant at low elevations along the same flow path during the dry periods. However, at high elevations along the flow path, silicate weathering was the dominant process taking place. The findings of this study demonstrated the influence of hydrogeochemical processes in changing the water chemistry along the flow paths. In conclusion, the study showed the value of utilising various assessment tools as complementary techniques to improve the understanding about hydrogeochemical processes, and its influence on evolution of groundwater chemistry and quality. Based on the findings of the study the following recommendations were made for future studies; the sample points or sample boreholes in the study Catchment should be increased; and to have more sampling trips to enable better comparison between the possible processes

The central aim of this thesis is to give further insights into the structural properties of the calcite(104) surface and especially to unravel its surface reconstruction by clarifying the contradicting reports of the (2 × 1) and row-pairing reconstruction. Within this thesis, the pristine as well as the CO and H2O-covered calcite(104) surface is investigated for the first time with non-contact atomic force microscopy (NC-AFM) operated at 5 K. CO terminated tips are used in the measurements to benefit from the improved contrast capabilities and detailed understanding of contrast formation with these tips.

Yes / The Mg/Ca ratios of biogenic calcite is commonly seen as a valuable palaeo-proxy for reconstructing past ocean temperatures. The temperature dependence of Mg/Ca ratios in bivalve calcite has been the subject of contradictory observations. The palaeoceanographic use of a geochemical proxy is dependent on initial, rigorous calibration and validation of relationships between the proxy and the ambient environmental variable to be reconstructed. Shell Mg/Ca ratio data are reported for the calcite of two bivalve species, Mytilus edulis (common mussel) and Pecten maximus (king scallop), which were grown in laboratory culturing experiments at controlled and constant aquarium seawater temperatures over a range from 10 to 20 C. Furthermore, Mg/Ca ratio data of laboratory- and fieldgrown M. edulis specimens were compared. Only a weak, albeit significant, shell Mg/Ca ratio¿temperature relationship was observed in the two bivalve species: M. edulis (r2=0.37, p<0.001 for laboratory-cultured specimens and r2=0.50, p<0.001 for field-cultured specimens) and P. maximus (r2=0.21, p<0.001 for laboratory-cultured specimens only). In the two species, shell Mg/Ca ratios were not found to be controlled by shell growth rate or salinity. The Mg/Ca ratios in the shells exhibited a large degree of variability among and within species and individuals. The results suggest that the use of bivalve calcite Mg/Ca ratios as a temperature proxy is limited, at least in the species studied to date. Such limitations are most likely due to the presence of physiological effects on Mg incorporation in bivalve calcite. The utilization is further limited by the great variability both within and among shells of the same species that were precipitated under the same ambient conditions

The geological sequestration of carbon dioxide (CO2) is one of the options of controlling the greenhouse gas emissions. However, leakage of CO2 from the storage reservoir is a risk associated with geological sequestration. Over longer times, large-scale groundwater motion may cause leakage of dissolved CO2 (CO2aq). The objectives of this thesis are twofold. First, the modelling study analyzes the leakage of CO2aq along the conducting pathways. Second, a relatively safer mode of geological storage is investigated wherein CO2aq is injected in a carbonate reservoir. A reactive transport model is developed that accounts for the coupled hydrological transport and the geochemical reactions of CO2aq in the porous media. The study provides a quantitative assessment of the impact of advection, dispersion, diffusion, sorption, geochemical reactions, temperature, and heat transport on the fate of leaking CO2aq. The mass exchange between the conducting pathway and the rock matrix plays an important role in retention and reactions of leaking CO2aq. A significant retention of leaking CO2aq is caused by its mass stored in aqueous and adsorbed states and its consumption in reactions in the rock matrix along the leakage pathway. Advection causes a significant leakage of CO2aq directly from the reservoir through the matrix in comparison to the diffusion alone in the rock matrix and advection in a highly conducting, but thin fracture. Heat transport by leaking brine also plays an important role in geochemical interactions of leaking CO2aq.  Injection of CO2aq is simulated for a carbonate reservoir. Injected CO2-saturated brine being reactive causes fast dissolution of carbonate minerals in the reservoir and fast conversion of CO2aq through considered geochemical reactions. Various parameters like dispersion, sorption, temperature, and minerals reaction kinetics are found to play important role in the consumption of CO2aq in reactions. / <p>Research Funders:</p><p>(i) Higher Education Commission (HEC) of Pakistan</p><p>(ii) Lars Erik Lundberg Scholarship Foundation, Sweden</p>

Thesis (MSc)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: The Northern Cape Province of South Africa has played host to numerous mining activities for over a century. To date, most of the mining activity has ceased, leaving the area laden with derelict mine sites and unlined tailings dumps. One such site is the Spektakel mine situated to the west of the town of Springbok. The unlined copper and sulphide rich tailings at the site have the potential to leach elevated concentrations of copper and acidic water into the Buffels River downslope of the site. This poses a threat to the surrounding communities that rely mainly on the river to supply water for drinking, livestock and irrigation. The soil surrounding the tailings dumps was characterised in terms of its mineralogical and chemical properties. The results indicate that the soil contains elevated concentrations of Cu2+, which is bound in the soil in the form of the secondary copper hydroxy mineral atacamite (Cu2(OH)3Cl). No other secondary copper minerals were identified at the site. Analysis of the solution present on the surface of the tailings dumps indicate that the tailings are the main source of the high Cu2+, Mg2+ and SO42- concentrations observed in the surrounding soils. As this solution migrates through the tailings dumps, into the soil, it accumulates Cl- through halite dissolution. The resulting acidic Cu2+, Mg2+, SO42- and Cl- solution reacts with the calcite in the soil, replacing it with atacamite. To determine why only a copper chloride mineral formed in the sulphate rich environment a synthetic solution with the composition of a solution in equilibrium with the soil was evaporated, both in the presence and absence of calcite. The results indicate that when the solution comes into contact with calcite, atacamite immediately precipitated, removing the Cu2+ from the solution. In the absence of calcite Cu2+ remains conservative, accumulating in the solution without precipitating a copper sulphate mineral. This establishes that the elevated Mg2+ concentration of the solution induces the formation MgSO4 aqueous complexes that reduce the activity of free sulphate, thus restricting copper sulphate mineral formation. The results from the soil characterization indicate that the atacamite stabilization mechanisms (circumneutral pH, high Cl- concentration and calcite) in the soil are diminishing. During sporadic rain events the acidic tailings solutions dissolve the calcite and temporarily reduce the Cl- concentration of the soil. To determine how these decreases will influence Cu2+ mobility in the soil, the stability of atacamite was tested by reducing the pH both in the presence and the absence of chloride. The results indicate that an elevated Cl- concentration and a pH > 6 stabilizes atacamite. A decrease in either of these parameters destabilizes atacamite and favours its dissolution. The study concludes that the current chemical conditions in the soil at Spektakel favour the stability of atacamite. However, continued sporadic rain events will reduce the Cl- concentration in the soil by increasing the SO42- concentration. This acidic solution will dissolve the calcite in the soil, thus reducing the buffering capacity of the soil, leading to the instability of atacamite, resulting in the leaching of large quantities of Cu2+ into the surrounding water bodies. / AFRIKAANSE OPSOMMING: Die mynbou bedryf was die ekonomiese dryfkrag van die Noord-Kaap Provinsie van Suid-Afrika vir meer as ‘n eeu. Die area was die gasheer vir ‘n verskeidenheid mynbou aktiwiteite tot die mynmaatskappye besluit het om mynproduksie te staak en die gebied te verlaat. Die mynmaatskappye het geen rehabilitasie aan die myne en mynhope verrig nie. Die verlate myne lê verspreid in die area met oop mynhope wat koper en ander swaar metale in die grond, sowel as in die water, na omliggende areas kan versprei. Een van dié verlate myne is die Spektakel myn 40 km wes van Springbok. Die mynhope by Spektakel kan moontlik koper en ander swaar metale in die Buffelsrivier, wat langs die myn verby loop, loog. Dit dien as ‘n bedreiging vir die omliggende gemeenskappe wat staatmaak op die water vir drinkwater en besproeiing. Die grond rondom die mynhope was ge-analiseer om te bepaal hoe erg ‘n bedreiging die mynhope vir die omgewing is. Die resultate dui daarop dat die grond hoë konsentrasies Cu2+ bevat wat vasgebind is in die sekondêre koper mineral atakamiet (Cu2(OH)3Cl). Geen ander sekondêre koper minerale is in die grond geïdentifiseer. Die analise van die oplossing wat bo-op die mynhoop aangetref is dui aan dat dié oplossing suur en gekonsentreerd is t.o.v. Cu2+, Mg2+ en SO42-. Terwyl die oplossing deur die mynhoop migreer los dit haliet in die grond op wat Cl- tot die oplossing byvoeg. Wanneer hierdie suur en Cu2+, Mg2+, SO42- en Cl- ryke oplossing met die kalsiet in die grond reageer word die kalsiet vervang met atakamiet (Garrels en Stine, 1948). Om vas te stel waarom slegs 'n koperchloried mineraal vorm in die sulfaat ryke grond was ‘n oplossing, met ‘n samestelling soortgelyk aan 'n oplossing in ewewig met die grond, verdamp in beide die teenwoordigheid en afwesigheid van kalsiet. Die resultate van die eksperiment dui daarop dat wanneer die oplossing in kontak kom met kalsiet atakamiet onmiddellik neerslaan en Cu2+ uit die oplossing verwyder. In die afwesigheid van kalsiet bly Cu2+ konserwatief in die oplossing; die Cu2+ hoop op in die oplossing en slaan nooit neer nie. Daar is vasgestel dat die verhoogde Mg2+ in die grondoplossing MgSO4 water komplekse vorm wat die aktiwiteit van SO42- verlaag en verhoed dat kopersulfaat minerale kan vorm. Verdere navorsing dui aan dat die chemiese meganismes wat atakamiet in die grond stabiliseer besig is om te kwyn. Gedurende sporadiese reën buie word die kalsiet in die grond opgelos deur die suur mynhoop oplossings wat die pH van die grond verlaag. Die mynhoop oplossing verryk ook die grond t.o.v SO42- wat die Cl- konsentrasie verlaag. Om te bepaal hoe hierdie afname in Cl- konsentrasie en pH die migrasie van Cu2+ beïnvloed was atakamiet oplossbaarheid bepaal. Atakamiet was onderskeidelik geplaas in ‘n suiwer water en chloried oplossing tewyl die pH verlaag was om te bepaal hoe atakamiet oplos in elk van die oplossings. Die resultate dui aan dat 'n verhoogde Cl- konsentrasie en pH > 6 atakamiet stabiliseer. Die afname van beide hierdie veranderlikes het veroorsaak dat atakamiet makliker ontbind en Cu2+ vrystel. Die gevolgtrekking van die studie is dat die huidige chemiese toestande in die grond by Spektakel gunstig is vir die stabiliteit van atakamiet. Met sporadiese reën buie neem die Cl- konsentrasie in die grond af en los kalsiet op. Hierdie afname in pH en Cl- konsentrasie maak atakamiet meer onstabiel wat gevolglik Cu2+ in die grond en water rondom Spektakel vrystel.

L'objectif de cette thèse est de déterminer expérimentalement les effets des réactions de dissolution/précipitation de la calcite (CaCO3) en milieux poreux sur les observables géophysiques, à différentes échelles. Elle s'inscrit dans le cadre de la recherche sur le stockage géologique du dioxyde de carbone (CO2). La première partie est consacrée à la conception et la réalisation d'expériences de percolation réactive de fluide riche en CO2 sur des échantillons décimétriques de carbonates, avec suivi en temps réel de la conductivité électrique de la roche et du fluide, du pH du fluide, de la perméabilité de la roche, mesures ponctuelles au cours des expériences de l'alcalinité et de la composition du fluide, et acquisition de profils de vitesses et d'atténuation des ondes sismiques le long de l'échantillon. Ceci, associé à une caractérisation quantitative des échantillons avant et après expérience à différentes échelles, a permis de montrer que l'évolution de la porosité dans les échantillons déterminée par les méthodes électriques et sismiques est en très bonne adéquation avec celle obtenue par la composition des prélèvements chimiques en sortie d'échantillon. À plus grande échelle, nous avons conçu et assemblé une cuve cylindrique, équipée pour effectuer des tomographies de résistivité électrique (ERT) 3D, et pour un suivi par Potentiel Spontané (PS) en surface. Le but de ce dispositif est de réaliser des expériences de précipitation de calcite en milieu granulaire (sable de Fontainebleau), avec un suivi géoélectrique des injections et de l'évolution de la porosité. Les développements expérimentaux, logiciels et tests présentés ont permis de rendre ce dispositif opérationnel pour l'imagerie géoélectrique d'expériences de percolation réactive. Enfin, sur le terrain, nous avons effectué une campagne d'acquisition multiparamètres autour de la source chaude de Syabru-Bensi, au Népal, sous la direction de Frédéric Perrier. Cette mission a consisté en la cartographie multi-méthodes du sous-sol d'un site comprenant une source d'eau chaude et un fort dégagement gazeux, avec notamment d'importantes concentrations de CO2, en faisant un analogue naturel de fuite lors d'un stockage géologique. Un objectif de cette étude est la compréhension de cette zone complexe, du couplage entre les différents phénomènes observés pour comprendre l'origine et le chemin permettant à ces quantités de gaz de parvenir en surface. s'agit également de déterminer la contribution de cette zone au bilan de carbone régional, et d'utiliser ce site pour déterminer la possibilité d'employer la mesure du flux de radon au sol comme précurseur sismique, pour la prédiction du futur grand séisme Himalayen.

L’objectif de ce travail est de concevoir, développer, mettre en œuvre et optimiser une technologie continue permettant une bonne maîtrise des réactions de précipitation, processus chimique rapide donnant naissance à une phase solide. Ce précipiteur est un réacteur multifonctionnel à lit fluidisé qui n’a pas connu le même essor que les cristallisoirs à lit fluidisé. Deux approches expérimentales ont été adoptées : (1) l’étude des phénomènes de mélange des réactifs et (2) l’étude de l’influence des conditions opératoires sur la précipitation d’un produit modèle. Le produit modèle choisi pour cette étude est la calcite, le polymorphe le plus stable du carbonate de calcium qui possède trois polymorphes : la vaterite, l’aragonite et la calcite. Cette dernière est obtenue via la réaction de précipitation entre les solutions de chlorure de calcium et de carbonate de sodium à une température de 20° C et en présence d’un agent complexant (citrate de sodium) pour orienter la forme cristalline recherchée. Une étude cinétique a été menée pour la détermination des cinétiques de nucléation et de croissance cristalline de la calcite en milieu citrate. Le réacteur à lit fluidisé, de volume de 10 L, constitué de deux zones : cylindrique de fluidisation et de classification des particules et cylindro-conique de décantation, a été conçu au Laboratoire des Sciences du Génie Chimique. L’étude du mélange global, réalisée à l’aide de la réaction de décoloration acide-base et l’étude hydrodynamique, réalisée à l’aide de suspensions de microbilles, ont permis de développer et d’optimiser ce réacteur multifonctionnel. La faisabilité de la précipitation de la calcite en lit fluidisé a été ensuite vérifiée. Les expériences effectuées en présence d’une charge solide conséquente ont permis de diminuer la sursaturation et de favoriser la croissance cristalline. Le précipité obtenu présente une distribution de taille relativement étroite et la forme des particules obtenues est sensiblement sphérique. Enfin, des essais de modélisation du réacteur à lit fluidisé ont été entrepris pour réaliser des simulations à l’aide du code de calcul commercial FLUENT / The objective of this work is to conceive, develop, implement and to optimize a continuous technology allowing a good control of the precipitation reactions, fast chemical process, giving birth to a solid phase. This precipitor is a multipurpose engine with fluidized bed which did not make the same great strides like fluidized bed crystallizers. Two experimental approaches were adopted : (1) the study of the mixing phenomena of the reagents and (2) the study of the influence of the operating conditions on the precipitation of a model product. The model product selected for this study is the calcite, the polymorphic most stable phase of calcium carbonate which has three polymorphs: vaterite, aragonite and calcite. The latter is obtained by the precipitation reaction between the calcium chloride and sodium carbonate solutions at a temperature of 20° C and a complexing agent (sodium citrate) to have the required crystalline form. A kinetic study was undertaken for the determination of the nucleation and crystalline growth kinetics of calcite in citrate medium. The fluidized bed reactor, having a volume of 10 L, consisted of two zones: cylindrical for fluidization and classification of the particles and cylindro-conical for decantation, was conceived at the Chemical Engineering Science Laboratory (LSGC). The study of mixing phenomena, performed using the decoloration acid-base reaction and the hydrodynamic study, carried out using suspensions of glass microballs, made it possible to develop and optimize this multipurpose reactor. The feasibility of the precipitation of calcite in a fluidized bed was then checked. The experiments carried out in the presence of an important solid content made it possible to decrease supersaturation and to support the crystalline growth. The precipitate obtained presents a relatively narrow size distribution and the particle shape is appreciably spherical. Lastly, the modelling tests of the fluidized bed reactor were undertaken to carry out simulations using the FLUENT commercial computer code