Geochemical processes involving the interaction of fluids and minerals occur in nearly every environment on the surface and in the crust of the Earth. The variety of fluid–mineral processes on the Earth is quite diverse, and these various processes can occur under a large range of geochemical conditions. Aqueous dissolution and alteration, hydration, protonation, solution–precipitation, diffusion, and fluid and isotope exchange are among the many fluid–mineral interaction processes that contribute to the overall cycling of elements on Earth. This dissertation uses analog experiments to examine fluid­–mineral interaction processes found in different geological environments and under a range of environmental conditions. The first part of this dissertation examines the reactive and diffusive exchange of oxygen isotopes that results from performing a dolomite breakdown experiment under a temperature, pressure, and fluid condition analogous to a contact metamorphic environment. The second two parts of the dissertation involve the development of new methods for the growth of nanocrystalline fayalite and intermediate composition olivine. The final two parts of this dissertation focus on the interaction of olivine with either H2O or acidic solutions (0.005 M H2SO4 or 0.01 M HCl) at low temperature and pressure. The first of these two parts experimentally uses different surface area olivine powders that are reacted with low pH fluids in non-buffered, closed system experiments where pH and solution composition are allowed to change. The second of these two parts uses various analytical techniques that can examines changes to the surfaces of olivine single crystals at the nanoscale resulting from experiments performed under environmental conditions where the fluid–mineral interaction transitions from dissolution at low temperature and pressure to alteration at moderate temperature and pressure. Though the individual projects contained within this dissertation are varied, they share the common theme of using experiments to examine fluid­–mineral interaction processes.

Edremit geothermal field with 42-62 &deg / C discharge temperatures is utilized for space heating. Alternation of permeable and impermeable units created two superimposed aquifers in the area: upper unconfined and lower confined. Water samples from 21 (hot, warm, cold) wells were taken in this study. 8 of these wells penetrate the deeper confined, while 13 penetrate the shallower unconfined aquifer. Geochemical analysis revealed Na+K&ndash / SO4 nature for the hot (&gt / 40&deg / C), Ca&ndash / HCO3 nature for the cold (&lt / 30&deg / C) and Ca&ndash / SO4 nature for the warm (30-40&deg / C) waters. &delta / 18O-&delta / D compositions point to a meteoric origin for all waters, while 14C analyses suggest longer subsurface residence times for the hot, compared to the cold/warm waters. Chemical and isotopic compositions indicate that &ldquo / mixing&rdquo / and &ldquo / water-rock interaction&rdquo / are the possible subsurface processes. When silica and cation geothermometers are evaluated together with fluid mineral equilibria calculations, a 110&deg / C reservoir temperature is expected in the field. Saturation indices indicate potential silica scaling for waters at temperatures lower than discharge temperatures. Hydrogeology of the study area is highly affected by faults. The groundwater is percolated (down to 3 km depth) via deep seated step faults, heated at depth and ascends to surface at the low lands, especially through intersection of buried, mid-graben faults. During its ascent towards surface, geothermal water invades the two superimposed aquifers and mixing between hot and cold waters takes place in the aquifers. Resource assessment studies suggest a 3.45x1013 kJ accessible resource base and 9.1 MWt recoverable heat energy for Edremit geothermal field with 90% probability.

Fluids play a vital role in essentially all geologic environments and processes, and are the principal media of heat and mass transfer in the Earth. The properties of geologic fluids can be diverse, as fluids occur at conditions ranging from ambient temperatures and pressures at Earth's surface, to extreme temperatures and pressures in Earth's deep interior. Regardless the wide ranges of conditions at which geologic fluids occur, fluid properties are described and governed by the same fundamental thermodynamic relationships. Thus, application of thermodynamic principles and methods allows us to decipher the properties and roles of geologic fluids, to help understand geologic processes. Fluid inclusions in minerals provide one of the best available tools to study the compositions of geological fluids. Compositions of fluid inclusions can be determined from microthermometric measurements, based on the vapor-saturated liquidus conditions of model chemical systems, or by various microanalytical techniques. The vaporsaturated liquidus relations of the system H2O-NaCl-CaCl2 have been modeled to allow estimation of fluid inclusion compositions by either microthermometric or microanalytical methods. Carbon capture and storage (CCS) in deep saline formations represents one option for reducing anthropogenic CO2 emissions into Earth's atmosphere. Availability of storage volume in deep saline formations is a significant component of injection and storage planning. Investigation of the volumetric properties of CO2, brine and CO2-saturated brine reveals that storage volume requirements are minimized when CO2 dissolves into brine. These results suggest that a protocol involving brine extraction, CO2 dissolution and re-injection may optimize CCS in deep saline formations. Numerical modeling of quartz dissolution and precipitation in a sub-seafloor hydrothermal system was used to understand the role of fluid-phase immiscibility ("boiling") on quartz-fluid interactions, and to predict where in the system quartz could deposit and trap fluid inclusions. The spatial distribution of zones of quartz dissolution and precipitation is complex, owing to the many inter-related factors controlling quartz solubility. Immiscibility exerts a strong control over the occurrence of quartz precipitation in the deeper regions of fluid circulation. / Ph. D.

Iron (oxyhydr)oxide concretions in the Navajo Sandstone of southern Utah have been extensively researched as Martian analogues. However, the discovery of calcium carbonate concretions in areas such as Coyote Gulch, Utah, has encouraged recent studies to understand the relationship between calcium carbonate spheroidal concretions as possible precursors to iron (oxyhydr)oxide concretions, and to determine the fluid chemistries involved in diagenesis. This is important because nucleation and precipitation mechanisms of these spheroidal calcium carbonate and iron (oxyhydr)oxide concretions and fluid mechanisms in iron rich environments could affect the preservation of possible biosignatures in other subsurface features on Mars. The elemental and mineralogical compositions of the concretions were examined in order to determine physical and chemical features shared by the two types of concretions and did show that they share similar morphologies; however, the Coyote Gulch concretions are calcite cemented (~30 wt.%), with secondary iron (oxyhydr)oxide precipitation and decreases in calcite in transects away from the calcium carbonate concretions. Several chemical and mineralogical differences exist between the two separate populations of concretions, possibly due to regional variability of reacting phases in fluid systems. Spring fluids emanating from the Navajo Sandstone in Coyote Gulch were tested to determine the fluids responsible for the development of any of the concretion mineralogies in the study area which could form in distinctive geochemical systems. Geochemical modeling performed in this research explored the question of fluid chemistry involved in concretion formation in the Navajo Sandstone and findings suggest that the calcite concretions formed prior to the precipitation of secondary iron (oxyhydr)oxides and may have provided a localized buffering environment for the precipitation of iron (oxyhydr)oxides. Paleofluid circulation, redox processes, and elemental mobility are examined using the geochemistry of Navajo Sandstone concretions and host rock. Various simulations applicable to diagenetic fluids in the studied concretions show the importance of salinity and pH in paleoaquifers in order to precipitate mineral assemblages similar to those found in the Navajo Sandstone. Widespread dissolution features, major and trace element distributions, and geochemical modeling identified feasible fluid-rock interactions in paleofluids, including the importance of limited H2S gas and the limited feasibility of hydrocarbon rich fluids in concretion formation using current data. A universal mechanism for calcium carbonate to iron (oxyhydr)oxide concretion formation could be applied on other planets and provide exciting implications in the search for carbon rich redox gradients which could support life in the subsurface of otherwise inhospitable planets.