Two-phase flow, ubiquitous to waterflood oil recovery, geological CO2 storage, and groundwater remediation, is strongly influenced by wettability, and made more complex under mixed-wet conditions. Optimum wettability for such operations is not well established due to limited experimental data and difficulties in their interpretation. This thesis investigates the impact of mixed-wettability, characterised by advancing contact angle θa on capillary pressure, relative permeability, and waterflood displacement. Using a Darcy scale simulator, relative permeability kr, capillary pressure Pc, and residual oil saturation Sor were extracted by history matching production and pressure drop data from centrifuge brine invasion and waterflood displacements completed for a range of θa. As θa increased, a larger |Pc| was required to displace oil from mixed-wet cores at high initial oil saturation. End point oil and brine permeability decreased with increasing θa. A permeability enhancement, such that kr > 1, was measured both when the flowing phase was wetting and non-wetting and was attributed to a slippage at the oil/brine interface directly correlated to θa. Residual oil saturation decreased monotonically with increasing θa while core-averaged remaining oil saturation at the end of the waterflood exhibited a non-monotonic dependence on θa. Simulations of the waterfloods revealed that both significant capillary end effects and premature termination of the waterflood in the laboratory contribute to the deviation between remaining and residual saturations. This work demonstrates that the former is not representative of the latter, as it has been assumed in a number of studies in the literature. Both corefloods and microfluidic waterfloods show the importance of combining experimental studies with simulation for correct interpretation of the measurements especially under capillary dominated flow.

Fluid flow rates and pathways in partially-welded, fractured, unsaturated tuff are investigated in a sloping borehole (DSB-1) cored from the surface to a perched aquifer at the Apache Leap near Superior, Arizona. Suspected water-bearing fractures were identified in the borehole using video and geophysical logs. Pore water extracted from cores associated with these fractures proved to have elevated ¹⁴C activity relative to pore waters from intermediate depths. Pore water from the deepest fracture interval contained post-bomb ¹⁴C. Low tritium concentrations in most samples indicates imbibition from each flow is small relative to the volume of water in the pores, but cumulative imbibition over time is significant based on ¹⁴C distribution through the unsaturated zone. The saturated zone beneath DSB-1 is a mixture of fracture flows with older aquifer water. Estimates based on ¹⁴C and ³H data indicate half of the water in the local aquifer originated from fractures near DSB-1. Geochernical models incorporating pore-water, surface-runoff, aquifer-water and mineral chemistry suggest that fracture flow may also be the predominant source of recharge for the older aquifer water. Water and carbon are extracted from core samples using uni-axial compression and a new vacuum distillation technique. Distillation is shown to be an effective method when carbon extraction is not possible by other methods. Mass yields from distillation provide evidence that there may be a substantial reservoir of carbon adsorbed to mineral phases. Carbon-14 activity of formation air samples from intervals with low air permeability reflect the composition of water imbibed from fracture flows at those depths. In zones of higher permeability, atmospheric contamination is suspected even though SF₆ (injected as a tracer during drilling) concentrations had not diminished. An independent investigation on the carbon isotopic composition of soil-zone CO₂ demonstrates the need to correct soil-respired CO₂ samples for CO₂ contamination in base reagents and for fractionation during sample collection. The minimum δ¹³C-shift from soil CO₂ to soil-respired CO₂ is also shown to be a function of the δ¹³C of soil organic material rather than a fixed 4.4%₀ as previously thought.

Thesis (Ph. D.)--Pennsylvania State University, 1990. / Vita. Includes bibliographical references.

The aim of this thesis is to determine the sources, controls and risk aspects of fluoride in surface water and groundwater in a region of southeastern Sweden where the fluorine-rich 1.45 Ga circular Götemar granite (5 km in diameter) crops out in the surrounding 1.8 Ga granites and quartz monzodiorites (TIB rocks). The materials of this thesis include both primary data, collected for the purpose of this thesis, and a large set of secondary data, retrieved from the Swedish Nuclear Fuel and Waste Management Co., the Swedish Geological Survey and the Kalmar County Council. A characteristic feature of the area is high fluoride concentrations in all kinds of natural waters, including surface waters (such as streams) and groundwater in both the Quaternary deposits (regolith groundwater) and bedrock fractures (fracture groundwater). A number of potential sources and controls of the high fluoride concentrations were investigated, including a variety of geological, mineralogical, mineral-chemical and hydrological features and processes. For the stream waters and regolith groundwater, high fluoride concentrations were correlated with the location of the Götemar granite. This finding is explained by the discharge of fluoride-rich groundwater from fractures in the bedrock and/or the release of fluoride due to the weathering of fluorine-bearing minerals in the Quaternary deposits; however, the Quaternary deposits had considerably lower fluoride concentrations than the underlying bedrock. The high fluoride concentrations in the fresh fracture groundwater (up to 7.4 mg/L) in the TIB-rocks are proposed to be the result of long residence times and the alteration/dissolution of fluorine-bearing primary and secondary minerals along the fracture walls. In terms of risk aspects, this thesis shows that fluoride can add to the transport and inorganic complexation of aluminium in humic-rich, acidic streams. Additionally, 24 % of the children in households with private wells in Kalmar County were assessed to be at risk of excess fluoride intake based on the WHO drinking water guideline value (1.5 mg/L). However, the risk increased significantly when instead the US EPA reference dose (0.06 mg/kg-day) was used, both when all relevant exposure pathways were taken into account as well as water consumption alone. Hence, it is shown that the risk of an excess intake of fluoride is strongly dependent on the basis for evaluation.

One way to reduce the amount of CO2 in the atmosphere for the mitigation of climate change is to capture the CO2 and inject it into geological formations. The most important public concern about carbon capture and storage (CCS) is whether stored CO2 will leak into groundwater sources and finally into the atmosphere. To prevent the leakage, the possible leakage paths and the mechanisms triggering the paths must be examined and identified. It is known that the leakage paths can be due to CO2 - rock interaction and CO2 &ndash / well interaction. The objective of this research is to identify the geochemical reactions of the dissolved CO2 in the synthetic formation water with the rock minerals of the Sayindere cap rock by laboratory experiments. It is also aimed to model and simulate the experiments using ToughReact software. Sayindere formation is the cap rock of the Caylarbasi, a southeastern petroleum field in Turkey. The mineralogical investigation and fluid chemistry analysis of the experiments show that calcite was dissolved from the cap rock core as a result of CO2- water- rock interaction. Using the reactive transport code TOUGHREACT, the modeling of the dynamic experiment is performed. Calcite, the main primary mineral in the Sayindere is dissolved first and then re-precipitated during the simulation process. The decreases of 0.01 % in the porosity and 0.03% in permeability of the packed core of the Sayindere cap rock are observed in the simulation. The simulation was continued for 25 years without CO2 injection. However, the results of this simulation show that the porosity and permeability are increased by 0.001 % and 0.004 %, respectively due to the CO2-water-rock mineral interaction. This shows that the Sayindere cap rock integrity must be monitored in the field if application is planned.

No description available.

La caractérisation géochimique et isotopique des eaux souterraines de la « zone minéralisée de l’Entre-Deux-Mers » indique une origine commune de la minéralisation, directement liée à la minéralogie des formations captées par les forages.La géochimie montre que les interactions eau-roche sont majoritairement influencées par la présence d’évaporites, mais que d’autres interactions mettant en jeu des carbonates, des silicates et des argiles existent. Un modèle géochimique d’acquisition de la minéralisation reconstitue parfaitement la chimie des eaux souterraines à l’échelle de la zone d’étude. Ce modèle, construit en se basant sur la géochimie des eaux et sur la minéralogie des formations tertiaires du nord du Bassin aquitain, met à l’équilibre des eaux avec des formations carbonatées et évaporitiques. Afin de mieux comprendre la distribution latérale et verticale des formations tertiaires et leur minéralogie, une approche paléogéographique et sédimentologique a permis de localiser les différents horizons riches en sulfates et/ou en fluorures, mais aussi de comprendre leur origine de dépôt. En se basant sur l’hydrogéologie, la paléogéographie, la minéralogie et la géochimie, des hypothèses de répartition de la minéralisation à l’échelle du forage ont pu être testées. Les résultats de la modélisation couplée hydrodynamique–transport reconstituent la chimie des eaux prélevées par les forages de la « zone minéralisée de l’Entre-Deux-Mers ». Au vu de ces résultats, un modèle avec obturation des horizons riches en sulfates et en fluorures a été testé et les résultats obtenus ouvrent des perspectives pour des futures recherches. Ce travail a donc permis de comprendre l’origine de la minéralisation des eaux de « la zone minéralisée de l’Entre-Deux-Mers », mais aussi de proposer des améliorations et des perspectives pour une meilleure gestion d’une des principales ressources en eau potable de la Gironde. / Geochemical and isotopic characterizations of groundwaters in the "mineralized Entre-Deux-Mers area" indicate a common origin of the mineralization, directly linked to the mineralogy of the formations abstracted by drilling.Geochemistry shows that water-rock interactions are mainly influenced by the presence of evaporites, and that but that other interactions involving carbonates, silicates and clays exist. A geochemical model based on the water geochemistry and mineralogy of the Tertiary formations of northern Aquitaine Basin fix waters in equilibrium with evaporitic and carbonated formations. This model reconstitutes perfectly the groundwaters’ chemistry across the study area and explains the mineralization acquisition. Improving the understanding of the lateral and vertical distribution of tertiary formations and their mineralogy requires a sedimentological and paleogeographical approach. This approach allowed to locate the different layers rich in sulphates and/or fluoride and to understand also their origin.Based on hydrogeology, paleogeography, mineralogy and geochemistry, the distribution of the mineralization has been tested at the borehole scale. The results of this coupled hydrodynamic-transport modeling reconstitute the chemistry of the groundwaters in the "mineralized Entre-Deux-Mers area." A model, that considers the sealing of sulphates- and fluorides-rich layers has been tested and its results highlights future research perspectives. This work has allowed understanding the origin of the mineralization of the waters "of the mineralized Entre-Deux-Mers area" and also suggests improvements and prospects for sustainable management of a major drinking water resource in Gironde.

Mid-ocean ridge hydrothermal systems are known to extend to deep levels of the oceanic crust, including the plutonic section, but little is known about the timing and nature of fluid-rock interactions at these levels. To investigate the temporal and spatial characteristics of hydrothermal alteration in the lower crust, this study investigates a suite of hydrothermally altered (<5 to >20% hydrous alteration) gabbroic rocks recovered from the Hess Deep Rift, where 1.2 Ma fast-spreading East Pacific Rise crust is well-exposed. These samples were altered to amphibole-dominated assemblages with chlorite-rich samples occurring in a restricted region of the field area. Hornfels, indicative of reheated, previously altered rocks, are clustered in the central part of the field area. The entire sample suite has elevated 87Sr/86Sr (mean: 0.70257±0.00007 (2σ), n=16) with respect to fresh rock (0.7024). Bulk rock 87Sr/86Sr is strongly correlated with percentage of hydrous alteration and weakly correlated with bulk rock Sr content. The distribution of Sr in igneous and metamorphic minerals suggests that greenshist-facies alteration assemblages (chlorite, actinolitic amphibole, albitic plagioclase) lose Sr to the fluid while amphibolite-facies secondary assemblages (secondary hornblende, anorthitic plagioclase) take up Sr. The temperature-dependent mobilization of Sr in hydrothermal systems has implications for the 87Sr/86Sr and ultimately fluid/rock ratio calculations based on the assessed 87Sr/86Sr systematics. Considering Sr behaviour, minimum fluid/rock ratios of ~1 were calculated for the plutonic section. Due to the large uncertainty regarding fluid Sr composition at depth and the sensitivity of fluid/rock ratio calculations on this parameter, a model combining the sheeted dike complex and the plutonic section to one hydrothermal system is introduced, yielding a fluid/rock ratio of 0.5. This value may be more realistic since the fluid composition entering and exiting the sheeted dike complex is better constrained. The regional distribution of hornfelsed material with elevated 87Sr/86Sr suggests that fluid ingress into the upper plutonics at Hess Deep occurred on-axis in a dynamic interface of a vertically migrating axial magma chamber (AMC) and the base of the hydrothermal system. / Graduate

Dans cette étude, nous cherchons à dresser le bilan de l’altération à l’échelle de l’île de Mayotte (en surface et en souterrain), à contraindre l’impact des facteurs de contrôle dominant l’altération, puis à caractériser les processus impliqués dans les fractionnements des isotopes du silicium à l’échelle du profil d’altération.Deux campagnes d’échantillonnage incluant des eaux de rivières et des eaux souterraines ont été réalisées en saison humide et sèche, complétées par le prélèvement mensuel de 5 rivières. La prise en compte des crues (3 % de l’année) dans le calcul des taux d’altération moyens annuels en rivière a entraîné une augmentation de ≈32 % du bilan annuel. Le taux d’altération chimique global de l’île de Mayotte s’élève à 94 t/km²/an (81 t/km²/an en surface & 131 t/km²/an en souterrain). Nos résultats mettent en avant le rôle prépondérant des écoulements souterrains dans le transport de matériel dissous directement à l’océan. La contribution du domaine souterrain au bilan de l’altération diminue avec l’âge des formations, soulignant l’implication de l’âge des roches du bassin versant comme paramètre clé dans le contrôle des taux d’altération.Les isotopes du Si ont été analysés sur des roches totales le long de profils d’altération associés à différentes conditions d'altération du régolite : météorique (basse température) ou hydrothermale (haute température). À l’échelle du profil, les deux types de régimes ont montré un appauvrissement en 30Si en fonction du degré d’altération. À l’échelle du minéral, le fractionnement des isotopes du Si s’est révélé plus négatif pendant la précipitation de kaolinite secondaire à haute température qu’à basse température. / In this study, we seek to establish the weathering budget at the scale of the island of Mayotte (rivers and groundwater), to constrain the impact of dominant control factors to the weathering both locally and at a global scale, and then to characterize the processes involved in the fractionation of silicon isotopes across the weathering profile.Two field campaigns, in order to sample river water and groundwater, were carried out during wet and dry season, supplemented by the monthly monitoring of 5 rivers. By taking account of river floods (3% of the year) in the calculation of average annual weathering rates in the river has increased the annual weathering budget by ≈32%. The overall rate of Mayotte Island chemical weathering is 94 t/km²/yr (81 t/km²/yr from surface & 131 t/km²/yr from underground). Our results highlight the important role of groundwater flow to the dissolved material export directly to the ocean. The contribution of groundwater to the weathering budget decreases with the age of the geological formations, highlighting the involvement of the age of the rocks of the watershed as a key parameter in the weathering rates control.Si isotopes were analyzed for whole rock along two weathering profiles associated with different alteration conditions of the regolith: meteoric (low temperature) or hydrothermal (high temperature). At the weathering profile scale, the two types of alteration regimes showed 30Si depletion as a function of the degree of weathering. At the mineral scale, Si isotope fractionation was more negative during the secondary kaolinite precipitation at high temperatures than at low temperatures.