Groundwater overexploitation can cause the collapse of coastal aquifers. The goal of this study was to apply a template, the computer code SEAWAT to evaluate the behavior of the salt wedge Coastal Aquifer System, which has studied the case of complex Barreira/Marituba in Part Coast Metropolitan Region of Maceió-AL. In addition they were analyzed physicochemical indexes to characterize the study area and verify the source of salt contamination. The model calibration was performed in two parts. The underground flow calibration obtained a correlation coefficient between calculated hydraulic loads and observed of 0.764 and the calibration concentration of Total Dissolved Solids, which has very close to the salt concentration value, obtained a 0.682 correlation coefficient for the year 2015 . Since then analyzed two different scenarios, which allowed us to verify the effect of groundwater exploitation in the salt wedge for the year 2025. The first considered the existing exploitation by 2015 without pumping increments. As a result, it was found advancing saline wedge area into two areas, an area that suffers decrease, besides the formation of cones with vertical rise of the seawater. In the second scenario were added licenses of water works as well and plus the assumption of 32 new pumping wells installation, according to the city's growth. However, in this case, it was not possible to see variations in the mix zone for the first scenario for the year 2025. The analysis of hydrogeological indices pointed to higher chloride concentrations in the region close to the line of the Atlantic Ocean, with little influence of nitrate and, in general, showed the existence of seawater intrusion. / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A exploração indiscriminada de água subterrânea pode causar o colapso dos aquíferos costeiros. O objetivo deste trabalho foi aplicar um modelo, o código computacional SEAWAT, para avaliar o comportamento da cunha salina em Sistema Aquífero Costeiro, onde foi estudado o caso do Complexo Barreira/Marituba na costa de Parte da Região Metropolitana de Maceió-AL. Ademais foram analisados índices físico-químicos para caracterizar a região de estudo e verificar a fonte de contaminação salina. A calibração do modelo foi realizada em duas vertentes. A calibração de fluxo subterrâneo obteve um coeficiente de correlação entre cargas hidráulicas calculadas e observadas de 0,764 e a calibração de concentração de Sólidos Totais Dissolvidos, que possui valor muito próximo à concentração de sal, obteve um coeficiente de correlação de 0,682 para o ano de 2015. A partir de então foram analisados dois cenários distintos, que permitiram verificar o efeito da explotação de água subterrânea na cunha salina para o ano de 2025. O primeiro considerou a explotação existente até 2015, sem acréscimos de bombeamentos. Como resultado, verificou-se o avanço da cunha salina em duas áreas do domínio, uma área que sofre recuo, além da formação de cones com ascensão vertical da água do mar. No segundo cenário foram adicionadas as licenças de obras hídricas como poços e mais a hipótese de instalação de 32 novos poços de bombeamento, de acordo com o crescimento da cidade. Porém, neste caso, não foi possível visualizar variações na zona de mescla em relação ao primeiro cenário para o ano de 2025. A análise dos índices hidrogeológicos apontou para maiores concentrações de cloretos na região próxima à linha do Oceano Atlântico, com pouca influência do nitrato e, no geral, indicaram a existência de intrusão de água do mar.

Dans un contexte de réduction internationale des émissions de gaz à effet de serre, les techniques de Captage Transport et Stockage de ce{CO2} (CTSC) apparaissent comme une solution à moyen terme particulièrement efficace. En effet, les capacités de stockage géologique pourraient s'élever jusqu'à plusieurs millions de tonnes de ce{CO2} injectées par an, soit une réduction substantielle des émissions atmosphériques de ce gaz. Une des cibles privilégiées pour la mise en place de cette solution sont les aquifères salins profonds. Ces aquifères sont des formations géologiques contenant une saumure dont la salinité est souvent supérieure à celle de la mer la rendant impropre à la consommation. Cependant, cette technique fait face à de nombreux défis technologiques; en particulier la précipitation des sels, dissous dans l'eau présente initialement dans l'aquifère cible, suite à son évaporation par le ce{CO2} injecté. Les conséquences de cette précipitation sont multiples, mais la plus importante est une modification de l'injectivité, c'est-à-dire des capacités d'injection. La connaissance de l'influence de la précipitation sur l'injectivité est particulièrement importante tant au niveau de l'efficacité du stockage et de l'injection qu'au niveau de la sécurité et de la durabilité du stockage. Le but de ces travaux de thèse est de comparer l'importance relative des phénomènes négatif (colmatage) et positif (fracturation) consécutifs à l'injection de ce{CO2} et à la précipitation des sels. Au vu des nombreux résultats de simulations et de modélisation dans la littérature décrivant le colmatage de la porosité, il a été décidé de porter l'accent sur les effets mécaniques de la cristallisation des sels et la possible déformation de la roche mère. Une modélisation macroscopique et microscopique, tenant compte de deux modes possibles d'évaporation induits par la distribution spatiale de l'eau résiduelle a donc été développée afin de prédire le comportement mécanique d'un matériau poreux soumis à un assèchement par injection de ce{CO2}. Les résultats montrent que la pression de cristallisation consécutive à la croissance d'un cristal en milieu confiné peut atteindre des valeurs susceptibles localement de dépasser la résistance mécanique du matériau, soulignant ainsi l'importance de ces phénomènes dans le comportement mécanique global de l'aquifère. Sur le plan expérimental, les travaux ont porté sur l'utilisation d'un nouveau prototype de percolation réactive afin de reproduire le comportement d'une carotte de roche soumise à l'injection et ainsi obtenir l'évolution des perméabilités dans des conditions similaires à celle d'un aquifère / In a context of international reduction of greenhouse gases emissions, CCS (ce{CO2} Capture and Storage) appears as a particularly interesting midterm solution. Indeed, geological storage capacities may raise to several millions of tons of ce{CO2} injected per year, allowing to reduce substantially the atmospheric emissions of this gas. One of the most interesting targets for the development of this solution are the deep saline aquifers. These aquifers are geological formations containing brine whose salinity is often higher than sea water's, making it unsuitable for human consumption. However, this solution has to cope with numerous technical issues, and in particular, the precipitation of salt initially dissolved in the aquifer brine. Consequences of this precipitation are multiple, but the most important is the modification of the injectivity i.e. the injection capacity. Knowledge of the influence of the precipitation on the injectivity is particularly important for both the storage efficiency and the storage security and durability. The aim of this PhD work is to compare the relative importance of negative (clogging) and positive (fracturing) phenomena following ce{CO2} injection and salt precipitation. Because of the numerous simulations and modelling results in the literature describing the clogging of the porosity, it has been decided to focus on the mechanical effects of the salt crystallization and the possible deformation of the host rock. A macroscopic and microscopic modelling has then been developed, taking into account two possible modes of evaporation induced by the spatial distribution of residual water, in order to predict the behavior of a porous material subjected to the drying by carbon dioxide injection. Results show that crystallization pressure created by the growth of a crystal in a confined medium can reach values susceptible to locally exceed the mechanic resistance of the host rock, highlighting the importance of these phenomena in the global mechanical behavior of the aquifer. At the experimental level, the study of a rock core submitted to the injection of supercritical carbon dioxide has been proceeded on a new reactive percolation prototype in order to obtain the evolution of permeabilities in conditions similar to these of a deep saline aquifer

The primary objective was to predict the relative storage capacity of carbonate rocks relevant for carbon dioxide sequestration. To achieve this, a detailed pore scale characterization of model carbonate rocks, Indiana Limestone and Pink Dolomite, was conducted utilizing micro-computed tomography (microCT) data using pore network modeling and invasion percolation simulations. For the first time in literature, Pink Dolomite’s pore space characteristics were analyzed. A secondary objective was to compare thresholding techniques as applied to carbonates which exhibit dual porosity (porosity at multiple length scales). The analysis showed the sensitivity of existing methods to the thresholding technique, imaging method and material. Overall, the contributions of this work provide an assessment of two carbonates relevant for carbon capture and storage at the pore scale; and a preliminary assessment into thresholding dual porosity carbonates.

The primary objective was to predict the relative storage capacity of carbonate rocks relevant for carbon dioxide sequestration. To achieve this, a detailed pore scale characterization of model carbonate rocks, Indiana Limestone and Pink Dolomite, was conducted utilizing micro-computed tomography (microCT) data using pore network modeling and invasion percolation simulations. For the first time in literature, Pink Dolomite’s pore space characteristics were analyzed. A secondary objective was to compare thresholding techniques as applied to carbonates which exhibit dual porosity (porosity at multiple length scales). The analysis showed the sensitivity of existing methods to the thresholding technique, imaging method and material. Overall, the contributions of this work provide an assessment of two carbonates relevant for carbon capture and storage at the pore scale; and a preliminary assessment into thresholding dual porosity carbonates.

Saline aquifers and depleted hydrocarbon fields situated beneath the North Sea are currently being proposed as storage repositories for anthropogenic CO2 captured from point source emitters in the UK and mainland Europe. Two experimental sites are already operating successfully offshore Norway: Sleipner since 1996 and Snøhvit since 2007, collectively storing several million tonnes of CO2/year in the sub-surface. Despite the apparent success of these current projects, one of the major public and scientific concerns is the ability of storage sites to retain CO2 on the millennial timescales required for CO2 plume stabilisation and dissolution. Some areas of the North Sea are also known to contain palaeo-gas seepage pathways within overburden sediments that overlie deeper hydrocarbon reservoirs (e.g. Witch Ground Graben). These areas either need to be avoided for CO2 storage or rigorously assessed in terms of leakage risk. Since the Sleipner storage site lies within such a province, this thesis delivers a detailed evaluation of the Nordland Group overburden and a critical assessment of its long-term sealing capability for CO2. From interpretation and detailed mapping of a baseline 3D seismic dataset (acquired before CO2 injection operations commenced in 1996), we have identified numerous palaeo-migration pathways and high-amplitude seismic anomalies within the Nordland Group overburden sediments deposited above the Sleipner CO2 storage site. We attributed these features to thermogenic or biogenic gas migration, accumulation and bio-degradation over geological time. We also mapped a complex network of sand-filled, glacial channels and tunnel valleys distributed within a few hundred metres below seabed and highlighted their significance as potential fluid migration networks and/or secondary storage containment for leaking CO2. Of further significance, we confirmed that these overburden features also create spatial density variations that impact on the accuracy of seismic time-depth conversions, resulting in the probability of topographic distortions being propagated into seismic interpretations and models. To the best of our knowledge no such detailed mapping of the Nordland Group overburden at Sleipner has been undertaken previously. To determine whether the top layer of the CO2 plume at Sleipner might encounter these relict pathways as it ascends and migrates laterally beneath the caprock, we evaluated the critical column heights required for a CO2 accumulation to enter such a pathway under a range of storage conditions for a CH4/CO2/brine system; assuming that these pathways currently contain methane gas. Risking scenarios were based on a range of phase saturation, pressure, temperature, density, viscosity, interfacial tension and wettability conditions likely to be encountered at depths commensurate with the caprock at Sleipner. We concluded that given certain conditions at the caprock, CO2 could leak more easily into palaeo-migration pathways than CH4 (i.e. at lower entry pressures and therefore smaller column heights), assuming that brine densities and, most importantly, pore radii have not changed significantly over geological time (i.e. no cementation or dissolution has taken place). To further understand the dynamic significance of these palaeo-migration pathways, channels and tunnel valleys, including their ability to form inter-connected leakage/migration networks, we constructed a series of high-resolution 3D models of the Sleipner storage site and overburden, then used stochastic basin modelling and simulation techniques to investigate the processes involved during the introduction of CO2 into the storage site over a prolonged time period. Models were populated with geological, stratigraphic and structural information derived from our seismic interpretation. Flow simulations were calibrated to published data and matched to the present-day plume distribution. The absence of observational reservoir pressure and temperature data from Sleipner introduces significant uncertainty to model outcomes with respect to CO2 density and column height estimates and to surmount this difficulty we constrained the caprock temperature to CO2 density estimates obtained from the most recent gravity data observations at Sleipner. We concluded that the overburden heterogeneity is significant and palaeo-migration pathways, highpermeability channels and tunnel valleys at Sleipner may become potential migration pathways for CO2 as the plume continues to spread laterally over the coming decade, but the possible storage response is difficult to quantify given the absence of sufficient overburden rock property information and accurate pressure and temperature data for the storage site. The overall conclusion from this work is that insufficient information was collected within the Sleipner area prior to storage site development and too many significant studies which should have been performed as a pre-requisite (e.g. obtaining a caprock sample for laboratory testing of potential seal capacity), were actually performed some years after CO2 injection operations had already commenced. The pressure and temperature conditions at the caprock depth for the Sleipner storage site are also marginal in terms of maintaining CO2 above critical point conditions in dense phase and thus maximising storage efficiency. Most significantly, no rigorous overburden mapping and risking was performed for Sleipner (such as the work described in this thesis), thus the fact that no leakage has been detected at Sleipner is more due to good fortune than following best practices. Hopefully, our work has highlighted these key deficiencies so that future CO2 storage site feasibility and development studies will be performed more diligently.

Für eine effiziente und nachhaltige Nutzung von Georeservoiren sind bestmögliche Reservoirmanagementverfahren erforderlich. Oft setzen diese Verfahren auf Tracer-Tests. Dabei enthalten die aufgezeichneten Tracersignale integrale Informationen der Reservoireigenschaften. Tracer-Tests bieten somit eine leistungsfähige Technik zur Charakterisierung und Überwachung der bewirtschafteten Georeservoire. Im Gegensatz zu Tracer-Tests mit konservativen Tracern, welche bereits etablierte Testroutinen zur Verfügung stellen, ist die Verwendung von reaktiven Tracern ein neuer Ansatz. Aufgrund unpassender physikalisch-chemischer Modelle und/oder falschen Annahmen ist die Analyse und Interpretation von reaktiven Tracersignalen jedoch oft verzerrt, fehlinterpretiert oder sogar unmöglich. Reaktive Tracer sind dennoch unersetzbar, da sie durch die gezielte Ausnutzung selektiver und spezifischer Reaktionen mögliche Metriken von Reservoirtestverfahren auf einzigartige Weise erweitern. So liefern reaktive Tracer für ein integriertes Reservoirmanagement geforderten Aussagen über Reservoirmetriken wie z.B. Wärmeaustauschflächen oder in-situ Temperaturen. Um Unsicherheiten bei der Auswertung von Tracerexperimenten zu reduzieren, werden theoretische und experimentelle Untersuchungen zu hydrolysierenden Tracern vorgestellt. Diese Tracer sind durch ihre Reaktion mit Wasser charakterisiert. Einerseits können sie als thermo-sensitive Tracer Informationen über Temperaturen und abgekühlte Anteile eines beprobten Reservoirs liefern. Für die Interpretation von thermo-sensitiven Tracerexperimenten sind die Kenntnis der zugrunde liegenden Reaktionsmechanismen sowie bekannte Arrhenius-Parameter Voraussetzung, um die verwendete Reaktion pseudo erster Ordnung nutzen zu können. Darüber hinaus ermöglichen die verwendeten Verbindungen durch ihre Fluoreszenzeigenschaften eine Online-Messung. Um die Empfindlichkeit und praktischen Grenzen thermo-sensitiver Tracer zu untersuchen, wurden kontrollierte Laborexperimente in einem eigens dafür entwickelten Versuchsaufbau durchgeführt. Dieser besteht aus zwei seriell geschalteten Säulen, die beide mit Sand gefüllt sind und jeweils auf eine eigene Temperatur eingestellt werden können. Somit ist es möglich, verschiedene thermische Einstellungen zu betrachten. Die untersuchten experimentellen Szenarien imitieren größtenteils Feldanwendungen: Durchflussexperimente sowie auch Experimente mit einer Umkehr der Fließrichtung. Darüber hinaus wurde untersucht, ob thermo-sensitive Tracer auch sensitiv gegenüber der Position der Temperaturfront sind. Dabei wurden die Tracer kontinuierlich oder gepulst injiziert. Die Ergebnisse bestätigen die zugrunde liegende Theorie experimentell. Wenn die pH-Abhängigkeit der Hydrolyse bei der Analyse berücksichtigt wird, kann eine Temperaturschätzung mit einer Genauigkeit und Präzision von bis zu 1 K erreicht werden. Die Schätzungen sind von Verweilzeit und gemessenen Konzentrationen unabhängig. Weiterhin lässt sich eine Schätzung über den ausgekühlten Anteil des Systems erhalten. Durch die steuerbaren und definierten Laborbedingungen ist es erstmals möglich, die geforderte Anwendbarkeit von thermo-sensitiven Tracern belastbar nachzuweisen. Des Weiteren wird eine zweite Anwendung hydrolysierender Tracer vorgeschlagen. Beim Lösen von CO2 für „Carbon Capture and Storage“-Anwendungen hängt die Effizienz maßgeblich von der Grenzfläche zwischen CO2 und der Sole in tiefen Reservoiren ab. Somit ist diese Metrik wichtig, um die Effizienz der CO2 Auflösung in Wasser zu bewerten. Die gezielt entwickelten Kinetic-Interface-Senitive-Tracer (KIS-Tracer) nutzen, zusätzlich zur Hydrolyse an der Grenzfläche, die unterschiedlichen Lösungseigenschaften von Tracer und Reaktionsprodukt im entsprechenden Fluid. Somit lassen sich potentiell Aussagen über die Dynamik der Grenzfläche machen. Neben dem grundlegenden Konzept sowie den theoretischen Tracer-Anforderungen wird eine erste Anwendung im Laborexperiment vorgestellt. Diese zeigt das erfolgreiche, zielorientierte Moleküldesign und bietet eine experimentelle Basis für ein makroskopisches numerisches Modell, mit welchem numerische Simulationen verschiedener Testszenarien durchgeführt werden, um das Zusammenspiel von KIS-Tracer und dynamischer Grenzfläche zu untersuchen. Aufgrund der Temperaturabhängigkeit der Reaktionsgeschwindigkeit hydrolysierender Tracer werden in der Regel auch thermische Signale aufgezeichnet. Der letzte Teil prüft die Möglichkeit, Informationen aus den aufgezeichneten Temperaturen zu extrahieren. Für ein idealisiertes Einzelkluftsystem wird eine Reihe von analytischen Lösungen diskutiert. Aus thermischen Injektion-/Entzugsversuchen können damit räumliche und zeitliche Profile abgeleitet werden. Mit der Verwendung von mathematisch effizienten Inversionsverfahren wie der iterativen Laplace-Transformation lassen sich rechentechnisch effiziente Realraum-Lösungen ableiten. Durch die Einführung von drei dimensionslosen Kennzahlen können die berechneten Temperaturprofile auf Bruchbreite oder Wärmetransportrate, wechselnde Injektions-/ Pumpraten und/oder auf in der Nähe beobachtbare räumliche Informationen analysiert werden. Schließlich werden analytische Lösungen als Kernel-Funktionen für nichtlineare Optimierungsalgorithmen vorgestellt. Zusammenfassend bearbeitet die vorliegende Arbeit den Übergang zwischen Tracerauswahl und Traceranwendung. Die Ergebnisse helfen Planungs- und Analyseunsicherheiten zu reduzieren. Dies wird bezüglich der Empfindlichkeit gegenüber Temperaturen, Kühlungsanteilen, flüssig/flüssig-Grenzfläche, Kluftbreite und Wärmetransportrate gezeigt. Somit bieten die vorgestellten Tracerkonzepte neue Metriken zur Verbesserung von Reservoirmanagementverfahren. Die experimentellen Ergebnisse und die neuen analytischen Modelle ermöglichen einen tiefen Einblick in die kollektive Rolle der Parameter, welche die Hydrolyse und den Wärmetransport in Georeservoiren kontrollieren.