Contamination of surface and ground water has emerged as one of the most important environmental issues in developed and developing countries. Bioremediation of groundwater takes advantage of bacteria present in the environment to transform toxic compounds to non-toxic metabolites. This biotechnology holds the potential for fast, inexpensive, and effective water decontamination. However, it is still poorly understood and usually not fully controlled due to the lack of information describing the natural phenomena involved. Therefore, a better understanding of the phenomena involved during bioremediation of groundwater could help in the design and implementation of more efficient technologies. The main objective of the present research is to assess how pore-scale physical factors, such as pore-scale velocity, affect the degradation potential of contaminants during transport in groundwater. The target chemicals studied were chlorinated ethenes because they are commonly found in contaminated groundwater sites. To achieve the research objective, the following were employed: a mathematical model that links pore scale processes to the macro-scale representation of contaminant transport; development of numerical tools to solve the mathematical model; and experimental elucidation of the influence of pore-scale flow velocity on the biodegradation of contaminants using column experiments. Results from the mathematical model and experiments were used to elucidate the inter-relationship between physical and biological phenomena at the micro scale. The influence of flow velocity through the porous media (a physical factor) on the biological structure (microbial community in the porous media) was assessed. The results of this investigation contribute to the bioremediation of contaminated groundwater understanding with new insights on the importance of physical transport factors on the biodegradation potential. For example, flow velocity is shown to have an important effect on the degradation potential of chlorinated ethenes. Additionally, the mathematical model and numerical tools have potential application to many other reactive transport problems, including: adsorption onto activated carbon, reaction in packed beds of catalyst, chemical transport in streambeds, and separation in chromatographic columns.

Contamination of surface and ground water has emerged as one of the most important environmental issues in developed and developing countries. Bioremediation of groundwater takes advantage of bacteria present in the environment to transform toxic compounds to non-toxic metabolites. This biotechnology holds the potential for fast, inexpensive, and effective water decontamination. However, it is still poorly understood and usually not fully controlled due to the lack of information describing the natural phenomena involved. Therefore, a better understanding of the phenomena involved during bioremediation of groundwater could help in the design and implementation of more efficient technologies. The main objective of the present research is to assess how pore-scale physical factors, such as pore-scale velocity, affect the degradation potential of contaminants during transport in groundwater. The target chemicals studied were chlorinated ethenes because they are commonly found in contaminated groundwater sites. To achieve the research objective, the following were employed: a mathematical model that links pore scale processes to the macro-scale representation of contaminant transport; development of numerical tools to solve the mathematical model; and experimental elucidation of the influence of pore-scale flow velocity on the biodegradation of contaminants using column experiments. Results from the mathematical model and experiments were used to elucidate the inter-relationship between physical and biological phenomena at the micro scale. The influence of flow velocity through the porous media (a physical factor) on the biological structure (microbial community in the porous media) was assessed. The results of this investigation contribute to the bioremediation of contaminated groundwater understanding with new insights on the importance of physical transport factors on the biodegradation potential. For example, flow velocity is shown to have an important effect on the degradation potential of chlorinated ethenes. Additionally, the mathematical model and numerical tools have potential application to many other reactive transport problems, including: adsorption onto activated carbon, reaction in packed beds of catalyst, chemical transport in streambeds, and separation in chromatographic columns.

In the light of increasing demand and diminishing supplies a sustainable urban water management for Melbourne and other cities will need to include water recycling and reuse of reclaimed water and stormwater. One key issue in stormwater reuse is the need for storage between times of collection until times of demand. Aquifer storage and recovery (ASR) would be a valuable option as it has limited space requirements and restricts loss from evaporation. However, stormwater commonly contains elevated levels of heavy metals, of which Zn and Cu are the most mobile. Stormwater also contains suspended solids, organic carbon, oxygen and nutrients, which influence the behaviour of injected metals and induce geochemical changes in the aquifer. While stormwater ASR has been practiced in limestone aquifers in South Australia, field data for sandy aquifers, which are more prevalent around Melbourne, are very limited. Risk assessment regarding the potential impact of stormwater ASR on the quality of the aquifer and groundwater resources in sandy aquifer is therefore necessary. After a characterisation of stormwater from different Melbourne catchments confirmed comparatively high concentrations of Zn and Cu in stormwater, three siliceous aquifer sediments were used in a series of batch sorption experiments as well as column experiments imitating one ASR cycle to assess the impact of different parameters on Zn and Cu behaviour. The reactive geochemical transport model PHT3D was then modified to simulate experimental results with the outlook that it could be used as a predictive tool for long term evaluation. The study showed that Zn adsorption was limited and desorption of large fractions occurred, indicating that injected amounts of Zn are mobile and would mainly be recovered. In contrast, Cu adsorption was higher and desorption was limited, indicating that injected amounts of Cu would mainly accumulate in the aquifer. The release of metals was triggered by reduction in pH, increase in ionic strength and particle mobilisation. Metal concentrations were also increased after storage phases, while minor sediment constituents, especially organic matter, significantly reduce metal mobility. The different role of dissolved and solid organic carbon is critical in understanding Cu behaviour during stormwater ASR. Pretreatment of stormwater to reduce the injection of colloids, organic carbon and metals are recommended to limit metal accumulation in the subsurface. Monitoring of water quality throughout the ASR cycle would be encouraged to validate the current findings with field data. Special attention should be paid to backflushed water quality to ensure correct disposal.

Explosives used in the mining industry release nitrate into the environment, causing concerns for the water quality in local river-systems. One way of reducing the nitrate loading into the environment is through a woodchip bioreactor. Water is passed through the bioreactor, where denitrifying microbial communities use the organic carbon from the substrate for energy, together with the nitrate. The efficiency of the denitrification process depends on various factors, including the type of carbon source selected and the temperature. To determine a suitable organic substrate to use in colder environments, column experiments were conducted, comparing different woodchip types. Three columns contained woodchips from pine, spruce and birch. In the fourth column, barley wheat was mixed with pine woodchips. An influent solution was pumped into the columns contained 50 mg/L nitrate-nitrogen. The effluent water was sampled and analysed twice per week for nitrate, nitrite and ammonium concentrations. The pH and alkalinity were analysed weekly to determine that denitrification was taking place. Three column conditions were tested. During the initial period, the columns were kept in 21 °C with a hydraulic residence time (HRT) of 6.3 days. In the following period, the columns were refrigerated at a temperature of 5°C. During the final period, the HRT was lowered to 3.2 days. After a 106-day runtime, it could be concluded that pine woodchips were the most effective substrate for denitrification in 5 °C temperature. The column with pine woodchips removed nitrate efficiently and produced the least amount of by-products and released DOC with a short HRT. The pine woodchips and barley straw column had high nitrite accumulation, and the nitrate removal rate in the birch and spruce woodchip columns was low in 5 °C conditions. / Sprängmedel som används inom gruvindustrin släpper ut nitrat i miljön, vilket kan leda till problem med vattenkvaliteten i lokala vattensystem. Ett sätt att reducera mängden nitrat som släpps ut är genom en bioreaktor med träflis. Vatten passeras genom bioreaktorn, där denitrifierande microbakteriella grupper använder det organiska kolet från substratet för energi, tillsammans med nitratet. Effektiviteten av den denitrifierande processen beror på flertalet faktorer, däribland vilken sorts kolkälla som valts ut och vilken temperatur bioreaktorn håller. För att identifiera ett bra organiskt substrat att använda i kallt klimat genomfördes ett kolumnexperiment som jämförde olika sorters träflis. Tre kolonner innehöll träflis från tall, gran och björk. I en fjärde kolonn blandades kornhalm med träflis från tall. En lösning med koncentrationen 50 mg/L kväve i form av nitrat pumpades in i kolonnerna. Utloppsvattnet från de fyra kolonnerna analyserades två gånger per vecka för koncentration av nitrat, nitrit och ammonium. pH och alkalinitet analyserades varje vecka för att se att denitrifikation skedde. Tre olika förutsättningar testades i kolonnerna. I den första perioden hölls kolonnerna i 21 °C med en hydraulisk uppehållstid på 6,3 dagar. I den följande perioden kyldes kolonnerna till 5 °C. I den sista perioden sänktes uppehållstiden till 3,2 dagar. Efter 106 dagar gick det att fastställa att tall-träflisen var det mest effektiva substratet för denitrifikation i 5 °C. Kolonnen med träflis från tall sänkte nitrathalten i vattnet och producerade minst biprodukter, samt frigjorde organiskt kol även vid kort uppehållstid. Kolonnen med tallflis och kornhalm ackumulerade mycket nitrit, och kolonnerna med träflis från björk och gran hade låga nivåer av nitrat-rening när temperaturen sänktes till 5 °C.

It is fundamental to investigate the biodegradability of chemicals and their potential (eco)toxicological effects under near-environmental conditions in order to identify and thereby avoid potential risks to humans, animals and the environment in the event of their release. Established as a policy object at the European level, the risks, which are posed by anthropogenic pollution, ideally need to be reduced to a minimum, if not eliminated completely, in the near future. To achieve this goal, an assessment of chemicals, based on international consensus, is required, which builds on the results of standardized experiments and is constantly supplemented by computer-based approaches. Establishing structure-property relationships is one way to immediately classify organic trace substances as ‘degradable’, or ‘potentially persistent’, as well as as hormonally ‘active’ or ‘inactive’. The extent to which these relationships are applicable to the substance group of benzophenone-type UV filters was investigated in this work. Some derivatives, which only differ in the type and position of their substituents on the aromatic rings, are suspected of acting as endocrine disruptors. Despite the high probability of them being released into the environment, and the toxicologically relevant properties, there are no mechanistic degradation studies so far that take enough derivatives into consideration to discuss the substitution pattern as a possible influential factor. To close the identified gaps, experiments on primary as well as ultimate degradation were carried out with up to ten different benzophenones, changing various parameters and adapting the experimental setup. Studies on the complete mineralizability, compliant with the standardized OECD Guideline No. 301F, showed that the respective substitution pattern is a decisive factor, while the mere presence of certain functional groups plays a minor role. To yield additional information on the time-dependent formation of primary degradation products, an LC-MS/MS method was developed that served to quantify benzophenones in various environmental matrices during a monitoring campaign, in addition to tracking primary degradation at the laboratory scale. The detection of 4-hydroxybenzophenone, which meets the structural criteria for multi-hormonal effects and was identified as a microbial degradation product of benzophenone, confirmed that the formation of transformation products needs to be given greater consideration in relation to toxicological issues. On this evidence, the structure-dependent endocrine effects of benzophenone-type UV filters, the transformation product 4-hydroxybenzophenone, and three other degradation products were determined using recombinant yeast-based reporter gene assays. Hydroxyl groups are the prevalent substituents of benzophenone-type UV filters, and the ruling structural elements, which influence microbial biodegradation and endocrine activity. Their investigation revealed a new fundamental but unexpected relationship: Primary degradation can slow down further degradation through the incorporation of hydroxyl groups. This simultaneously increases the risk of a formation of estrogen-active transformation products. This aspect underlines the need to include the occurrence of transformation products, especially under realistic conditions, in the overall risk assessment of chemicals. In this context, the application of quantitative structure-activity relationships (QSAR) plays a crucial role and, the suitability thereof was verified in this work – focusing on benzophenones. The empirically proven relationship between substitution pattern and degradability helps to improve the reliability of QSAR models for benzophenones as well as for structurally similar compounds, and forms the basis for further studies of this specific relationship at the enzymatic level.:DECLARATION OF CONFORMITY DECLARATION OF INDEPENDENT WORK PREFACE ACKNOWLEDGMENT KURZFASSUNG ABSTRACT LIST OF ABBREVIATIONS AND ACRONYMS 1 CONTEXTUAL FRAMEWORK AND OBJECTIVES 2 STATE OF KNOWLEDGE ABOUT THE BIODEGRADATION OF BENZOPHENONES 2.1 INTRODUCTION 2.2 ENTRY PATHS INTO THE ENVIRONMENT AND HAZARDOUS EFFECTS 2.2.1 Environmental occurrence and possible routes of discharge 2.2.2 (Eco)toxicity and endocrine disrupting properties 2.3 BIODEGRADATION 2.3.1 Aerobic biotransformation 2.3.2 Anoxic/anaerobic biotransformation 2.3.3 Transformation mediated through fungi and higher organisms 2.4 PHOTOLYTIC TRANSFORMATION 2.5 CONCLUSIONS 3 TRACE ANALYSIS IN ENVIRONMENTAL SAMPLES AND THE ENDOCRINE EFFECTS 3.1 INTRODUCTION 3.2 MATERIAL AND METHODS 3.2.1 Chemicals and materials 3.2.2 LC-MS/MS method development 3.2.2.1 MS parameters 3.2.2.2 LC parameters 3.2.2.3 Sample preparation 3.2.2.4 Validation 3.2.2.5 Application of the method to environmental monitoring 3.2.3 Biodegradation 3.2.4 Yeast-based reporter gene assays 3.3 RESULTS AND DISCUSSION 3.3.1 LC-MS/MS method development 3.3.1.1 Sample preparation 3.3.1.2 Validation 3.3.1.3 Application of the method for environmental samples 3.3.2 Biodegradation 3.3.3 Endocrine activity 3.3.3.1 Estrogenic and antiestrogenic activities 3.3.3.2 Estrogenic activity during biotransformation 3.3.3.3 Androgenic and antiandrogenic activities 3.4 CONCLUSION 4 PRIMARY AND ULTIMATE DEGRADATION 4.1 INTRODUCTION 4.2 MATERIAL AND METHODS 4.2.1 Chemicals and materials 4.2.2 Primary degradation 4.2.2.1 Abiotic river water 4.2.2.2 Biotic river water 4.2.2.3 Suboxic river water 4.2.2.4 River water amended with mineral solution 4.2.3 Ready biodegradability 4.2.4 Column experiments 4.2.5 Docking studies 4.2.6 LC-MS/MS Analysis 4.3 RESULTS AND DISCUSSION 4.3.1 Primary degradation 4.3.1.1 Abiotic river water 4.3.1.2 Biotic river water 4.3.1.3 Suboxic river water 4.3.1.4 River water amended with mineral solution 4.3.2 Ready biodegradability 4.3.3 Column experiments 4.3.3.1 Breakthrough curves and pretests 4.3.3.2 Removal tests 4.3.4 Structure-biodegradability relationships 4.4 CONCLUSIONS 5 SYNTHESIS 5.1 SUMMARIZING DISCUSSION 5.2 COMPARISON TO IN SILICO RESULTS 5.2.1 Biodegradability 5.2.2 Estrogenicity 5.3 CONCLUSION 6 APPENDIX 6.1 APPENDIX A 6.2 APPENDIX B 6.3 APPENDIX C 6.4 APPENDIX D 7 REFERENCES

The applicability and adequacy of three modeling approaches to describe and predict breakthough curves (BTCs) for non-reactive solutes in statistically homogeneous porous media were numerically and experimentally investigated. Modeling approaches were: the convection-dispersion equation (CDE) with scale-dependent dispersivity, mobile-immobile model (MIM), and the fractional convection-dispersion equation (FCDE). In order to test these modeling approaches, a prototype laboratory column system was designed for conducting miscible displacement experiments with a free-inlet boundary. Its performance and operating conditions were rigorously evaluated. When the CDE with scale-dependent dispersivity is solved numerically for generating a BTC at a given location, the scale-dependent dispersivity can be specified in several ways namely, local time-dependent dispersivity, average time-dependent dispersivity, apparent time-dependent dispersivity, apparent distance-dependent dispersivity, and local distance-dependent dispersivity. Theoretical analysis showed that, when dispersion was assumed to be a diffusion-like process, the scale-dependent dispersivity was locally time-dependent. In this case, definitions of the other dispersivities and relationships between them were directly or indirectly derived from local time-dependent dispersivity. Making choice between these dispersivities and relationships depended on the solute transport problem, solute transport conditions, level of accuracy of the calculated BTC, and computational efficiency The distribution of these scale-dependent dispersivities over scales could be described as either as a power-law function, hyperbolic function, log-power function, or as a new scale-dependent dispersivity function (termed as the LIC). The hyperbolic function and the LIC were two potentially applicable functions to adequately describe the scale dependent dispersivity distribution in statistically homogeneous porous media. All of the three modeling approaches described observed BTCs very well. The MIM was the only model that could explain the tailing phenomenon in the experimental BTCs. However, all of them could not accurately predict BTCs at other scales using parameters determined at one observed scale. For the MIM and the FCDE, the predictions might be acceptable only when the scale for prediction was very close to the observed scale. When the distribution of the dispersivity over a range of scales could be reasonably well-defined by observations, the CDE might be the best choice for predicting non-reactive solute transport in statistically homogeneous porous media. / Ph. D.

The number of hardened surfaces has increased as a result of urbanization, and thus also the amount of road stormwater. Road stormwater can transport pollutants that have been released on road areas to surrounding recipients. Two substances that are found in particularly high concentrations in road storm water are copper and zinc. At high concentrations of these substances, toxic effects occur which are particularly harmful to aquatic organisms. This report intends to investigate how well the filter material Polonite purifies road stormwater from copper and zinc. Polonite is a reactive filter material made of the sedimentary rock Opoka, which binds substances such as copper and zinc by adsorption. In this thesis, a laboratory experiment has been carried out where it has been investigated how well different amounts of Polonite adsorb copper and zinc during different time periods. The results show that the concentrations of copper and zinc generally decreased over time and with an increasing amount of Polonite. Furthermore, a simulation of how Polonite's purification capacity decreases over time has been created. The simulation showed that Polonite's ability to purify stormwater according to the guideline values ceases after 133 days for copper and 325 days for zinc. Data collected from a column experiment was then compared with the simulation. The comparison showed that the simulation for zinc was in good agreement with the data from the column experiment, while the data for copper were more different from the simulation.  Conclusions drawn are that Polonite can be a good solution for sustainable road stormwater management as it can purify zinc and copper in accordance with the recommended guideline values. The results also show that Polonite has a better ability to purify zinc than copper and that it can purify zinc for a longer period of time. Moreover, other aspects such as economics need to be investigated in future studies to establish with certainty that Polonite is a good solution for the purification of road stormwater in large-scale treatment plants. / Till följd av urbaniseringen ökar antalet hårdgjorda ytor, och därmed även mängden vägdagvatten. Vägdagvatten kan transportera föroreningar som uppkommit på vägområden till omgivande recipienter. Två ämnen som hittas i särskilt höga koncentrationer i vägdagvatten är koppar och zink.  Vid höga koncentrationer av dessa ämnen uppstår toxiska effekter som är särskilt skadliga för vattenlevande organismer. Denna rapport ämnar att undersöka hur väl filtermaterialet Polonite renar vägdagvatten från koppar och zink. Polonite är ett reaktivt filtermaterial som genom adsorption kan rena vägdagvatten. I detta arbete har en laboration utförts där det har undersökts hur väl olika mängder Polonite adsorberar koppar och zink under olika tidsperioder. Resultatet visar att halterna koppar och zink generellt minskar med tiden samt med ökande mängd Polonite. Vidare skapades en simulering av hur Polonites reningsförmåga minskar med tiden.  Slutsatser som dragits är att Polonite kan vara en god lösning för hållbar vägdagvattenhantering då det kan rena koppar och zink i enlighet med de rekommenderade riktvärdena. Resultatet visar även att Polonite har en bättre förmåga att rena zink än koppar samt att det kan rena zink under en längre tidsperiod. För att med säkerhet fastställa att Polonite är en bra lösning för rening av vägdagvatten i storskaliga reningsanläggningar behöver flera aspekter såsom ekonomi undersökas i framtida studier.

Ce travail vise à étudier le couplage entre écoulement et interactions physico-chimiques dans les sols, dans différentes conditions de saturation en eau, afin d’améliorer la prédiction du devenir des polluants. Il s’agit de comprendre en quoi le taux de saturation du milieu affecte la réactivité du sol vis-à-vis des polluants, et d’évaluer le pouvoir prédictif du transport de solutés réactifs étudié en milieu saturé sur la réactivité en conditions non saturées. Différents processus sont considérés : l’échange de cations calcium-zinc sur un milieu poreux modèle (sable-kaolinite), la sorption et désorption d’un composé organique sur une terre non contaminée, le transport de polluants prioritaires tels que les HAP sur une terre de friche industrielle. Dans chaque cas, des expériences en colonne de laboratoire ont été conduites en conditions d’écoulement saturé et non saturé permanent, permettant tout d’abord la caractérisation de l’hydrodynamique, puis l’étude du couplage avec la réactivité. Les courbes de percée obtenues ont été ensuite modélisées avec des codes tels que CXTFIT. On a montré l’influence de la teneur en eau du milieu sur le transport réactif, variable suivant le type de réaction considéré, la structure des milieux jouant également un rôle important. L’échange d’ions sur le milieu modèle n’est globalement pas affecté par la teneur en eau, dans une gamme proche de la saturation. En revanche, une plus forte sorption et une plus faible mobilisation des polluants organiques ont été observées en conditions non saturées. Le transport réactif de ces composés ne peut donc pas être prédit en conditions non saturées à partir de mesures en milieu saturé, qui peuvent surestimer le transport / The aim of this work was to study the link between water flow and physical and chemical interactions in soils under variably water flow conditions, in order to improve the prediction of contaminants fate. It deals with understanding how the porous media water content can modify soil reactivity towards contaminants, and assessing the possibility to predict reactivity under unsaturated conditions with reactive solute transport studied in saturated porous media. Various processes were considered: cations exchange calcium-zinc on a model porous media (sand-kaolinite), sorption and desorption of an organic compound on a non polluted soil, transport of priority contaminants such as PAHs on an industrial contaminated soil. In each case, experiments were carried out with soil columns at the laboratory scale under saturated and unsaturated steady-state flow conditions, in order to characterize at first hydrodynamics and then to study the link with reactivity. Modeling of the breakthrough curves was then performed with codes such as CXTFIT. We showed an influence of porous media water content on reactive transport which was different as a function of the interaction. Porous media structure must also be taken into account. Ions exchange on a model porous media was not globally modified by the water content varying in a range close to saturation. On the contrary, higher sorption and lower migration of organic contaminants were observed under unsaturated conditions. Reactive transport of these compounds cannot therefore be predicted under unsaturated conditions with tests performed on saturated porous media which may overestimate transport

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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.