The aim of this thesis was to investigate the impact of a direct oxygen injection as a potential remediation strategy for contaminated aquifers on a bench scale. The mass transfer between a multi-component trapped gas phase and a mobile water phase was studied. Column experiments with dynamically compressed sediments and a direct gas injection of pure oxygen gas were performed. In addition, a new developed kinetic multi-component model was used to describe the experiments. The amount of gas that could be captured in the pore space during direct oxygen injection and the time needed for a complete dissolution of the trapped gas phase were determined. Varying influences of different gases already dissolved in the mobile water phase on the dissolution process of a trapped oxygen gas phase were described for different flow regimes and confirmed by the model results. Finally, on the basis of the experimental and model results obtained in this thesis, predictions for an application of a direct oxygen injection in the field were discussed.

Contaminate transport in vadose is a huge concern since the vadose zone is the main passage way for ground water recharge. Understanding this process is crucial in order to prevent contamination, protect and rehabilitate ground water resources. Reactive transport models are instrumental for such purposes and there are numerous solute transport simulation programs for both ground water and vadose zone but most of this models are limited to simple Linear, Langmuir and Freundlich sorption models and first order decay and fail to simulate more complex geochemical reactions that are common in the vadose zone such as cation exchange, surface complexation, redox reaction and biodegradation. So it is necessary to enhance capabilities of solute transport models by incorporating well tested hydrogeochemical models like PHREEQC in to them to be able closely approximate the geochemical transport process in the subsurface. In this PhD research a new reactive transport model called VS2DRT was created by coupling existing public domain solute and heat transport models VS2DT, VS2DH with hydro-chemical model PHREEQC using non-iterative operator splitting technique. VS2DRT was compiled using MinGW compiler using tools like autotools and automake. A graphical user interface was also created using QT creator and Argus ONE numerical development tools. The new model was tested for one dimensional conservative Cl transport, surface complexation, cation exchange, dissolution of calcite and gypsum, heat and solute transport as well as for two dimensional cation exchange cases. Their results were compared with VS2DT, VS2DH, HP1 and HP2 models and the results are in good agreement.

Die Aufgabenstellung der vorliegenden Arbeit ergab sich aus der Notwendigkeit organische Schwefelverbindungen in stark belasteten wäßrigen Proben zu identifizieren, um das toxische Potential dieser Wässer abschätzen zu können. Bei der chromatographischen Trennung und Identifizierung der einzelnen Komponenten traten insbesondere dann Probleme auf, wenn die einzelnen Komponenten in Konzentrationsbereichen auftraten die um Größenordnungen differierten. Da auch durch selektive Detektion unbekannte Komponenten nicht direkt identifiziert werden können, wurde angestrebt durch geeignete Probenvorbereitungsschritte einerseits die gesuchten Zielsubstanzen anzureichern und andererseits störende Matrixbestandteile abzutrennen. Ziel der vorliegenden Arbeit war es effektive und möglichst selektive Verfahren zu entwickeln, um organische Schwefelverbindungen aus wäßrigen Proben anzureichern. Im Rahmen dieser Arbeit wurden zwei Möglichkeiten erarbeitet. Für die Anreicherung von leicht- bis mittelflüchtigen Substanzen erwies sich die Adsorption an Ag2S aus der Gasphase als geeignet. Zur Extraktion mittel- bis schwerflüchtiger Verbindungen wurde eine Festphasenextraktionstechnik an einem mit Blei(II)ionen modifizierten Kationenaustauschermaterial entwickelt. Ein Vergleich beider Techniken erfolgte mit dem Verfahren der Festphasenmikroextraktion (SPME). Die adsorptive Anreicherung an Ag2S wurde mit einem Membranextraktionsschritt (ME) , Thermodesorption (TD) und GC/MS gekoppelt. Wie die SPME kann sie für den Nachweis leicht- bis mittelflüchtiger Verbindungen aus flüssigen, festen und gasförmigen Proben eingesetzt werden. Gegenüber der Festphasenmikroextraktion ermöglicht sie den Einsatz größerer Probemengen, was in niedrigeren Nachweisgrenzen (oberer bis mittlerer ng/l-Bereich) resultiert. Nachteile der entwickelten Technik bilden der höhere experimentelle Aufwand und die längeren Analysenzeiten. Das Festphasenextraktionsverfahren an dem mit Pb(II)ionen beladenen Kationenaustauschermaterial erlaubt gegenüber der SPME ebenfalls die Anwendung größerer Probenmengen und höherer Konzentrationen. Beide Verfahren zeigen vergleichbare Nachweisgrenzen (unterer µg/l - bis oberer ng/l-Bereich) für die verwendeten Modellsubstanzen. Sowohl durch die adsorptive Anreicherung an Silbersulfid als auch durch die Festphasenextraktion an Pb(II)-modifizierten Ionenaustauschmaterialien wird die Identifizierung unbekannter organischer Schwefelverbindungen in stark belasteten Proben erheblich erleichtert. Beide Methoden bilden als einfache und leistungsfähige Techniken wirkungsvolle Ergänzungen zu bereits etablierten Anreicherungsverfahren. Neben der Identifizierung und Analyse können die Techniken ebenfalls zur Entfernung von schwefelhaltigen Substanzen aus verschiedenen Matrizes dienen. Anwendungsmöglichkeiten der entwickelten Methoden bestehen neben der Umweltanalytik auch in der Lebensmittelchemie.

This study focuses on the environmental impact assessment of trace elements concentrations in spent shale, which is the main residual besides gas and steam from the utilization of oil shale. The study area El-Lajjun covers 28 km2, located in the centre of Jordan approximately 110 km south of Amman. It belongs mainly to the Wadi Mujib catchment and is considered to be one of the most important catchments in Jordan. The Wadi El-Lajjun catchment area (370 km2) consists of two main aquifer systems: The intermediate aquifer (Amman Wadi As Sir Aquifer or B2/A7) and the deep sandstone aquifer (Kurnub/Ram Group Aquifer). The B2/A7 aquifer (Upper Cretaceous) is considered as the main source of fresh water in Jordan. El-Lajjun oil shale was deposited in a sedimentary basin and comprises massive beds of brown-black, kerogen-rich, bituminous chalky marl. The oil shale was deposited in shallow marine environment. It is by definition a sedimentary rock containing organic material in the rock matrix. The shale oil extraction is an industrial process to decompose oil shale and to convert the kerogen into shale oil by hydrogenation, pyrolysis or by a thermal dissolution. Several classifications of extraction technologies are known; the classification with respect to the location where the extraction takes place distinguishes between off-site, on-site, and in situ. The oil shale utilization may have serious repercussions on the surrounding environment if these issues are not investigated and evaluated carefully. Ten representative oil shale rock samples with a total weight about 20 kg were collected from different localities of oil shale exposures in the study area. A standardized laboratory Fischer Assay test was performed with the samples to determine oil shale characteristics and to obtain spent shale, which was used in this study for further investigations. Sequential extraction was used to evaluate the changes in the mobility and distribution of the trace elements: Ti, V Cr, Co, Zn, As Zr, Cd, Pb and U. Column leaching experiments were performed to simulate the leaching behavior of the above elements from oil shale and spent shale to evaluate the possible influence on the groundwater in the study area. The concentrations in the leachate were below the maximum contaminant levels of the Environmental Protection Agency (EPA) for drinking water and the Jordanian standards for drinking water. An immobilization method by using Kaolin was applied to reduce the mobilization and bioavailability of the trace elements fraction that are contained in the spent shale. Immobilization was evaluated as a function of liquid-solid ratio (solid-liquid partitioning) and as a function of pH. A comparison between the results obtained from column leaching experiments and the results that were obtained from immobilization for the oil shale and spent shale samples indicated that the immobilization reduced the mobility of the trace element except for Ti, V, and Cr. However, even the concentrations of these elements were lower than the maximum acceptable limits of the Jordanian Standard Specifications for waste water. The catchment of the study area (Wadi El-Lajjun catchment) is ungauged. Therefore, the soil conservation service (SCS) runoff curve number method was used for predicting direct runoff from rainfall. The results obtained showed that the infiltration of water is very small (approximately 0.6 cm/year) and rarely can´t reach the groundwater through the oil shale beds. Thus, a contamination of groundwater is unlikely under normal conditions. DRASTIC was used to assess groundwater vulnerability for the B2/A7 aquifer with respect to pollution by oil shale utilization. The aquifer vulnerability map shows that the area is divided into three zones: low (risk index 10-100; intermediate (risk index 101–140) and high groundwater vulnerability (risk index 141-200). The high risk areas are small and mainly located in the northeastern corner of the El-Lajjun graben, where the hydraulic conductivity is relatively high and rocks are highly fractured and faulted. The water table of the deep sandstone aquifer (Kurnub/Ram group) in the El-Lajjun area is relatively deep. At least two geological formations above the Kurnub aquifer are aquitards and protect the deep aquifer. However, the area is highly fractured and thus there is a certain possibility for contact with surface pollutants. Finally, further research with respect to trace elements including REE elements and isotopes in the intermediate and deep sandstone aquifers are highly recommended. Isotopic signatures will be very helpful to investigate to which extend hydraulic connections between the aquifers exist. Further and in particular mineralogical studies on the spent shale and the possibilities for industrial utilization are recommended because huge quantities of spent shale are expected. Because most oil shale extraction technologies especially the power generation require considerable amounts of water detailed studies on water supply for the oil shale treatment have to be performed.

This study focuses on the environmental impact assessment of trace elements concentrations in spent shale, which is the main residual besides gas and steam from the utilization of oil shale. The study area El-Lajjun covers 28 km2, located in the centre of Jordan approximately 110 km south of Amman. It belongs mainly to the Wadi Mujib catchment and is considered to be one of the most important catchments in Jordan. The Wadi El-Lajjun catchment area (370 km2) consists of two main aquifer systems: The intermediate aquifer (Amman Wadi As Sir Aquifer or B2/A7) and the deep sandstone aquifer (Kurnub/Ram Group Aquifer). The B2/A7 aquifer (Upper Cretaceous) is considered as the main source of fresh water in Jordan. El-Lajjun oil shale was deposited in a sedimentary basin and comprises massive beds of brown-black, kerogen-rich, bituminous chalky marl. The oil shale was deposited in shallow marine environment. It is by definition a sedimentary rock containing organic material in the rock matrix. The shale oil extraction is an industrial process to decompose oil shale and to convert the kerogen into shale oil by hydrogenation, pyrolysis or by a thermal dissolution. Several classifications of extraction technologies are known; the classification with respect to the location where the extraction takes place distinguishes between off-site, on-site, and in situ. The oil shale utilization may have serious repercussions on the surrounding environment if these issues are not investigated and evaluated carefully. Ten representative oil shale rock samples with a total weight about 20 kg were collected from different localities of oil shale exposures in the study area. A standardized laboratory Fischer Assay test was performed with the samples to determine oil shale characteristics and to obtain spent shale, which was used in this study for further investigations. Sequential extraction was used to evaluate the changes in the mobility and distribution of the trace elements: Ti, V Cr, Co, Zn, As Zr, Cd, Pb and U. Column leaching experiments were performed to simulate the leaching behavior of the above elements from oil shale and spent shale to evaluate the possible influence on the groundwater in the study area. The concentrations in the leachate were below the maximum contaminant levels of the Environmental Protection Agency (EPA) for drinking water and the Jordanian standards for drinking water. An immobilization method by using Kaolin was applied to reduce the mobilization and bioavailability of the trace elements fraction that are contained in the spent shale. Immobilization was evaluated as a function of liquid-solid ratio (solid-liquid partitioning) and as a function of pH. A comparison between the results obtained from column leaching experiments and the results that were obtained from immobilization for the oil shale and spent shale samples indicated that the immobilization reduced the mobility of the trace element except for Ti, V, and Cr. However, even the concentrations of these elements were lower than the maximum acceptable limits of the Jordanian Standard Specifications for waste water. The catchment of the study area (Wadi El-Lajjun catchment) is ungauged. Therefore, the soil conservation service (SCS) runoff curve number method was used for predicting direct runoff from rainfall. The results obtained showed that the infiltration of water is very small (approximately 0.6 cm/year) and rarely can´t reach the groundwater through the oil shale beds. Thus, a contamination of groundwater is unlikely under normal conditions. DRASTIC was used to assess groundwater vulnerability for the B2/A7 aquifer with respect to pollution by oil shale utilization. The aquifer vulnerability map shows that the area is divided into three zones: low (risk index 10-100; intermediate (risk index 101–140) and high groundwater vulnerability (risk index 141-200). The high risk areas are small and mainly located in the northeastern corner of the El-Lajjun graben, where the hydraulic conductivity is relatively high and rocks are highly fractured and faulted. The water table of the deep sandstone aquifer (Kurnub/Ram group) in the El-Lajjun area is relatively deep. At least two geological formations above the Kurnub aquifer are aquitards and protect the deep aquifer. However, the area is highly fractured and thus there is a certain possibility for contact with surface pollutants. Finally, further research with respect to trace elements including REE elements and isotopes in the intermediate and deep sandstone aquifers are highly recommended. Isotopic signatures will be very helpful to investigate to which extend hydraulic connections between the aquifers exist. Further and in particular mineralogical studies on the spent shale and the possibilities for industrial utilization are recommended because huge quantities of spent shale are expected. Because most oil shale extraction technologies especially the power generation require considerable amounts of water detailed studies on water supply for the oil shale treatment have to be performed.

Environmental pollution has become a global concern as consequence of industrializa-tion and urbanization. The ongoing subsurface contamination by dense non-aqueous phase liquids (DNAPLs) bears tremendous hazardous potential for humans and ecosys-tems including aquifer systems. Intended or accidental spill events have led to a vast number of registered sites affected by DNAPL type chemicals. Despite the existence of novel techniques for their exploration, characterization and remediation, economical constraints often limit efforts for risk prevention or reduction, so that information and data to characterize highly complex DNAPL contamination scenarios are often insuffi-cient and compensated by natural attenuation of groundwater-dissolved contaminant plumes. Especially, knowledge on the DNAPL source zone geometry (SZG) and source zone formation are critically required yet very scarce. Against the previously stated background, this cumulative doctoral dissertation critically examined the processes of DNAPL source zone formation at laboratory scale. A comprehensive literature review identified current limitations and open research questions in the latter research field, revealing evidence for the relevance of SZG for plume response at different scales. Giv-en only a limited number of published studies related to DNAPL source zone formation, two simplified experimental setups mimicking source zone formation in an initially fully water-saturated aquifer were developed and intensively tested. The performance of aqueous and non-wetting phase dyes was evaluated for DNAPL release into three non-consolidated porous media using reflective optical imaging in combination with a cus-tom-made image processing and analysis (IPA) framework. The latter suite allowed for the generation of physically plausible DNAPL saturation distributions with determinable level of uncertainty. Then, a limited number of DNAPL release experiments were per-formed under controlled ambient as well as with boundary and initial conditions to generate robust observation data, while further adopting the IPA framework. The latter data was introduced into a numerical multiphase flow model. While most system pa-rameters could be directly determined, the parameters defining the capillary pressure-saturation and relative permeability-saturation retention curves were inversely deline-ated through a classical Monte Carlo analysis. Overall, the successfully calibrated nu-merical setup mimicking the transient DNAPL source zone formation allowed to quanti-fy uncertainties related to the experiment, IPA framework and model setup configura-tion. In addition, a number of new research questions pointing towards future im-provements of laboratory-scale methodologies to understand DNAPL contamination were derived. Especially in light of numerous existing contaminated sites with unclear history and even more vague future, given by potential impacts through climate change and anthropogenic activity, an increasing need for sophisticated strategies to better un-derstand DNAPL contamination and to reduce hazard potential is expected.:Statement I List of publications II Abstract VI Acknowledgements and funding information IX List of figures XIII List of tables XIV Abbreviations and symbols used in the main text XV 1 Introduction and background 1-1 1.1 Motivation of this thesis 1-1 1.2 Incorporation of this thesis in research projects 1-4 1.3 Definition of objectives and workflow strategy of this thesis 1-5 1.4 Formal structure of this thesis 1-11 2 Existing knowledge on DNAPL contamination 2-1 3 Fundamentals of DNAPL migration in porous media 3-1 3.1 Basic concepts for multiphase flow in porous media 3-1 3.2 Capillary pressure-saturation correlation 3-3 3.3 Relative permeability-saturation correlation 3-5 3.4 Balance equations for laminar fluid phase flow in porous media 3-7 4 Core research complex A : Development of a framework for the semi-automatized generation of DNAPL saturation distribution observation data 4-1 5 Core research complex B : Experimental and model-based simulation of DNAPL source zone formation 5-1 6 Summary and conclusions 6-1 6.1 Summary of perceptions for each main section of this thesis 6-1 6.2 New research questions with regard to DNAPL source zone formation at the laboratory scale 6-5 6.3 General recommendations for future works related to DNAPL contamination 6-8 References Ref-1 Appendix I : ENGELMANN ET AL. (2019a) App I-1 Published journal article App I-1 Appendix II : ENGELMANN ET AL. (2019b) App II-1 Published journal article App II-1 Electronic Supplementary Material 1 : Unprocessed raw TIFF format images used for IPA frame-work evaluation App II-26 Electronic Supplementary Material 2 : Sensitivities for color model change and binary conversion algorithms App II-36 Electronic Supplementary Material 3 :Relevance of spatially non-uniform illumination correction and background exclusion App II-76 Appendix III : ENGELMANN ET AL. (2021) App III-1 Published journal article App III-1 Electronic Supplementary Material 1 : Unprocessed raw TIFF format images for IPA framework ap-plication App III-30 Electronic Supplementary Material 2 : Processed images with all intermediate steps of IPA frame-work application App III-58 Electronic Supplementary Material 3 : IPA fitness App III-86 Electronic Supplementary Material 4 : Partial objective functions App III-87 Electronic Supplementary Material 5 : Model verification App III-93

Die Aufgabenstellung der vorliegenden Arbeit ergab sich aus der Notwendigkeit organische Schwefelverbindungen in stark belasteten wäßrigen Proben zu identifizieren, um das toxische Potential dieser Wässer abschätzen zu können. Bei der chromatographischen Trennung und Identifizierung der einzelnen Komponenten traten insbesondere dann Probleme auf, wenn die einzelnen Komponenten in Konzentrationsbereichen auftraten die um Größenordnungen differierten. Da auch durch selektive Detektion unbekannte Komponenten nicht direkt identifiziert werden können, wurde angestrebt durch geeignete Probenvorbereitungsschritte einerseits die gesuchten Zielsubstanzen anzureichern und andererseits störende Matrixbestandteile abzutrennen. Ziel der vorliegenden Arbeit war es effektive und möglichst selektive Verfahren zu entwickeln, um organische Schwefelverbindungen aus wäßrigen Proben anzureichern. Im Rahmen dieser Arbeit wurden zwei Möglichkeiten erarbeitet. Für die Anreicherung von leicht- bis mittelflüchtigen Substanzen erwies sich die Adsorption an Ag2S aus der Gasphase als geeignet. Zur Extraktion mittel- bis schwerflüchtiger Verbindungen wurde eine Festphasenextraktionstechnik an einem mit Blei(II)ionen modifizierten Kationenaustauschermaterial entwickelt. Ein Vergleich beider Techniken erfolgte mit dem Verfahren der Festphasenmikroextraktion (SPME). Die adsorptive Anreicherung an Ag2S wurde mit einem Membranextraktionsschritt (ME) , Thermodesorption (TD) und GC/MS gekoppelt. Wie die SPME kann sie für den Nachweis leicht- bis mittelflüchtiger Verbindungen aus flüssigen, festen und gasförmigen Proben eingesetzt werden. Gegenüber der Festphasenmikroextraktion ermöglicht sie den Einsatz größerer Probemengen, was in niedrigeren Nachweisgrenzen (oberer bis mittlerer ng/l-Bereich) resultiert. Nachteile der entwickelten Technik bilden der höhere experimentelle Aufwand und die längeren Analysenzeiten. Das Festphasenextraktionsverfahren an dem mit Pb(II)ionen beladenen Kationenaustauschermaterial erlaubt gegenüber der SPME ebenfalls die Anwendung größerer Probenmengen und höherer Konzentrationen. Beide Verfahren zeigen vergleichbare Nachweisgrenzen (unterer µg/l - bis oberer ng/l-Bereich) für die verwendeten Modellsubstanzen. Sowohl durch die adsorptive Anreicherung an Silbersulfid als auch durch die Festphasenextraktion an Pb(II)-modifizierten Ionenaustauschmaterialien wird die Identifizierung unbekannter organischer Schwefelverbindungen in stark belasteten Proben erheblich erleichtert. Beide Methoden bilden als einfache und leistungsfähige Techniken wirkungsvolle Ergänzungen zu bereits etablierten Anreicherungsverfahren. Neben der Identifizierung und Analyse können die Techniken ebenfalls zur Entfernung von schwefelhaltigen Substanzen aus verschiedenen Matrizes dienen. Anwendungsmöglichkeiten der entwickelten Methoden bestehen neben der Umweltanalytik auch in der Lebensmittelchemie.

Die Arbeit besteht aus mehreren Studien zur Quantifizierung des Grundwasserstroms in Seen (Exfiltration; engl.: lacustrine groundwater discharge, LGD) und damit verbundener Nährstoffeinträge. In zwei einleitenden Kapiteln dieser Arbeit werden eine Gründe für die Vernachlässigung der Grundwasserexfiltration (LGD) in Seen und der daran gekoppelten Nährstoffeinträge identifiziert. Diese Literaturstudien fassen den aktuellen Kenntnisstand zum Einfluss des Grundwassers auf die Hydrologie von Seen und ihre Nährstoffhaushalte zusammen. Den Kern der vorliegenden Arbeit bilden zwei empirische Studien, die sich mit der Quantifizierung der grundwasserbürtigen Phosphor (P)-Fracht in den Arendsee in Deutschland befassen. Das Gesamtvolumen des Grundwasserzustroms wird basierend auf der Grundwasserneubildung im Einzugsgebiet des Sees ermittelt. Lokale Muster der Grundwasserexfiltration werden anhand von Temperaturtiefenprofilen des Seesediments bestimmt. Eine Kombination der Ergebnisse ermöglicht es, die quantitativen Daten mit lokalen Informationen zu unterstützen. Die Untersuchung der Grundwasserqualität zeigt, dass die P-Konzentrationen im Grundwasser im besiedelten Bereich teilweise stark erhöht sind. Als Konsequenz daraus haben die grundwasserbürtigen P-Frachten einen Anteil von mehr als 50% an der gesamten externen P-Last des Arendsees. Das Grundwasser ist damit eine maßgebliche Ursache für die Eutrophierung des Gewässers. Drei weitere Studien widmen sich der Entwicklung und Optimierung von Ansätzen zur qualitativen und quantitativen Bestimmung der Grundwasserexfiltration in Seen. Die kritische Auseinandersetzung mit den Ergebnissen der Studien zeigt die Notwendigkeit weiterer Forschung zur Verbesserung und Standardisierung der Methoden zur Bestimmung von LGD und damit verbundenen Stofftransporten auf. Der Fall des Arendsees sollte alle, Wissenschaftler und Praktiker, dazu motivieren, das Grundwasser als relevante Eutrophierungsquelle in Betracht zu ziehen. / The present work is a collection of studies on lacustrine groundwater discharge (LGD) and groundwater-borne phosphorus (P) loads. For a number of reasons, groundwater exfiltration (i.e., LGD) is often not considered in water and nutrient budgets of lakes. This is also and especially true for P which was often regarded to be immobile in groundwater until recently. Two chapters review the scientific literature regarding the impacts of groundwater on hydrology and nutrient budgets of lakes, respectively. They present mechanisms and processes of LGD as well as techniques and methods to measure LGD and related nutrient transports. Moreover, numbers of LGD volumes and loads reported in literature are presented. The core of the present work is represented by two case studies dealing with the quantification of P loads from LGD to a lake in Germany. A combination of different methods is applied to overcome the problem of quantitative large scale LGD determination without losing local spatial information. P concentrations in groundwater and LGD are investigated by detailed spatial water sampling. The results reveal that P is actually present in concentrations far above natural background concentrations in the urban groundwater. LGD-derived P loads account for more than 50% of the overall external P loads to the lake and by that contribute significantly to lake eutrophication. Three further studies are devoted to the development and improvement of approaches to determine LGD. Critical reviews of the above mentioned studies reveal the need for further research in order to standardize and improve methods for LGD and mass load determination. It is found that the appropriate method for LGD determination depends on the spatial scale of interest. The identification of P introduced by LGD as a main driver of lake eutrophication is an important finding which should encourage scientists, policy makers, and lake managers to consider groundwater as a relevant P source for lakes.