Stoffumsatzreaktionen und hydraulische Prozesse im Boden und Grundwasser können in Tieflandeinzugsgebieten zu einer Nitratretention führen. Die Untersuchung dieser Prozesse in Raum und Zeit kann mit Hilfe geeigneter Modelle erfolgen. Ziele dieser Arbeit sind: i) die Entwicklung eines geeigneten Modellansatzes durch Kombination von Teilmodellen zur Simulation des N-Transportes im Boden und Grundwasser von Tieflandeinzugsgebieten und ii) die Untersuchung von Wechselwirkungen zwischen Gebietseigenschaften und N-Transport unter besonderer Berücksichtigung der potentiellen N-Zufuhr in die Oberflächengewässer. <br /> <br /> Der Modellansatz basiert auf der Kombination verschiedener Teilmodelle: das Bodenwasser- und -stickstoffmodell mRISK-N, das Grundwassermodell MODFLOW und das Stofftransportmodell RT3D. Zur Untersuchung der Wechselwirkungen mit den Gebietseigenschaften muss die Verteilung und Verfügbarkeit von Reaktionspartnern berücksichtigt werden. Dazu wurde ein Reaktionsmodul entwickelt, welches chemische Prozesse im Grundwasser simuliert. Hierzu gehören die Mineralisation organischer Substanz durch Sauerstoff, Nitrat und Sulfat sowie die Pyritoxidation durch Sauerstoff und Nitrat. Der Modellansatz wurde in verschiedenen Einzelstudien angewandt, wobei jeweils bestimmte Teilmodelle im Vordergrund stehen. Alle Modellstudien basieren auf Daten aus dem Schaugrabeneinzugsgebiet (ca. 25 km&#178;), in der Nähe von Osterburg(Altmark) im Norden Sachsen-Anhalts. <br /> <br /> Die folgenden Einzelstudien wurden durchgeführt: i) Evaluation des Bodenmodells anhand von Lysimeterdaten, ii) Modellierung eines Tracerexperimentes im Feldmaßstab als eine erste Anwendung des Reaktionsmoduls, iii) Untersuchung hydraulisch-chemischer Wechselwirkungen an einem 2D-Grundwassertransekt, iv) Flächenverteilte Modellierung von Grundwasserneubildung und Bodenstickstoffaustrag im Untersuchungsgebiet als Eingangsdaten für nachfolgende Grundwassersimulationen, und v) Untersuchung der Ausbreitung von Nitrat im Grundwasser und des Durchbruchs in die Oberflächengewässer im Untersuchungsgebiet auf Basis einer 3D-Modellierung von Grundwasserströmung und reaktivem Stofftransport. <br /> <br /> Die Modellstudien zeigen, dass der Modellansatz geeignet ist, die Wechselwirkungen zwischen Stofftransport und &ndash;umsatz und den hydraulisch-chemischen Gebietseigenschaften zu modellieren. Die Ausbreitung von Nitrat im Sediment wird wesentlich von der Verfügbarkeit reaktiver Substanzen sowie der Verweilzeit im Grundwasserleiter bestimmt. Bei der Simulation des Untersuchungsgebietes wurde erst nach 70 Jahren eine der gegebenen Eintragssitutation entsprechende Nitratkonzentration im Grundwasserzustrom zum Grabensystem erreicht (konservativer Transport). Die Berücksichtigung von reaktivem Stofftransport führt zu einer deutlichen Reduktion der Nitratkonzentrationen. Die Modellergebnisse zeigen, dass der Grundwasserzustrom die beobachtete Nitratbelastung im Grabensystem nicht erklären kann, da der Großteil des Nitrates durch Denitrifikation verloren geht. Andere Quellen, wie direkte Einträge oder Dränagenzuflüsse müssen ebenfalls in Betracht gezogen werden. Die Prognosefähigkeit des Modells für das Untersuchungsgebiet wird durch die Datenunsicherheiten und die Schätzung der Modellparameter eingeschränkt. Dennoch ist der Modellansatz eine wertvolle Hilfe bei der Identifizierung von belastungsrelevanten Teilflächen (Stoffquellen und -senken) sowie bei der Modellierung der Auswirkungen von Managementmaßnahmen oder Landnutzungsveränderungen auf Grundlage von Szenario-Simulationen. Der Modellansatz unterstützt auch die Interpretation von Beobachtungsdaten, da so die lokalen Informationen in einen räumlichen und zeitlichen Zusammenhang gestellt werden können. / Chemical transformations and hydraulic processes in soil and groundwater often lead to an apparent retention of nitrate in lowland catchments. Models are needed to evaluate the interaction of these processes in space and time. The objectives of this study are <br /> <br /> i) to develop a specific modelling approach by combining selected modelling tools simulating N-transport and turnover in soils and groundwater of lowland catchments, ii) to study interactions between catchment properties and nitrogen transport. Special attention was paid to potential N-loads to surface waters. The modelling approach combines various submodels for water flow and solute transport in soil and groundwater: The soil-water- and nitrogen-model mRISK-N, the groundwater flow model MODFLOW and the solute transport model RT3D. In order to investigate interactions of N-transport and catchment characteristics, the distribution and availability of reaction partners have to be taken into account. Therefore, a special reaction-module is developed, which simulates various chemical processes in groundwater, such as the degradation of organic matter by oxygen, nitrate, sulphate or pyrite oxidation by oxygen and nitrate. The model approach is applied to different simulation, focussing on specific submodels. All simulation studies are based on field data from the Schaugraben catchment, a pleistocene catchment of approximately 25 km&#178;, close to Osterburg(Altmark) in the North of Saxony-Anhalt. The following modelling studies have been carried out: i) evaluation of the soil-water- and nitrogen-model based on lysimeter data, ii) modelling of a field scale tracer experiment on nitrate transport and turnover in the groundwater as a first application of the reaction module, iii) evaluation of interactions between hydraulic and chemical aquifer properties in a two-dimensional groundwater transect, iv) modelling of distributed groundwater recharge and soil nitrogen leaching in the study area, to be used as input data for subsequent groundwater simulations, v) study of groundwater nitrate distribution and nitrate breakthrough to the surface water system in the Schaugraben catchment area and a subcatchment, using three-dimensional modelling of reactive groundwater transport.<br /> <br /> The various model applications prove the model to be capable of simulating interactions between transport, turnover and hydraulic and chemical catchment properties. The distribution of nitrate in the sediment and the resulting loads to surface waters are strongly affected by the amount of reactive substances and by the residence time within the aquifer. <br /> <br /> In the Schaugraben catchment simulations, it is found that a period of 70 years is needed to raise the average seepage concentrations of nitrate to a level corresponding to the given input situation, if no reactions are considered. Under reactive transport conditions, nitrate concentrations are reduced effectively. Simulation results show that groundwater exfiltration does not contribute considerably to the nitrate pollution of surface waters, as most nitrate entering soils and groundwater is lost by denitrification. Additional sources, such as direct inputs or tile drains have to be taken into account to explain surface water loads. <br /> <br /> The prognostic value of the models for the study site is limited by uncertainties of input data and estimation of model parameters. Nevertheless, the modelling approach is a useful aid for the identification of source and sink areas of nitrate pollution as well as the investigation of system response to management measures or landuse changes with scenario simulations. The modelling approach assists in the interpretation of observed data, as it allows to integrate local observations into a spatial and temporal framework.

Reactive Transport Models (RTMs) provide quantitative tools to analyze the interaction between transport and biogeochemical processes in subsurface environments such as aquatic sediments and groundwater flow. A tremendous amount of research has shown the role and impact of scaling behavior of the reactive systems which stems from geologic heterogeneity. Depending on the kinetics of the reactions, different types of formulations have been proposed to describe reactions in RTMs. We introduce a novel quantitative criteria on the range of validity of local equilibrium assumption (LEA) in aquatic sediments with irreversible heterogeneous sorption reactions. Then we present a one-dimensional (1-D) early diagenetic module, MATSEDLAB, developed in MATLAB. The module provides templates for representing the reaction network, boundary conditions and transport regime, which the user can modify to fit the particular early diagenetic model configuration of interest. We describe the theoretical background of the model and introduce the MATLAB pdepe solver, followed by calibration and validation of the model by a number of theoretical and empirical applications. Finally, we introduce a new pore-scale model using lattice Boltzmann (LB) approach. It uses an iterative scheme for the chemical transport-reaction part and recent advances in the development of optimal advection-diffusion solvers within the lattice Boltzmann method framework. We present results for the dissolution and precipitation of a porous medium under different dynamical conditions, varying reaction rates and the ratio of advective to diffusive transport (Pe, Peclet number) for linear reactions. The final set of calculations considers sorption reactions on a heterogeneous porous medium. We use our model to investigate the effect of heterogeneity on the pore-scale distribution of sorption sites and the competition between three different sorption reactions.

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.

Brackish springs are relatively frequent phenomena in coastal carbonate formations and their existence has been extensively reported in Mediterranean coasts. In fact, more than 300 brackish springs have been identified only in the coast of the former Yugoslavia. They essentially consist of inland or submarine karst outlets discharging waters with flow-dependent salinity. The phenomenon is particularly surprising in inland springs, where high flow rates with significant salinities (presumably coming from the sea) may be discharged several meters above sea level. In addition to its scientific interest, brackish springs hold a strategic potential as a source of water in areas with often limited water resources. In order to design their appropriate management a quantitative understanding of their controlling mechanisms both in general and at every particular spring has to be achieved.These mechanisms have been studied for many years but some controversy still remains. It is clear that they are related to deep well developed karst systems. Under these conditions, groundwater flows in a turbulent mode through a network of interconnected conduits immersed in a porous matrix with slow Darcyan flow velocities. Surprisingly, different models to explain the functioning of the system, although based on different conceptual and methodological approaches lead to similar results. This sugests that a global study on the salinitzation mechanisms of brackish springs should be undertaken. Here, we first derive the equations governing turbulent flow for density-dependent fluids and describe different mechanisms of salinization of inland brackish springs, in order to compare with the spring discharge and concentration response for those mechanisms of salinization.The insights gained in this analysis are applied to the study of S'Almadrava spring (Mallorca, Spain). This spring discharges up to 2 m3/s with salinities of 20 mS/cm at an elevation of 8 m.a.s.l. It generally displays an inverse relation between discharge rate and concentration (i.e., discharging higher salinity waters for low flow rates, and vice versa). A hypothetical but geologically feasible dual permeability model is proposed to reproduce observed salinity variations for both the dry and wet seasons but also to explain the secondary salinity peaks observed after every rainfall event. Model results agree with observations, but the lack of geological information at depth impedes model validation. Therefore, a second validation of the conceptual model is undertaken based on high-frequency geochemical observations. Due to the highly dynamic conditions of the system, the geochemical data was analyzed using fully coupled reactive transport modelling. The interpretation of geochemical data not only helps on validating conceptual models but also yields information on the water-rock interaction processes occurring at deep carbonate systems. In fact, one of the processes initially proposed to explain the occurrence of well-developed karst systems at depth, is the enlargement of tectonic fissures by carbonate dissolution due to the mixing of fresh and seawater.The theory of dissolution by mixing waters is based on the fact that when two solutions are mixed, concentrations in the mixture are volume weighted averages of the two end-members, but the thermodynamic activities of the species controlling the water-mineral reactions are non linear functions of the mixing ratio. Therefore, two end-member solutions in equilibrium with a solid phase could lead to an undersaturated mixture depending on several factors, most notably CO2 content and ionic strength. Observation of mixing and carbonate dissolution at depth has not been possible because of technical difficulties. More accessible to observation is the seawater mixing zone in coastal aquifers where calcite undersaturation and/or calcite dissolution have been reported numerous times. Yet, dissolution in coastal environments is not always clear and oversaturation or lack of dissolution in mixing zones have also been described. This apparent inconsistency on field observations around the world prompted the studies of the second part of the thesis. Flow-through laboratory experiments were performed in CO2-controlled atmosphere in order to quantify the dependence of the dissolution of calcite with the mixing ratio, and the role that CO2 variations may have on enhancing the dissolution capacity of the mixture. Results show that, although dissolution occurs, the major carbonate dissolution in aquifers must be considered only in a geological time scale. Sanford and Konikow (1989) predicted the location and magnitude of long term porosity development of coastal aquifers, based on a two step method. We compare their results with a reactive transport model approach in 1D and 2D, showing that reactive transport is required to properly understand the phenomenon because it is found that dissolution is controlled not only by geochemical factors but also by the rate at which fresh and salt water mix (i.e., by dispersion).

It is important to understand the processes that influence the critical zone (CZ) evolution to ensure its sustainability. This thesis reports on laboratory and field experiments designed to measure the behavior of biogenic and lithogenic chemical species and their interaction in the CZ from column to pedon to catchment scales. We postulated that interactions between organic matter and rock-derived metals drive coupled processes of carbon stabilization and chemical weathering and denudation in the Jemez River Basin Critical Zone Observatory (JRB-CZO). First, we observed that secondary mineral coatings (Al and Fe (oxy)hydroxides) on primary silicate surfaces play a major role in sequestering aromatic and "humified" dissolved organic matter (DOM) into sorbate form, significantly retarding their subsurface transport. Further, reinfusion to OM-reacted-porous-media of a different DOM source resulted in exchange reactions consistent with a zonal model of OM adsorption at mineral surfaces. This dissertation also aimed to examine the influence of water and DOM fluxes on the CZ weathering processes. Rare earth elements (REE) were selected because of their coherent trends in reactivity toward organic ligands common to soils. Specifically, trends in REE fractionation were explored for their utility to inform on biogeochemical weathering processes in forested terrain in the JRB-CZO. Mineral weathering mechanisms are expected to differentially influence REE release, fractionation, and transport and the relative importance of such processes should be reflected in REE signatures of bulk soil, pore and surface waters. Our studies showed: (1) REE depletion trends with depth in bulk soils are correlated with topographically-induced variation in water and dissolved organic carbon (DOC) flux (reflected in negative correlations between total water and C fluxes) and solid phase REE concentrations measured at the same depths; (2) REE and DOC concentrations in stream waters were strongly correlated during snowmelt periods of high discharge, consistent with REE complexation and mobilization in association with organic ligands during shallow subsurface flow; (3) preferential sequestration of Eu occurs during formation of secondary Mn(IV)-oxides, explaining patterns of Eu enrichment in bulk soils; and (4) the incremental increase in positive Ce-anomalies with depth in bulk soils are apparently controlled by adsorption/co-precipitation with secondary Fe-(oxy)hydroxide minerals.

Reactive transport models are essential tools for predicting contaminant fate and transport in the subsurface and for designing effective remediation strategies. Sound understanding of subsurface mixing in heterogeneous porous media is the key for the realistic modeling of reactive transport. This dissertation aims to investigate the extent of mixing and improve upscaling effective macroscopic models for mixing-controlled reactive transport in connected heterogeneous formations, which usually exhibit strongly anomalous transport behavior. In this research, a novel approach is developed for an accurate geostatistical characterization of connected heterogeneous formations transformed from Gaussian random fields. Numerical experiments are conducted in such heterogeneous fields with different connectivity to investigate the performance of macroscopic mean transport models for simulating mixing-controlled reactive transport. Results show that good characterization of anomalous transport of a conservative tracer does not necessarily mean that the models may characterize mixing well and that, consequently, it is questionable that the models capable of characterizing anomalous transport behavior of a conservative tracer are appropriate for simulating mixing-controlled reactive transport. In connected heterogeneous fields with large hydraulic conductivity variances, macroscopic mean models ignoring concentration variations yield good prediction, while in fields with intermediate conductivity variances, the models must consider both the mean concentration and concentration variations, which are very difficult to evaluate both theoretically and experimentally. An innovative and practical approach is developed by combining mean conservative and reactive breakthrough curves for estimating concentration variations, which can be subsequently used by variance transport models for prediction. Furthermore, a new macroscopic framework based on the dual-permeability conceptualization is developed for describing both mean and concentration variation for mixing-controlled reactive transport. The developed approach and models are validated by numerical and laboratory visualization experiments. In particular, the new dual-permeability model demonstrates significant improvement for simulating mixing-controlled reactive transport in heterogeneous media with intermediate conductivity variances. Overall, results, approaches and models from this dissertation advance the understanding of subsurface mixing in anomalous transport and significantly improve the predictive ability for modeling mixing-controlled reactive transport in connected heterogeneous media.

La contamination des aquifères de proche subsurface par les intrants d'origine agricole (nitrates) est un problème mondial.L'utilisation excessive d'engrais depuis plusieurs décennies a impacté la qualité des masses d'eau souterraines et soulève des enjeux pour la santé humaine comme pour celle des écosystèmes. Les nitrates dans les aquifères peuvent être réduits en diazote gazeux par l'activité microbienne hétérotrophique (la biomasse microbienne obtenant l'énergie nécessaire à ce processus via le carbone organique issu de la surface) et/ou par l'activité autotrophique (la biomasse microbienne obtenant cette fois ci son énergie depuis une source proche, lithologique). Les taux de dénitrification sont très variables spatialement, et sont régulés par l'interaction entre la structure des flux d'eau souterrains avec l'activité biogéochimique. Localiser l'activité biogéochimique dans les aquifères est difficilement réalisable à l'échelle des bassins versants, mais paraît crucial pour la gestion des masses d'eau souterraines. Bien que les processus de l'activité microbienne ne puissent pas être entièrement résolus à l'échelle locale, ce manuscrit de thèse propose une caractérisation des taux de dénitrification à l'échelle du bassin versant, basée sur l'analyse de données et sur une approche de modélisation intégrée. Cette thèse propose d'utiliser de manière extensive des traceurs conservatifs et réactifs associés aux flux d'eau souterraine et des modèles de transport afin d'identifier les contrôles géologiques et biogéochimiques sur les capacités de dénitrification dans les aquifères. Cette méthodologie a été appliquée à un aquifère libre cristallin de 76 km² situé en Bretagne. A partir des concentrations en CFC-12, O2, NO3- et N2 dissous mesurées dans 16 puits, il a été possible de reconstituer les chroniques d'apports de nitrate dans la zone saturée et de définir les variations spatio-temporelles de la dénitrification. Il est prouvé ici que la dénitrification est en premier lieu contrôlée par la position des donneurs d'électron. Ce travail propose un cadre d'interprétation général sur la base de l'utilisation combinée et complémentaire des traceurs et sur la modélisation semi-explicite pour estimer à l'échelle régionale les capacités de dénitrification et les stocks de nitrates dans les aquifères. / Unconfined shallow aquifers in agricultural areas are contaminated by nitrates worldwide. Excessive fertilization over the last decades has affected groundwater quality as well as human and ecosystem wellbeing. Nitrate in groundwater can be microbially reduced to dinitrogen gas by heterotrophic (microbes obtaining their energy from surface-derived organic carbon) and autotrophic (microbes obtaining their energy from a lithological source) processes. However, denitrification rates are highly spatially variable, following involved interactions between groundwater flow structures and biogeochemical activity. The location of biogeochemical activity in the aquifer is difficult to access at the catchment scale, but of vast importance to gain predictive capabilities for groundwater management. Even though microbial processes cannot be resolved at the local scale, this dissertation proposes a catchment scale characterization of denitrification rates based on an integrated model- and data-driven approach. The dissertation proposes an extensive use of conservative and reactive tracers combined with groundwater flow and transport models to identify the geological and biogeochemical controls on aquifer denitrification capacities. The methodology is applied to a crystalline unconfined aquifer of 76 km2 size in Brittany, France. Based on CFC-12, O2, NO3-, and dissolved N2 concentrations measured in 16 wells, it is possible to reconstruct historical nitrate inputs to the saturated zone and to define spatiotemporal denitrification activity. It is shown that denitrification is primarily controlled by the location of electron donors. The dissertation proposes a general interpretation framework based on tracer information combined with complementary semi-explicit lumped parameter models to assess regional denitrification capacities and nitrate legacy.

Le devenir des polluants dans les sols constitue un enjeu environnemental majeur. Dans ce travail, nous apportons une contribution à quelques méthodes numériques pour la simulation de l’écoulement et du transfert de polluants en milieu poreux variablement saturés. La propagation d’un contaminant dans les milieux souterrains dépend en premier lieu des caractéristiques de l’écoulement qui le transporte. Dans la première partie de ce travail, nous présentons la méthode des éléments finis mixtes hybrides pour la résolution de l’équation de Richards. Une procédure de condensation de la masse est proposée pour éviter l’apparition d’oscillations non physiques, notamment lors de la simulation de problèmes d’infiltration dans un milieu initialement sec.Dans la deuxième partie de ce travail, la méthode ELLAM (Eulerian-Lagrangian Localized Adjoint Method) est utilisée pour la modélisation du transport réactif en milieux fortement hétérogènes. En effet, les résultats obtenus pour le transport linéaire, décrit par l’équation d’advection-dispersion, avec les ELLAM sont très encourageants. La méthode ELLAM permet (i) de s’affranchir des contraintes de discrétisations spatiale ettemporelle imposées avec les méthodes eulériennes classiques, (ii) de conserver la masse et (iii) de traiter toutes les conditions aux limites. Par ailleurs, nous proposons une nouvelle formulation des ELLAM (C_ELLAM) permettant d’éviter les oscillations numériques et de limiter la diffusion numérique générées parla formulation standard.Dans la dernière partie, le code de calcul élaboré avec la formulation C_ELLAM est utilisé pour la caractérisation de la macrodispersion dans les milieux hétérogènes. Pour ce faire, il est indispensable de disposer d’outils de simulation précis et efficaces car cette étude est basée sur une méthode Monte Carlo nécessitant la réalisation d’un très grand nombre de simulations sur des grilles de calcul de l’ordre du million de mailles. Les résultats obtenus sont comparés avec une étude antérieure basée sur le Random WalkParticle Method. / The fate of contaminants in soils is a major environmental challenge. In this work, we develop efficient and reliable numerical tools for simulation of water flow and distribution prediction of pollutants in variably saturated porous media. In the first part of this document, the mixed hybrid finite element method is presented for solving Richard’s equation. A mass lumping technique is proposed to avoid unphysical oscillations when sharp infiltration fronts are simulated. In the second part of this work, the Eulerian Lagrangian Localized Adjoint Method (ELLAM) is used for modeling reactive transport in highly heterogeneous domains. Solute transport is described mathematically by the advection-dispersion and results obtained with ELLAM are very encouraging. ELLAM allows (i)overcoming spatial and time discretizations constraints imposed by classical Eulerian method, (ii)conserving mass and (iii) treating general boundary conditions naturally in the formulation. Moreover, we introduce a new ELLAM scheme (C_ELLAM) which avoid unphysical oscillations and reduce the numerical dispersion generated by the standard formulation.In the last part of this document, the C_ELLAM scheme is used to characterize the macrodispersion of a nonreactive solute in heterogeneous domains. This study is based on Monte Carlo simulations andtherefore requires highly efficient simulators. Our results are compared with previous work using Random Walk Particle Method to solve the advection-dispersion equation.

Reactive transport modeling is an important approach to understand water dynamics, mass transport and biogeochemical processes from the hillslope to the catchment scale. It has a wide range of applications in the fields of e.g. water resource management, contaminanted site remediation and geotechnical engineering. To simulate reactive transport processes at a hillslope or larger scales is a challenging task, which involves interactions of complex physical and biogeochemical processes, huge computational expenses as well as difficulties in numerical precision and stability. The primary goal of the work is to develop a practical, accurate and efficient tool to facilitate the simulation techniques for reactive transport problems towards hillslope or larger scales. The first part of the work deals with the simulation of water flow in saturated and unsaturated porous media. The capability and accuracy of different numerical approaches were analyzed and compared by using benchmark tests. The second part of the work introduces the coupling of the scientific software packages OpenGeoSys and IPhreeqc by using a character-string-based interface. The accuracy and computational efficiency of the coupled tool were discussed based on three benchmarks. It shows that OGS#IPhreeqc provides sufficient numerical accuracy to simulate reactive transport problems for both equilibrium and kinetic reactions in variably saturated porous media. The third part of the work describes the algorithm of a parallelization scheme using MPI (Message Passing Interface) grouping concept, which enables a flexible allocation of computational resources for calculating geochemical reaction and the physical processes such as groundwater flow and transport. The parallel performance of the approach was tested by three examples. It shows that the new approach has more advantages than the conventional ones for the calculation of geochemically-dominated problems, especially when only limited benefit can be obtained through parallelization for solving flow or solute transport. The comparison between the character-string-based and the file-based coupling shows, that the former approach produces less computational overhead in a distributed-memory system such as a computing cluster. The last part of the work shows the application of OGS#IPhreeqc for the simulation of the water dynamic and denitrification process in the groundwater aquifer of a study site in Northern Germany. It demonstrates that OGS#IPhreeqc is able to simulate heterogeneous reactive transport problems at a hillslope scale within an acceptable time span. The model results shows the importance of functional zones for natural attenuation process. / Modellierung des reaktiven Stofftranports ist ein wichtiger Ansatz um die Wasserströmung, den Stofftransport und die biogeochemischen Prozesse von der Hang- bis zur Einzugsgebietsskala zu verstehen. Es gibt umfangreiche Anwendungsgebiete, z.B. in der Wasserwirtschaft, Umweltsanierung und Geotechnik. Die Simulation der reaktiven Stofftransportprozesse auf der Hangskala oder auf größeren Maßstäbe ist eine anspruchsvolle Aufgabe, da es sich um die Wechselwirkungen komplexer physikalischer und biogeochemischen Prozesse handelt, die riesigen Berechnungsaufwand sowie numerischen Schwierigkeiten bezogen auf die Genauigkeit und die Stabilität nach sich ziehen. Das Hauptziel dieser Arbeit besteht darin, ein praktisches, genaues und effizientes Werkzeug zu entwickeln, um die Simulationstechnik für reaktiven Stofftransport auf der Hangskala und auf größeren Skalen zu verbessern. Der erste Teil der Arbeit behandelt die Simulation der Wasserströmung in gesättigten und ungesättigten porösen Medien. Das Anwendungspotential und die Genauigkeit verschiedener numerischer Ansätze wurden mittels einiger Benchmarks analysiert und miteinander verglichen. Der zweite Teil der Arbeit stellt die Kopplung der wissenschaftlichen Softwarepakete OpenGeoSys und IPhreeqc mit einer stringbasierten Schnittstelle dar. Die Genauigkeit und die Recheneffizienz des gekoppelten Tools OGS#IPhreeqc wurden basierend auf drei Benchmark-Tests diskutiert. Das Ergebnis zeigt, dass OGS#IPhreeqc die ausreichende numerische Genauigkeit für die Simulation reaktiven Stofftransports liefert, welcher sich sowohl auf die Gleichgewichtsreaktion als auch auf die kinetische Reaktion in variabel gesättigten porösen Medien beziehen. Der dritte Teil der Arbeit beschreibt zuerst den Algorithmus der Parallelisierung des OGS#IPhreeqc basierend auf dem MPI (Message Passing Interface) Gruppierungskonzept, welcher eine flexible Verteilung der Rechenressourcen für die Berechnung der geochemischen Reaktion und der physikalischen Prozesse wie z.B. Wasserströmung oder Stofftransport ermöglicht. Danach wurde die Leistungsfähigkeit des Algorithmus anhand von drei Beispielen getestet. Es zeigt sich, dass der neue Ansatz Vorteile gegenüber die konventionellen Ansätzen für die Berechnung von geochemisch dominierten Problemen bringt. Dies ist vor allem dann der Fall, wenn nur eingeschränkter Nutzen aus der Parallelisierung für die Berechnung der Wasserströmung oder des Stofftransportes gezogen werden kann. Der Vergleich zwischen der string- und der dateibasierten Kopplung zeigt, dass die erstere weniger Rechenoverhead in einem verteilten Rechnersystem, wie z.B. Cluster erzeugt. Der letzte Teil der Arbeit zeigt die Anwendung von OGS#IPhreeqc für die Simulation der Wasserdynamik und der Denitrifikation im Grundwasserleiter eines Untersuchungsgebietes in NordDeutschland. Es beweist, dass OGS#IPhreeqc in der Lage ist, reaktiven Stofftransport auf der Hangskala innerhalb akzeptabler Zeitspanne zu simulieren. Die Simulationsergebnisse zeigen die Bedeutung der funktionalen Zonen für die natürlichen Selbstreinigungsprozesse.

The efficiency to improve the water quality of industrial and municipal wastewater in a constructed wetland/filter basin treatment system was investigated. The wetland system was constructed in a closed phosphate mine used for clay settling and sand tailings in Polk County, Florida. During 18-months of monitoring the chemical/microbiological composition of treated wetland water remained relatively constant, despite significant seasonal variations in temperature, rainfall and humidity. The following changes in water quality between input and output were observed: substantial decrease of water temperature (up to 10°C), reduction of As, SO4, F, Cl, NO3, NO2, Br, Na, K, Ca, and Mg, change in pH from 9 to 6.5-7, increase of H2S (up to 1060 micrograms/L), and a change from positive to negative ORP. There were no exceedances of the primary drinking water standards, volatile organic compounds, synthetic organic compounds, and radionuclides, but a number of exceedances for the secondary drinking water standards (Al, F, Fe, Mn, color, odor, total dissolved solids, and foaming agents). The concentration of fecal and total coliform bacteria in the wetland water was high, but subsequently reduced during filtration in the filter basin from 30 - 730 and 1000 - 7000 count/100 mL to < 2 and < 100 count/ 100 mL, respectively. To resolve the complex hydrogeological conditions a combined isotope/chemical mass-balance approach was applied. The results were the following: (1) the composition of water in the wetland varied throughout the period of the study; (2) a change in isotopic composition along the wetland flow path; (3) the wetland contained mainly wastewater (88 - 100 %) during normal pumping operations; however, hurricanes and inconsistent pumping added low conductivity water directly and triggered enhanced groundwater inflow into the wetland of up to 78 %; (4) the composition of water in monitor wells was mostly groundwater dominated; however periodically seepage from a water body to the north was detected; and (5) seepage from adjacent water bodies into the wetland was not identified during operation, which would indicate a potential water loss from the wetland. To test if the wetland system could be a prospective pre-treatment option for water used in aquifer storage and recovery (ASR) scenarios, a set of bench-scale leaching experiments was carried out using rocks from the Avon Park Formation, the Suwannee Limestone and the Ocala Limestone. Since As in the Floridan Aquifer was mainly present as an impurity in the mineral pyrite the elevated iron and sulfide concentrations in the wetland water were thought to prevent pyrite dissolution. The experiments which covered a range of redox conditions showed that the amount of As released from the aquifer matrix was not perfectly correlated with the bulk rock As concentration, nor the redox state of the water. The following important results were obtained: (1) the highest concentration of As was leached from the Avon Park Formation and the lowest - from the Suwannee Limestone, although the Ocala Limestone had the lowest bulk rock As; (2) minor to no As was released using native Floridan groundwater; (3) Tampa tap water, which chemically and physically resembled the ASR injection water, caused the As leaching of up to 27 micrograms/L, which was higher than the As drinking water standard; (4) the wetland and filter basin waters caused the highest release of As (up to 68 micrograms/L), which was unexpected because those water types were less oxygenated than Tampa tap water and thus should be less aggressive; (5) the in-situ filtration of the wetland water through a 0.2 micrometer membrane resulted in a reduction of As from 30 microgram/L to 16 microgram/L; and (5) the UV treatment significantly reduced both fecal and total coliform bacteria, but facilitated the increase of DO in initial waters, a change from negative to positive ORP, and the increase of As concentration in leachates. The experiments confirmed that perturbations of native aquifer conditions caused the release of As from the Floridan aquifer matrix, although the reaction may not be as simple as the dissolution of pyrite by oxygen, but additionally governed by a complex set of factors including the ORP of the system, SO4²?/S², Fe³?/Fe²?, dissolved organic carbon and microbial activity. In addition, the trend of As leaching could be governed by a set of factors, such as the porosity and permeability of the aquifer matrix influencing the rate and degree of free water saturation, amount of pyrite to be exposed to the preferential water flow paths, limited surface reactivity of pyrite with favored reactions on fractured mineral surfaces, the concentration and the selective leaching of As from individual pyrite crystals. To characterize and verify the geochemical processes in the column experiments, the Geochemist's Workbench reactive transport models (React and X1t) were developed. Results from the models correlated well to those from the column experiments and confirmed the following: (1) the water-rock reaction between the aquifer matrix and native groundwater was favorable for pyrite stability preventing the release of As into solution; (2) the injection of oxidizing surface water into reducing native groundwater caused a change in redox potential of the system thus promoting the dissolution of pyrite, and (3) 1D reactive transport model of water-rock reaction between the aquifer matrix and surface water indicated a diverse behavior of As along the column, such as the oxidative dissolution of pyrite, mobilization and simultaneous sorption of As onto neo-formed HFO, followed by the reductive dissolution of HFO and secondary release of adsorbed As, and the potential non-oxidative dissolution of pyrite contributing the additional source of As to the solution.