The transport of contaminants in groundwater system is strongly influenced by various aquifer heterogeneity factors such as spatial aquifer heterogeneity of hydraulic conductivity and reactive substances distribution. The contaminants transport can be simulated by using numerical reactive transport models, and their fate can be possibly even predicted. Furthermore, reactive transport modeling is an essential tool to get a profound understanding of hydrological-geochemical complex processes and to make plausible predictions of assessment. The goal of this work is to improve our understanding of the groundwater contaminants fate and transport processes in heterogeneous aquifer systems, with a focus on nitrate problems. A large body of knowledge of the fate and transport of nitrogen species has been achieved by previous works, however, most previous models typically neglect the interrelation of physical and chemical aquifer heterogeneities on the contaminant fate and redox transformation, which is required for predicting the movement and behavior of nitrate and quantifying the impact of uncertainty of numerical groundwater simulation, and which motivates this study. The main research questions which are answered in this work are how aquifer heterogeneity influences on the nitrate fate and transport and then, what is the most influential aquifer heterogeneity factor must be considered. Among the various type of aquifer heterogeneity, physical and chemical aquifer heterogeneities are considered. The first part of the work describes groundwater flow system and hydrochemical characteristics of the study area (Hessian Ried, Germany). Especially, data analyses are performed with the hydrochemical data to identify the major driving force for nitrate reduction in the study area. The second part of the work introduces a kinetic model describing nitrate removal by using numerical simulation. The resulting model reproduces nitrate reduction processes and captures the sequence of redox reactions. The third and fourth parts show the influence of physical and chemical aquifer heterogeneity with varying variance, correlation length scale, and anisotropy ratio. Heterogeneous aquifer systems are realized by using stochastic approach. Results, in short, show that the most influential aquifer heterogeneity factors could change over time. With abundant requisite electron donors, physical aquifer heterogeneity significantly influences the nitrate reduction while chemical aquifer heterogeneity plays a minor role. Increasing the spatial variability of the hydraulic conductivity increases the nitrate removal efficiency of the system in addition. If these conditions are reversed, nitrate removal efficiency varies by the spatial heterogeneity of the available initial electron donor. The results indicate that an appropriate characterization of the physical and chemical properties can be of significant importance to predict redox contamination transport and design long-term remediation strategies and risk assessment.

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.

Aerated treatment wetlands are an increasingly recognized nature–based technology for thetreatment of domestic and industrial wastewater. As biodegradation is the most importanttreatment mechanism in aerated wetlands, these systems heavily rely on mechanical aerationmediated oxygen transfer to supply the dissolved oxygen demand of the associated microbialcommunity. In the last decade, research on aerated wetlands has evolved, however, majorquestions on aeration, the associated oxygen transfer and the quantitative link to treatmentperformance still remain unknown. Answering these questions can further improve aeratedwetland design to optimize treatment efficacy and economical efficiency. This dissertation investigated the link of oxygen transfer to the air flow rate of aerationand elucidated the associated impact on treatment performance for organic carbon and nitrogenin horizontal flow aerated wetlands. Therefore, a numerical process model includingone dimensional reactive transport was developed. This model describes the main processesinvolved in horizontal flow aerated wetlands: water flow, heat transport, transport of solubleand particulate wastewater pollutants, biodegradation by a network of bacterial communitiesand oxygen transfer through mechanical aeration. For model calibration and validation, pilot–scale experiments in horizontal flow aerated wetlands treating real wastewater were conducted.These included conservative tracer experiments as well as monitoring steady–state operationat variable air flow rates and aeration interruption. In general, the model was able to simulate conservative tracer transport as well as treatmentperformance for organic carbon and nitrogen at steady–state operation and aeration interruptionwith sufficient accuracy. A local sensitivity analysis of the calibrated parameters revealedporosity, hydraulic permeability and dispersion length as well as the oxygen transfer coefficientkLa as most important. When operating the wetland systems at steady–state, aeration provideda mostly aerobe environment, except at the influent zone. However, when aeration wasinterrupted, anaerobe process started to take over and treatment performance declined within3–4 days. The modeling elucidated that methanogenic and sulphate reducing bacteria can playa significant role for organic carbon removal during aeration interruption. Moreover, the modelrevealed a non–linear declining relationship of the air flow rate with oxygen transfer coefficientkLa and of kLa with treatment performance. The alteration of oxygen transfer by wastewaterpollutant concentration was then investigated in a laboratory–scale column experiment. Basedon this experiment, an empirical equation describing the inhibitory effect of soluble chemicaloxygen demand (CODs) on the oxygen transfer coefficient kLa was derived and incorporatedinto the process model. With the extended model several simulation scenarios were analyzedto quantify the impact of the inhibited oxygen transfer on treatment performance. It turnedout that the reduction of oxygen transfer by CODs will, most likely, be relevant only at highinfluent wastewater strength (CODs 300 mg L-1), low aeration (air flow rate 50 L m-2h-1) or when the aerated wetland design includes zoned aeration. With respect to secondarytreatment of domestic effluents at similar strength using a spatially uniform aeration, an airflow rate of approximately 150–200 L m-2 h-1 can be recommended as a reasonable compromisebetween treatment efficiency and robustness. If zoned aeration is intended (e.g. to create a redox zonation), however, the air flow rate should be increased to approximately 400 L m-2 h-1 to supress the inhibition of oxygen transfer by CODs concentration. Furthermore, the air flow rate at steady–state operation (50–500 L m-2 h-1) did not substantially affect the response in effluent concentrations for organic carbon and nitrogen. This means that at steady–state air flow rates of 50–500 L m-2 h-1 operation, treatment efficacy during aeration interruption will deteriorate and recover in a similar time. In conclusion, this dissertation provides quantitative insights into the mechanisms of aeration and treatment performance for organic carbon and nitrogen in horizontal flow aerated treatment wetlands. The findings obtained can support aerated treatment wetland design for research experiments and engineering applications. Therefore, this dissertation represents a significant advancement in the field of aerated treatment wetland research.