A major argument for incorporating deciduous tree species in coniferous forest stands is their role in the amelioration and stabilisation of biogeochemical cycles. Current forest management strategies in central Europe aim to increase the area of mixed stands. In order to formulate statements about the ecological effects of mixtures, studies at the stand level are necessary. In a mixed stand of Norway spruce (Picea abies (L.) Karst.) and silver birch (Betula pendula Roth) in the Ore Mountains (Saxony, Germany), the effects of these two tree species on chemical and microbial parameters in the topsoil were studied at one site in the form of a case study. Samples were taken from the O layer and A horizon in areas of the stand influenced by either birch, spruce or a mixture of birch and spruce. The microbial biomass, basal respiration, metabolic quotient, pH-value and the C and N contents and stocks were analysed in the horizons Of, Oh and A. Significantly higher contents of microbial N were observed in the Of and Oh horizons in the birch and in the spruce-birch strata than in the stratum containing only spruce. The same was found with respect to pH-values in the Of horizon and basal respiration in the Oh horizon. Compared to the spruce stratum, in the birch and spruce-birch strata, significantly lower values were found for the contents of organic C and total N in the A horizon. The findings of the case study indicated that single birch trees have significant effects on the chemical and microbial topsoil properties in spruce-dominated stands. Therefore, the admixture of birch in spruce stands may distinctly affect nutrient cycling and may also be relevant for soil carbon sequestration. Further studies of these functional aspects are recommended.

Objectives of thesis: 1.To evaluate the effect of pH and total hardness of water on the development of eggs in aquarium fish Corydoras paleatus, Corydoras paleatus albin, Tanichthys albonubes, Tanichthys albonubes gold, Aphyosemion gardneri, Aphyosemion gardneri gold. 2.Recommendation of optimal values of total hardness of water and pH for successful development of eggs for each monitored aquarium fish. Based on published data in available literature sources and on own experiments, it was evaluated how total water hardness (CM) and pH influences development of aquarium fish eggs of Aphyosemion gardneri, Aphyosemion gardneri gold, Tanichthys albonubes, Tanichthys albonubes gold, Corydoras paleatus, Corydoras paleatus albin.

Ce travail s’inscrit dans le cadre du projet Cigéo (Centre industriel de stockage géologique de déchets radioactifs) et a porté sur la valorisation des argilites du Callovo-Oxfordien sous forme de coulis d’injection activé alcalinement. Cette utilisation requiert un liant présentant une importante durée pratique d’utilisation (~24 heures) et une valeur de pH modérée (10-11). Ainsi l’activation thermique de l’argilite a dû être maitrisée afin d’accroitre la réactivité des espèces argileuses tout en limitant la décarbonatation, pour éviter la présence de calcium réactif. Une solution alcaline silicatée potassique, de réactivité modérée (Si/K = 0,70), a été utilisée pour l’activation alcaline des argilites calcinées. Afin de développer le coulis, il a été nécessaire de favoriser la réactivité de l’argilite par addition de métakaolin et d’incorporer des additifs à base de bore. Un coulis dont les caractéristiques correspondent à celles visées a ainsi été obtenu. Enfin, une étude du liant dans des conditions proches de celles de l’utilisation finale (injection entre la couche géologique d’argilites et le chemisage de déchets radioactifs) a été menée. Pour cela, le liant a été mis en contact avec un bloc d’argilites du Callovo-Oxfordien, à une température de 90 °C (température maximale en condition d’usage). Il a ainsi été mis en évidence qu’à 90 °C le réseau géopolymère se réorganise (intégration du bore dans le réseau et formation éventuelle de zéolite). La mise en contact du liant avec l’argilite géologique a aussi permis d’identifier une diffusion du potassium dans les argilites du Callovo-Oxfordien. / In the context of Cigéo project (geological industrial disposal for radioactive wastes), this work focuses on the valorization of Callovo-Oxfordian argillite by the formulation of an alkali-activated grout. This application required a high setting time (close to 24 hours) and a moderate pH value (10-11). Thus, the argillite thermal treatment has been adapted to alter clays minerals without decomposing carbonate species (to avoid the presence of reactive calcium). A potassium-based silicate solution, with moderated reactivity (Si/K = 0.70), has been used for the alkali-activation step. Concerning the grout formulation, it has been necessary to enhance the argillite reactivity by the insertion of metakaolin and to add boron-based compounds. The resulting grout was in accordance with the specification. Finally, a study of the binder in an environment close to the using conditions (injection between geological layer and a radioactive waste lining) has been investigated. In this aim, the binder has been casted in contact with the geological argillite at 90 °C. It was evidenced a network reorganization at 90 °C (boron integration in the network and possible formation of zeolite). Potassium diffusion from the binder to the argillite has also been observed.

Geosorption processes play an important role as retardation mechanism in subsurface transport of organic water constituents. Geosorption behaviour of Ionisable Hydrophobic Organic compounds (IHOCs) especially influence of dissolved natural organic materials on their sorption coefficients is poorly investigated. In this study influence of pH and NOM on the sorption of three different phenols (2-methyl-4,6-dinitrophenol, 2,4,6-trichlorophenol and pentachlorophenol) on a natural sandy aquifer material collected from a bank filtration site was studied in flow through column experiments. In first step the sorption coefficients of investigated phenols from NOM-free solutions with different pH values were determined. Single as well as multi (mixed) solutes experiments confirmed that there was no competition effect among the phenols investigated. An increasing sorption/retardation was observed with decreasing pH. A linear model was used to resolve the apparent sorption coefficient into an ionised species and neutral species component. This model allows a prediction of apparent sorption coefficients for any pH value. Analysis of data also revealed that the anion of 2-M-4,6-DNP show no significant sorption and a simple model based on the neutral form sorption coefficient was useful in predicting the apparent sorption coefficient over the entire pH range investigated. For 2,4,6-TCP and PCP, the anion sorption is much lower than that of the neutral species but cannot be neglected completely. For PCP, the anion sorption is even as high as the sorption of neutral 2,4,6-TCP. Thus for such hydrophobic phenols prediction of sorption based only on the partitioning of non-dissociated species may lead to an error, especially at high pH values (> pKa), where ionised form is present predominantly. On the other hand prediction of sorption based on the partitioning of non-dissociated species is useful at pH < pKa or in cases where the anion sorption can be neglected. The advantage of this prediction is that it allows predicting the pH-dependent sorption only on the basis of LFER correlations. It was shown that the organic carbon normalized sorption coefficients of the neutral forms of the phenols can be predicted better by solubility based regression correlations than by n-octanol-water partition coefficient based correlations. In second step the apparent sorption coefficients of investigated phenols from NOM-containing solutions (mixed solution of phenols dissolved in natural river water) with different pH values were determined; the sorption coefficients obtained from this step were compared with the results of the first step examinations. Analysis of data revealed that binding of 2-M-4,6-DNP by dissolved humic substances (DHS) reduces the sorption coefficient significantly. In contrast to it, the sorption of the more hydrophobic chlorinated phenols was not affected by DHS. A strong reduction of sorption onto aquifer material caused by complex formation with DHS was also observed for a second nitrophenol (2,4-DNP) and seems to be typically for nitrophenols. A combined sorption and complex formation model was proposed which could be used successfully to describe the effect of pH and NOM concentration on sorption reduction and to estimate binding constants. The binding constant found for 2-M-4,6-DNP is much higher than those reported by Ohlenbusch and Frimmel, 2001, for chlorophenols associated with Aldrich humic acid. This can be interpreted as a result of specific interactions between the nitrophenol and DHS. This phenomenon may cause an increase of the amount of nitrophenols, which can be transported with the groundwater flow and has to be considered in transport modelling, especially in cases where pH is lower than pKa. The models developed here are a useful tool to describe the influence of pH and NOM on geosorption processes and to estimate the Kd values which have to be used in transport models.

A major argument for incorporating deciduous tree species in coniferous forest stands is their role in the amelioration and stabilisation of biogeochemical cycles. Current forest management strategies in central Europe aim to increase the area of mixed stands. In order to formulate statements about the ecological effects of mixtures, studies at the stand level are necessary. In a mixed stand of Norway spruce (Picea abies (L.) Karst.) and silver birch (Betula pendula Roth) in the Ore Mountains (Saxony, Germany), the effects of these two tree species on chemical and microbial parameters in the topsoil were studied at one site in the form of a case study. Samples were taken from the O layer and A horizon in areas of the stand influenced by either birch, spruce or a mixture of birch and spruce. The microbial biomass, basal respiration, metabolic quotient, pH-value and the C and N contents and stocks were analysed in the horizons Of, Oh and A. Significantly higher contents of microbial N were observed in the Of and Oh horizons in the birch and in the spruce-birch strata than in the stratum containing only spruce. The same was found with respect to pH-values in the Of horizon and basal respiration in the Oh horizon. Compared to the spruce stratum, in the birch and spruce-birch strata, significantly lower values were found for the contents of organic C and total N in the A horizon. The findings of the case study indicated that single birch trees have significant effects on the chemical and microbial topsoil properties in spruce-dominated stands. Therefore, the admixture of birch in spruce stands may distinctly affect nutrient cycling and may also be relevant for soil carbon sequestration. Further studies of these functional aspects are recommended.

This master´s thesis deals about insulation and dielectric properties of water. It describes the structure of water, covalent and hydrogen bonds. It outlines primary chemical and physical properties of water and then it describes parameters of water - dynamic viscosity, conductivity, surface tension, pH and also describes dielectric properties - dielectric loss, loss factor, permittivity, polarization. Part of the work is practical section, which includes measurements of deionized water, destilled water, tap water and shows primary dependence such as dependence loss factor on frequency or relative permittivity on frequency.

Produced water is the largest waste product by volume in the oil industry and its treatment in onshore or offshore fields poses bigger and different challenges than what water engineers are used to encounter. Process to achieve reuse quality of this water is very expensive with many technical hurdles to overcome making the optimization of the treatment steps necessary. Electrocoagulation (EC) generates coagulants in-situ responsible for destabilizing oil droplets, suspended particles, and common pollutant in produced water. Furthermore, EC is a very efficient technology compared with traditional primary treatments used in the oil & gas industry and has several advantages such as: no hazardous chemical handling (which diminishes the risk of accident and logistic costs), high efficiency potential concerning boron removal, potential small footprint and less sludge generation. In this research, the treatment of produced water using EC was investigated in a practical manner for the oilfield to aim for a cleaner effluent for further processing and help to achieve a reuse quality. For this, an EC cell was designed using different parameters normally used in the literature to fit this scenario. After preliminary tests, the treatment time was set to 3 seconds. Response surface method (RSM) was employed to optimize the operating conditions for TOC removal on a broad quality of synthetic produced water while varying: salinity, initial oil concentration and initial pH. TOC was chosen to be the main response because of its importance in legislation and sensibility on the method. Furthermore, turbidity removal, change of pH value after EC in water with lack of buffer capacity, aluminum concentration and preliminary tests involving boron removal and influence of hydrogen carbonate were also studied. Real produced water was treated with EC to assess the optimum conditions obtained by the RSM showing the results were closely related. Finally, an estimation of volume required and operating cost for EC in the different types of produced water was made to assess how realistic it is for onshore and offshore applications.:ERKLÄRUNG DES PROMOVENDEN I ACKNOLEDGEMENT III ABSTRACT V TABLE OF CONTENT VII LIST OF FIGURES IX LIST OF TABLES X LIST OF EQUATIONS XII ABBREVIATIONS XIV 1. INTRODUCTION 1 2. PRODUCED WATER 6 2.1 Characterization of Oilfield Produced Water 6 2.2 Produced Water Management 10 2.2.1 Discharge and Regulations 10 2.2.2 Efforts on Reuse 11 2.2.3 Cost 14 3. PRODUCED WATER TREATMENT 17 3.1 Most Common Primary Treatment 17 3.1.1 Hydrocyclones 17 3.1.2 Flotation unit 18 3.2 Further Water Treatment Technologies 19 3.2.1 Membrane Process 19 3.2.1.1 Microfiltration 19 3.2.1.2 Ultrafiltration 21 3.2.1.3 Nanofiltration 23 3.2.1.4 Reverse Osmosis 24 3.2.1.5 Forward osmosis 24 3.2.2 Electrodialysis 25 3.2.3 Biological treatment 28 3.2.3.1 Aerobic and anaerobic process 28 3.2.3.2 Combining membrane and bio-reactor 29 3.2.4 Oxidative process 30 3.2.4.1 Oxidation process 30 3.2.4.2 Anodic oxidation 32 3.2.5 Thermal technology 34 3.2.5.1 Evaporation 34 3.2.5.2 Eutectic freeze crystallization 35 3.2.6 Adsorption and ion-exchange 36 3.3 Electrocoagulation 39 3.3.1 Colloidal Stability Theory 39 3.3.2 Theory of Electrocoagulation 40 3.3.3 Mechanism of Abatement of Impurities 44 3.3.4 Operational parameters and efficiency 49 4. MATERIALS AND METHODS 51 4.1 Analytical Techniques and Synthetic Solutions 51 4.1.1 Analytical Techniques 51 4.1.2 Synthetic Produced Water 51 4.2 Design of Experiment and Models 54 4.3 Experimental Protocol for EC 56 4 .4 Development of the new Electrocoagulation cell 57 4.5 Real Produced water 58 5. RESULTS AND DISCUSSION 59 5.1 Designing EC Cell Process 59 5.1.1 Computational Fluid Dynamics for EC manufacturing 59 5.2 Preliminary Experiments 61 5.2.1 TOC Removal and Residence Time Determination 61 5.2.2 Aluminum Concentration 64 5.3 Models Quality and Range of Validity 66 5.3.1 TOC Removal 66 5.3.2 Turbidity Removal 69 5.3.3 Final pH value 71 5.3.4 Ionic Strength and Interpolation for Different Salinities 73 5.3.5 Partial Conclusions 76 5.4 Evolution of the Final pH Value 78 5.5 Operation Region for Effective Treatment of Produced Water with EC 80 5.5.1 Produced Water with Low Salinity 80 Organic Compounds Removal 80 Turbidity Removal 83 5.5.2 Produced Water with Medium Salinity 84 Organic Compounds Removal 84 Turbidity Removal 86 5.5.3 Produced Water with High Salinity 87 Organic Compounds Removal 87 5.6 Influence of Hydrogen Carbonate 90 5.7 Real Produced water 91 5.8 Boron Removal 93 5.9 Estimation of the Size for EC in Full scale 94 5.10 Produced Water with Very Low Salinity and EC 95 5.11 Estimation of Operation Cost 96 6. CONCLUSION AND RECOMMENDATIONS 98 6.1 Conclusion 98 6.2 Recommendations for Future Work 101 Scale up on EC for upstream 101 Further processing and reuse 101 Online optimization for EC 101 Recommendations for any research related to upstream produced water 101 BIBLIOGRAPHY 102 APPENDIX A 117 APPENDIX B 120