The overall objective of this research was to gain an insight into the challenges encountered during chemical flooding under high hardness conditions. Different aspects of this problem were studied using a combination of laboratory experiments and simulation studies. Chemical Flooding is an important Enhanced Oil Recovery process. One of the major components of the operational expenses of any chemical flooding project, especially Alkali Surfactant Polymer (ASP) flooding is the cost of softening the injection brine to prevent the precipitation of the carbonates of the calcium and magnesium ions which are invariably present in the formation brine. Novel hardness tolerant alkalis like sodium metaborate have been shown to perform well with brines of high salinity and hardness, thereby eliminating the need to soften the injection brine. The first part of this research was aimed at designing an optimal chemical flooding formulation for a reservoir having hard formation brine. Sodium metaborate was used as the alkali in the formulation with the hard brine. Under the experimental conditions, sodium metaborate was found to be inadequate in preventing precipitation in the ASP slug. Factors affecting the ability of sodium metaborate to sequester divalent ions, including its potential limitations under the experimental conditions were studied. The second part of this research studied the factors affecting the ability of novel alkali and chelating agents like sodium metaborate and tetrasodium EDTA to sequester divalent ions. Recent studies have shown that both these chemicals showed good performance in sequestering divalent ions under high hardness conditions. A study of the geochemical species in solution under different conditions was done using the computer program PHREEQC. Sensitivity studies about the effect of the presence of different solution species on the performance of these alkalis were done. The third part of this research focused on field scale mechanistic simulation studies of geochemical scaling during ASP flooding. This is one of the major challenges faced by the oil and gas industry and has been found to occur when sodium carbonate is used as the alkali and the formation brine present in situ has a sufficiently high hardness content. The multicomponent and multiphase compositional chemical flooding simulator, UTCHEM was used to determine the quantity and composition of the scales formed in the reservoir as well as the injection and production wells. Reactions occurring between the injected fluids, in situ fluids and the reservoir rocks were taken into consideration for this study. Sensitivity studies of the effect of key reservoir and process parameters like the physical dispersion and the alkali concentration on the extent of scaling were also done as a part of this study. / text

No description available.

Mercury (Hg) is a global contaminant of ecosystems and human health risk, with complicated biogeochemical processes. Mercury sulfide (HgS) dissolution has been suggested as a key process in Hg cycling, as it could potentially increase the pool of inorganic Hg (iHg) for the production of methylmercury (MeHg). Despite previous sporadic observations of enhanced HgS dissolution under certain conditions, much remains unclear on mechanisms of HgS dissolution. The objective of my research was to advance the mechanistic understanding of HgS dissolution, concerning re-adsorption of released Hg, effects of thiol-ligands, and Hg speciation. Considering the lack of feasible techniques to differentiate dissolution and re-adsorption processes, I first developed an efficient method using isotope tracer and isotope dilution techniques to investigate the re-adsorption of released Hg during HgS dissolution. The HgS dissolution rate with consideration of re-adsorption was two times the rate calculated from detecting Hg alone in the presence of O2, indicating the importance of Hg re-adsorption during HgS dissolution. I further examined the role of Hg-ligand complexation in HgS dissolution and Hg(II) re-adsorption using a thermodynamic adsorption method, selecting L-cysteine (Cys) as a model compound for low molecular weight ligands and Waskish fulvic acid (FA) for natural dissolved organic matter (DOM). My results suggest that the presence of Cys enhanced HgS dissolution through the decreased re-adsorption of Hg-Cys complex, whereas Waskish FA inhibited HgS dissolution, possibly because of the adsorption of FA on HgS surface that covered dissolution sites. I further employed a geochemical modeling method to study Hg speciation and the relation of iHg speciation to MeHg, aiming to provide a methodological example for potentially evaluating the implications of Hg species distribution during HgS dissolution on MeHg production. I applied geochemical model PHREEQC to the Florida Everglades, a well-studied wetland with model input parameters available, to determine the distribution of iHg in surface water at different sites. The modeling results suggest that sulfide and DOM govern iHg speciation, and the Hg-sulfide and Hg-DOM species are related to MeHg in environmental media but not fish, suggesting the importance of iHg speciation in MeHg production and the complexity of Hg bioaccumulation.

The objective of the work described in this thesis was to understand sorption reactions of uranium occurring at the water-clay mineral interfaces in the presence and absence of arsenic and other inorganic ligands. Uranium(VI) removal by clay minerals is influenced by a large number of factors including: type of clay mineral, pH, ionic strength, partial pressure of CO2, load of the sorbent, total amount of U present, and the presence of arsenate and other inorganic ligands such as sulfate, carbonate, and phosphate. Both sulfate and carbonate reduced uranium sorption onto IBECO bentonite due to the competition between SO42- or CO32- ions and the uranyl ion for sorption sites, or the formation of uranyl-sulfate or uranyl-carbonate complexes. Phosphate is a successful ligand to promote U(VI) removal from the aqueous solution through formation of ternary surface complexes with a surface site of bentonite. In terms of the type of clay mineral used, KGa-1b and KGa-2 kaolinites showed much greater uranium sorption than the other clay minerals (STx-1b, SWy-2, and IBECO montmorillonites) due to more aluminol sites available, which have higher affinity toward uranium than silanol sites. Sorption of uranium on montmorillonites showed a distinct dependency on sodium concentrations because of the effective competition between uranyl and sodium ions, whereas less significant differences in sorption were found for kaolinite. A multisite layer surface complexation model was able to account for U uptake on different clay minerals under a wide range of experimental conditions. The model involved eight surface reactions binding to aluminol and silanol edge sites of montmorillonite and to aluminol and titanol surface sites of kaolinite, respectively. The sorption constants were determined from the experimental data by using the parameter estimation code PEST together with PHREEQC. The PEST- PHREEQC approach indicated an extremely powerful tool compared to FITEQL. In column experiments, U(VI) was also significantly retarded due to adsorptive interaction with the porous media, requiring hundreds of pore volumes to achieve breakthrough. Concerning the U(VI) desorption, columns packed with STx-1b and SWy-2 exhibited irreversible sorption, whereas columns packed with KGa-1b and KGa-2 demonstrated slow, but complete desorption. Furthermore, most phenomena observed in batch experiments were recognized in the column experiments, too. The affinity of uranium to clay minerals was higher than that of arsenate. In systems containing uranium and arsenate, the period required to achieve the breakthrough in all columns was significantly longer when the solution was adjusted to pH 6, due to the formation of the uranyl-arsenate complex. In contrast, when pH was adjusted to 3, competitive sorption for U(VI) and As(V) accelerated the breakthrough for both elements. Finally, experiments without sorbing material conducted for higher concentrations of uranium and arsenic showed no loss of total arsenic and uranium in non-filtered samples. In contrast, significant loss was observed after filtration probably indicating the precipitation of a U/As 1:1 phase.

Impacts from mining waste deposits on groundwater resources have been recognized invarious parts of the world; though varied in scale depending on the composition of mineralsbeing mined, the level of technology employed and environmental commitment of thedevelopers. Mining activities usually involve milling, concentrating, and processing of oreswhich will result in a huge amount of waste, called tailings, usually deposited inimpoundments as a slurry, composed of fine grained geological material (uneconomicalminerals), chemicals utilized in the processs, and water. Oxidation of these deposits, usuallycontaining sulphide minerals, may result in generation of an acidic, metal laden leachate,callled Acid Mine Drainage (AMD), which may have a devastating impact on thesurrounding groundwater resources. In this study, the stochastic LaSAR-PHREEQC reactive transport modeling approach is usedin order to evaluate the coupled effect of geochemical reactions and physical heterogeneity ofthe subsurface in the breakthrough of acidity and metal downstream of the source while theAMD transported in the water saturated zone of an impoundment. The tailings depositcalled Impoundment 1 at the Kristineberg mining site at the Skellefteå field, in northernSweden, is used as a case study to simulate pH buffering processes and attenuation of Zn.The objectives of the study are 1) to evaluate the relevance of different possible geochemicalprocesses in pH buffering and Zn attenuation; 2) to evaluate the effect of spatial variability ofthe physical processes of the groundwater system on the breakthrough of contaminants; and3) to evaluate the effect of the location and distribution of the source zone in terms of thedistance from the impoundment boundary. Simulation results of the presented model revealed that pH buffering from calcite andchlorite are important processes capable of counteracting the acidification from AMD.Dissolution of secondary Al(OH)3(s) is another important process capable of buffering pH.Precipitation of smithsonite, ZnCO3, is an important process for attenuation of Zn2+.Moreover, sorption of Zn2+ on ferric iron surfaces is found to be an important process forattenuation of the metal, depending on the available sorption surface sites. Flow variabilityhighly affects the breakthrough of the contaminants such that with increasing subsurfaceheterogeneity, earlier breakthrough of contaminants occurs. Moreover, increased variabilityresults in decreased peak loads, but longer duration of the load. / www.ima.kth.se

No description available.

Les doublets géothermiques sur aquifères superficiels jouent un rôle important en France pour le chauffage, le rafraichissement et la production d’eau chaude sanitaire des bâtiments. La pérennité de ces installations est cependant conditionnée par la possibilité de pouvoir garantir dans le temps la production puis la réinjection de l’eau souterraine. Le colmatage de la boucle géothermale est un problème majeur qui affecte de nombreuses installations sur l’ensemble du territoire français et remet en cause leur viabilité technico-économique. La compréhension et la prédiction de ce phénomène nécessite de nouveaux moyens de caractérisation et de modélisation des processus biogéochimiques couplés au fonctionnement des boucles géothermales dans des environnements de subsurface hétérogènes. Cette thèse a ainsi fait l’objet d’une nouvelle collaboration entre le laboratoire Géosciences Rennes et l’entreprise Antea group pour identifier les mécanismes à l’origine de ces phénomènes de colmatage et d’en caractériser les paramètres influents dans le but de construire un outil d’analyse des risques permettant l’anticipation de ces processus de colmatage. Le premier volet de la thèse expose la synthèse des typologies de colmatage (biogéochimique, chimique, biologique et physique). Cette synthèse est issue de l’étude de la littérature sur la problématique de colmatage des forages d’eau et des retours d’expérience concernant les doublets géothermiques recensés et étudiés durant cette thèse. Le second volet présente les inventaires régionaux des problématiques de colmatage recensées en France dans différents contextes hydrogéologiques. Ces inventaires ont permis de délivrer un état des lieux à grande échelle de la problématique de colmatage et d’étudier les contextes associés à chaque type de colmatage. Dans le troisième volet, de nouvelles méthodologies de caractérisation in-situ des phénomènes de colmatage biogéochimique liés à l’oxydation du manganèse et du fer sont présentées. Elles ont été développées dans le cadre de ces travaux de thèse à partir des investigations menées sur différents sites confrontés à des problèmes d’exploitation. Ces méthodologies d’investigations pluridisciplinaires couplent la mesure des propriétés hydrauliques, des concentrations en éléments chimiques et de la diversité microbienne afin d’identifier la problématique impactant le fonctionnement de l’installation et d’en définir in fine les causes. Le quatrième volet expose les résultats d’une campagne de terrain effectuée sur un doublet géothermique impacté par un processus de colmatage biogéochimique. Cette campagne a permis d’identifier les composantes clés de la réactivité biochimique impliquée dans le colmatage : distribution du flux, hétérogénéité chimique et diversité microbiologique. A l’aide du code de calcul PHREEQC, un modèle géochimique simulant les cinétiques de précipitation observées a été développé. Il permet l’étude quantitative des mécanismes biogéochimiques favorisant l’apparition rapide du colmatage. Enfin, les retours d’expériences de l’exploitation des doublets sur nappes superficielles ont démontré le besoin d’une méthodologie fiable d’analyse des risques, permettant d’anticiper l’apparition des processus de colmatage à chaque étape de la vie du projet. Ainsi, à partir de la synthèse de la littérature scientifique et technique et des conclusions des études menées durant cette thèse, les facteurs de risques d’apparition des phénomènes de colmatage ont été déterminés. L’analyse des risques de colmatage intégrant ces différents facteurs a été implémentée à travers l’élaboration de méthodes développées sous Python 3. L’outil ARCADE (Analyse des Risques de Colmatage et Aide à la Décision) a été conçu d’une part pour évaluer le risque et d’autre part pour informer l’utilisateur averti des bonnes pratiques et moyens préventifs. Ces bonnes pratiques d’analyse et de gestion préventive sont présentées dans le dernier volet de cette thèse. / The sustainability of geothermal systems using shallow aquifers for heating, cooling and hot water production depends on the possibility to ensure, over long time-scales, the production and the reinjection of groundwater in the aquifer. Clogging of the geothermal loop is a major issue affecting the technical and economic viabilities of numerous operations in France. The understanding and prediction of this phenomenon requires new methods of characterization and modelling of biogeochemical processes coupled to the operation of geothermal loops in heterogeneous subsurface environments. This thesis is thus the result of a new collaboration between the Géosciences Rennes lab and Antea group to identify the mechanisms at the origin of clogging phenomena and characterize their controlling parameters, in order to establish a risk assessment tool allowing the anticipation of clogging processes. The first part of the thesis describes the main clogging processes (biogeochemical, chemical, biological and physical). This synthesis is the result of (1) the study of the literature dealing with the clogging of water wells and (2) our feedbacks on the geothermal doublets identified and studied during this thesis. The second part presents the regional inventories of shallow geothermal systems impacted by clogging problems identified in different hydrogeological contexts in France. These inventories provide a large-scale perspective of clogging phenomena and allow to study the contexts associated with each type of clogging processes. In the third part, new methodologies for the in-situ characterization of biogeochemical clogging phenomena linked to manganese and iron oxidation are presented through case studies of sites affected by clogging issues. These interdisciplinary studies couple the measurement of hydraulic properties, chemical element concentrations and bacterial diversity, to identify the specific issue impacting the operation and to define its causes. The fourth part presents the results of an interdisciplinary field campaign carried out on a geothermal doublet impacted by a biogeochemical clogging process. This campaign documented the key components involved in mixing induced biogeochemical reactivity: flow distribution, chemical heterogeneity and microbiological diversity. Using PHREEQC, a geochemical model simulating observed kinetics of precipitation was developed in order to quantitatively explore the biogeochemical mechanisms favoring rapid clogging. Feedback from shallow geothermal systems operation has demonstrated the need for a reliable risk analysis methodology that allowed to anticipate the apparition of clogging processes at each stage of the project life (part 5). From the synthesis of the scientific & technical literature and the conclusions of the studies carried out during this thesis, the risk factors for the appearance of clogging phenomena were determined. A clogging risk analysis integrating these factors was implemented through the development of methods developed under Python 3. The methodology of the ARCADE tool (Analyse des Risques de Colmatage et Aide à la Décision) is designed to assess the risk and to inform users of good practices and preventive methods. These good practices for analysis and preventive methods are presented in the last part of this thesis.

Cette thèse a permis de mieux comprendre les mécanismes de complexation des terres rares par les acides humiques afin d'expliquer la variabilité des spectres de terres rares observée dans les eaux riches en matière organique. Cette étude montre que l'hétérogénéité des groupements fonctionnels complexants des acides humiques peut induire différents types de spectres de complexation des terres rares en fonction des conditions physico-chimiques. En effet, à pH acide, lorsque le rapport terres rares/acides humiques augmente, les terres rares se lient majoritairement à des sites carboxyliques multidentates puis monodentates qui ont, respectivement, une plus forte affinité pour les terres rares lourdes et intermédiaires. Lorsque le pH augmente, la participation de sites phénoliques devient plus importante pour les terres rares lourdes tandis que les légères restent liées à des sites carboxyliques. Des expériences de compétition entre les terres rares et le fer ou l'aluminium pour la complexation par les acides humiques ont également été réalisées. A pH neutre, Al est un plus fort compétiteur pour les terres rares légères, et se lie donc préférentiellement à des sites carboxyliques, tandis que Fe est un compétiteur pour toutes les terres rares, et se lie donc aussi bien aux sites carboxyliques que phénoliques. Ainsi, le rapport cation dissous/acides humiques, le pH et la natures des cations compétiteurs peuvent expliquer la variabilité des spectres de terres rares observée dans les eaux naturelles. De plus, les terres rares peuvent être utilisées comme sonde des mécanismes de complexation des cations par les acides humiques, comme ici pour Al et Fe.

Mining of lignite in Lusatia has a long history of over 100 years. The extracted brown coal is utilized to generate electricity in three large power plants: Jänschwalde, Boxberg, and Schwarze Pumpe. With an annual carbon dioxide (CO2) output of approximately 50 million tons, these power plants are among Germany’s large-scale CO2 emitters. The environmental impact from open-pit mining is of a considerable degree and currently poses a challenging problem. The groundwater deficit in 1990 was 7 billion m3 over a surface area of approximately 2100 km2 (Luckner, 2006a) and was bisected in value until today. Due to the decline of mining activity and the termination of mine drainage at most open pits in the Lusatian region, the groundwater table has recovered forming 28 pit lakes (Zschiedrich, 2011). The majority of the post mining lakes do not meet the quality standards for pH, iron or sulfate parameters; because of pyrite oxidation that produces acid mine drainage (Luckner, 2006b, Klapper and Schultze, 1995, Schultze et al., 2010). The post mining lakes in Lusatia have low pH values (3 – 4), high sulfate contents (up to 2800 ppm) as well as high iron concentrations (100 – 150 ppm). Lakes are flooded by groundwater and using surface water from Spree and Neisse River to achieve fast filling and dilution; however, due to the limited availability of surface water, further rehabilitation strategies for the region had to be investigated. Between 1970 and 1990, approximately 26 million m3 of suspended fly ash were deposited in the lake Burghammer and settled as an ash body at its base; where it may be used for rehabilitation. In a first experiment conducted in 2001 material from the ash body was picked up and redistributed throughout the lake. By this treatment the pH of the lake was raised temporarily; however, a sustainable remediation was not achieved. Based on these experiments it was investigated whether the ash reacts more sufficiently through additional CO2 injection or not. Aim was to combine the rehabilitation of acid mine lakes with the utilization of atmospheric carbon dioxide emissions from coal-fired power plants. The CO2 sequestration is achieved through the generation and accumulation of carbonates in the lake. The following equations describe the precipitation of carbonate by using CO2 and alkaline earth cations M: CO2 + MO → MCO3 (s) CO2 + M(OH)2 → MCO3 (s) + H2O Therefore, neutral pH conditions are necessary for the long-term accumulation of carbonates in the lakes. In laboratory investigations it was shown, that the 20 to 30 years old fly ash deposits of lake Burghammer can be used for carbonate sequestration and lake water treatment. Bivalent ions (Ca2+, Mg2+) are eluable and available for carbonate precipitation; on average we assumed 1 wt.-% of reactive calcium to be contained in the settled ash sediments. Settled fly ash sediments are less reactive than fresh fly ash from a power plant (e.g. Schwarze Pumpe). During batch experiments, we increased the buffering capacity to maximum values of 7 mmol/L. Beforehand no buffering capacity exists due to the low pH of 2.9 in the lake. Batch investigations provided a sequestration potential of 17 g CO2/kg ash sediment; in comparison fresh fly ash results in a sequestration potential of 33 g CO2/kg ash (Schipek and Merkel, 2008b, Schipek and Merkel, 2008a, Schipek, 2009). Based on the laboratory results a field experiment was conducted. In this field experiment gas injection lances were installed to a sediment depth of 12 m. Gaseous CO2 was applied with a pressure of 2.2 bar and 2.2 m³/h for 3 months and lake water was monitored during injection. Variations in total inorganic carbon due to diffusion processes of CO2 saturated pore waters could be observed. As the pilot experiment comprised only a small area of lake Burghammer no initial neutralisition (e.g. by a suction excavator) was possible. Thus, no further changes in water chemistry were observed. Drilling cores in the vicinity of the injection area provided mineralogical and geochemical conditions before and after CO2 treatment. No trace metal mobilization was found during CO2 injection. Most elements showed decreasing trends or didn’t change significantly. Calculated saturation indices for calcite indicated equilibrium conditions or slightly oversaturated conditions (SICalcite,average +0.12; SICalcite,median +0.31). Geochemical and mineralogical investigations proved that CO2 sequestration is possible with an average precipitation rate of 0.5 wt.-% (2.2 g CO2/kg). The maximum rate for carbonate precipitation was determined with 7.4 wt.-% Calcite, according to 32.6 g CO2 per kilogram treated ash. Besides the use of the settled fly ash as neutralizing agent in acidic mining lakes, laboratory and field investigations were conducted in order to improve in-lake liming. In batch and columns experiments, different liming agents (synthetic marble powder and industrial products) were tested and investigated. Significant differences in reactivity were obvious at pCO2 > 3.8 • 10-4 atm. Ions typical for acid mine drainage (e.g. Mn2+, Cd2+, SO42-) do have different effects on the kinetic of carbonate dissolution. Manganese concentrations typical for acidic mining lakes inhibit calcite dissolution. Cadmium has as well a significant influence on dissolution and kinetics. Only circa 50 % of the calcium concentration was reached with cadmium as inhibitor compared to the dissolution in pure water. Increased CO2 partial pressure might be used to compensate inhibtion by material impurities and/or water constituents. Column experiments showed that a multi-stage application of liming agent increases the efficiency of a lake treatment. The combination of a first application of calcite (up to pH 4.5) and further application of Ca(OH)2 seemed to be the most promising method. This treatment sheme was successfully applied in lake Burghammer from March 2009 – December 2010 (initial neutralisation and 6 follow-up treatments). Finally, it can be concluded, that in lignite mining districts in-lake treatment of acidic mining lakes is a seminal method to handle water quality problems. Using gaseous CO2 in combination with industrial by-products can be accounted as sustainable method for CO2 sequestration and for treatment of AMD. The advantage for mining areas lays in the prevention during treatment of acid mine lakes. Nevertheless, this method presents only a niche solution due to the dependence on alkaline materials, e.g. fly ash. The development of further strategies and optimization during lake water treatment by in-lake liming might improve the effectiveness of the method. Using calcite instead of NaOH or CaO as liming agent will provide advantages in being more economic and ecological (CO2 bilance). In order to enhance efficiency the use of calcite in combination with CO2 can be a worth considering suggesting. If meteorological parameters (wind) and lake specific characteristics (morphology, currents, etc.) will be considered efforts and costs for in-lake liming will be minimized. / Der Abbau von Braunkohle im Lausitzer Bergbaurevier hat seit über 100 Jahren Tradition. Die abgebaute Braunkohle wird dabei hauptsächliche zur Energieerzeugung in den drei großen Kraftwerken Jänschwalde, Boxberg und Schwarze Pumpe genutzt. Mit einem jährlichen Kohlenstoffdioxid (CO2) – Ausstoß von circa 50 Millionen Tonnen gehören diese Kraftwerke zu Deutschlands größten CO2-Emittenten. Der Einfluss auf die Umwelt durch Tagebau-Betrieb ist von beträchtlichem Ausmaß und bringt große Probleme mit sich. Im Jahr 1990 betrug das Grundwasser-Defizit im Lausitzer Bergbaurevier 7 Milliarden m³ auf einer Fläche von circa 2100 km² (Luckner, 2006a). Dieses Defizit hat sich bis zum heutigen Zeitpunkt halbiert. Durch den Rückgang der Bergbauaktivitäten und die Beendigung der Wasserhaltungsmaßnahmen in den meisten Tagebauen, hat der ansteigende Grundwasserspiegel 28 Tagebaufolgeseen geschaffen (Zschiedrich, 2011). Der überwiegende Teil der Tagebaufolgeseen ist aufgrund der Pyritoxidation, welche AMD (acid mine drainage) produziert, hinsichtlich der Wasserqualitätsparameter stark beeinflusst (Luckner, 2006b, Klapper and Schultze, 1995, Schultze et al., 2010). Die Tagebaufolgeseen im Lausitzer Bergbaurevier sind durch niedrige pH-Werte (3 – 4), hoche Sulfat-Konzentrationen (bis zu 2800 ppm) und hohe Eisengehalte (100 – 150 ppm) gekennzeichnet. Die entstehenden Seen sind hauptsächlich durch aufsteigendes Grundwasser und Oberflächenwasser aus den Flüssen Spree und Neisse geflutet. Aufgrund der geringen Verfügbarkeit von Oberflächenwasser mussten weitere Sanierungsmaßnahmen für die Region untersucht werden. Zwischen 1970 und 1990 wurden im Tagebaufolgesee Burghammer circa 26 Millionen m³ Flugasche-Suspension als Aschekörper abgelagert, wobei eine Nutzung zu Sanierungszwecken angedacht war. Im Rahmen einer Aschesedimentumlagerung im Jahr 2001 wurde der pH-Wert des Seewassers kurzzeitig angehoben, eine nachhaltige Sanierung fand jedoch nicht statt. Auf Grundlage dieser Ergebnisse wurde im Rahmen dieser Dissertation untersucht, ob die abgelagerten Aschesedimente nachhaltiger durch Einsatz von CO2 reagieren. Ziel war es die Sanierung von Tagebaufolgeseen mit der Reduktion von CO2-Emissionen aus Kohlekraftwerken zu kombinieren. Diese CO2-Sequestrierung sollte durch die Bildung und Ablagerung von Carbonaten im Seesediment erfolgen. Die Gleichungen (1) und (2) beschreiben dabei die Fällungsreaktion von Carbonaten aus CO2 mit dem Alkalimetall M (aus Oxiden bzw. Hydroxiden): CO2 + MO → MCO3 (s) CO2 + M(OH)2 → MCO3 (s) + H2O Zur Carbonatfällung und nachhaltigen Ablagerung sind neutrale pH-Bedingungen notwendig. In Laboruntersuchungen konnte gezeigt werden, dass die 20 bis 30 Jahre alten Flugaschesedimente zur CO2-Sequestrierung in Kombination mit Seewasserbehandlung genutzt werden können. Zweiwertige Ionen (Ca2+, Mg2+) sind aus den Aschesedimenten eluierbar und stehen für die Fällungsreaktion zur Verfügung. Durchschnittlich 1 Masse-% reaktives Calcium befindet sich in den Sedimenten. Die abgelagerten Aschesedimente sind dabei weniger reaktiv als frische Flugaschen aus Kohlekraftwerken (z.B. Schwarze Pumpe). In Batch-Versuchen mit Tagebaufolgesee-Wasser konnte die Säure-Pufferkapazität auf maximal 7 mmol/L erhöht werden. Sequestrierungs-Raten von 17 g CO2/kg Aschesediment wurden im Rahmen der Versuche erreicht. Im Vergleich dazu betrugen die Sequestrierungs-Raten in Versuchen mit frischen Flugaschen bis 33 g CO2/kg Asche (Schipek and Merkel, 2008b, Schipek and Merkel, 2008a, Schipek, 2009). Auf Grundlage dieser Laborergebnisse wurde ein Feldversuch im Tagebaufolgesee Burghammer geplant. Während diesem wurden Gasinjektionslanzen bis in eine Sedimenttiefe von 12 m im abgelagerten Aschesediment installiert. Gasförmiges CO2 wurde mit einem durchschnittlichen Druck von 2.2 bar und 2.2 m³/h für eine Dauer von 3 Monaten injiziert. Während dieser Zeit fand ein kontinuierliches Monitoring des Seewassers im Bereich der Injektion statt. Veränderungen des Gehaltes an TIC (total inorganic carbon) aufgrund von Diffusionprozessen von CO2-gesättigtem Porenwasser aus dem Aschekörper waren beobachtbar. Da der Feldversuch nur in einem begrenzten Bereich des Tagebaufolgesees Burghammer stattfand und keine Initialneutralisierung vorsah, konnten keine weiteren, großmaßstäblichen Veränderungen im Wasserkörper festgestellt werden. Bohrkernentnahmen im Umfeld des Behandlungsgebietes lieferten Aussagen bezüglich der mineralogischen und geochemischen Beschaffenheit vor und nach CO2-Injektion. Im Porenwasser wurde keine Spurenmetall-(re)-mobilisierung durch die Behandlung mit CO2 festgestellt. Nahezu alle Elemente zeigten einen abnehmenden Trend durch die Behandlung mit CO2, bzw. keine signifikanten Veränderungen. Modellierte Sättigungsindizes für Calcit wiesen auf Gleichgewichtsbedingungen oder leichte Übersättigung bzgl. Calcit hin (SICalcit, Mittelwert +0.12; SICalcit, Median +0.31). Geochemische und mineralogische Untersuchungen zeigten, daß CO2-Sequestrierung mit einer durchschnittlichen Fällungsrate von 0.5 Masse-% (2.2 g CO2/kg Aschesediment) erreicht wurde. Die maximale Fällungsrate wurde mit 7.4 Masse-% Calcit bestimmt, dies entspricht einer Festlegung von 32.6 g CO2/ kg Aschesediment. Neben der Nutzung der abgelagerten Aschesedimente zur Behandlung des Tagebaufolgeseewassers wurden desweiteren Labor- und Feldversuche durchgeführt um In-Lake-Behandlungen mit industriellen Kalkprodukten zu optimieren. In Batch- und Säulenversuchen wurden verschiedene Kalkprodukte (synthetisches Marmorpulver und industrielle Produkte) getestet und untersucht. Signifikante Unterschiede auf die Reaktivität wurde bei erhöhten CO2-Partialdrücken (pCO2 > 3.8 • 10-4 bar) beobachtet. Wasserinhaltsstoffe, die typisch für AMD sind (z.B.. Mn2+, Cd2+, SO42-) zeigten einen signifikanten Einfluss auf die Calcit-Lösungskinetik. Mangankonzentrationen, wie sie in Lausitzer Tagebaufolgeseen vorkommen, zeigten – ebenso wie Cadmium - eine inhibitierende Wirkung auf die Kinetik. Im Vergleich zu Versuchen mit destilliertem Wasser wurden nur ungefähr 50 % der Calcium-Gleichgewichtskonzentration mit Cadmium als Inhibitor erreicht. Erhöhte CO2-Partialdrücke könnten genutzt werden, um die inhibitierende Wirkung von vorhanden Materialverunreinigungen und/oder Wasserinhaltsstoffen zu kompensieren. Säulenversuche zeigten, dass der mehrstufige Einsatz von Kalkprodukten die Effizienz während einer Seewasserbehandlung erhöht. Die Kombination einer Erstbehandlung mit Kalksteinmehl (bis pH 4.5), und einer Behandlungsfortsetzung mit Ca(OH)2 erwies sich als wirkungsvollste Methode. Dieses Behandlungsschema (Initialneutralisation, 6 Nachfolgebehandlungen) wurde im Tagebaufolgesee Burghammer von März 2009 – Dezember 2010 erfolgreich angewandt. Zusammenfassend lässt sich sagen, dass in ehemaligen Bergbaurevieren die In-Lake-Behandlung von Tagebaufolgeseen eine zukunftsträchtige Methode zur Behandlung von Wasserqualitätsproblemen darstellt. Die Nutzung von gasförmigen CO2 in Kombination mit industriellen „Abfall-Produkten“ kann als nachhaltige Methode zur CO2-Sequestrierung und zur Behandlung von AMD bezeichnet werden. Der Vorteil in Bergbaurevieren liegt dabei in der Vorbeugung der Entstehung von Wasserqualitätsproblemen. Dennoch stellt diese Methode nur eine Nischenlösung aufgrund der Verfügbarkeit der alkalischen Materialien (Flugasche) dar. Die Entwicklung und Optimierung weiterführender Strategien zur In-Lake-Behandlung durch Kalkung wird zur Effizienzerhöhung beitragen. Die Nutzung von Kalksteinmehl anstelle von NaOH bzw. CaO als Neutralisationsprodukt wird Vorteile hinsichtlich ökonomischer und ökologischer Sicht (CO2-Bilanz) mit sich führen. Um die Effizienz beim Einsatz von Kalksteinmehl zu steigern, kann der Einsatz von CO2 in Betracht gezogen werden. Sobald meteorologische Parameter (Wind) und see-spezifische Merkmale (Morphologie, Strömungen, etc.) berücksichtigt werden, kann der Aufwand und die Kosten für In-Lake-Behandlungen minimiert werden.

The Biscayne Aquifer is a primary source of water supply in Southeast Florida. As a coastal aquifer, it is threatened by saltwater intrusion (SWI) when the natural groundwater flow is altered by over-pumping of groundwater. SWI is detrimental to the quality of fresh groundwater sources, making the water unfit for drinking due to mixing and reactions with aquifer minerals. Increasing water demand and complex environmental issues thus force water utilities in South Florida to sustainably manage saltwater intrusion and develop alternative water supplies (e.g., aquifer storage and recovery, ASR). The objectives of this study were to develop and use calibrated geochemical models to estimate water quality changes during saline intrusion and during ASR in south Florida. A batch-reaction model of saltwater intrusion was developed and important geochemical reactions were inferred. Additionally, a reactive transport model was developed to assess fate and transport of major ions and trace metals (Fe, As) at the Kissimmee River ASR. Finally, a cost-effective management of saltwater intrusion that involves using abstraction and recharge wells was implemented and optimized for the case of the Biscayne Aquifer. Major processes in the SWI areas were found to be mixing and dissolution-precipitation reactions with calcite and dolomite. Most of the major ions (Cl, Na, K, Mg, SO4) behaved conservatively during ASR while Ca and alkalinity were affected by carbonate reactions and cation exchange. A complex set of reactions involving thermodynamic equilibrium, kinetics and surface complexation reactions was required in the ASR model to simulate observed concentrations of Fe and As. The saltwater management model aimed at finding optimal locations and flow rates for abstraction and recharge wells. Optimal solutions (i.e., minimum total salt and total cost Pareto front) were produced for the Biscayne Aquifer for scenarios of surface recharge induced by climate change-affected precipitation. In general, abstraction at the maximum rate near the coast and artificial recharge at locations much further inland were found to be optimal. Knowledge developed herein directly supports the understanding of SWI caused by anthropogenic stressors, such as over-pumping and sea level rise, on coastal aquifers.