@phdthesis{Wriedt2004,
  author    = {Wriedt, Gunter},
  title     = {Modelling of nitrogen transport and turnover during soil and groundwater passage in a small lowland catchment of Northern Germany},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-0001307},
  school      = {Universit{\"a}t Potsdam},
  year      = {2004},
  abstract  = {Stoffumsatzreaktionen und hydraulische Prozesse im Boden und Grundwasser k{\"o}nnen in Tieflandeinzugsgebieten zu einer Nitratretention f{\"u}hren. 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 Ber{\"u}cksichtigung der potentiellen N-Zufuhr in die Oberfl{\"a}chengew{\"a}sser. 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 Verf{\"u}gbarkeit von Reaktionspartnern ber{\"u}cksichtigt werden. Dazu wurde ein Reaktionsmodul entwickelt, welches chemische Prozesse im Grundwasser simuliert. Hierzu geh{\"o}ren 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 N{\"a}he von Osterburg(Altmark) im Norden Sachsen-Anhalts. Die folgenden Einzelstudien wurden durchgef{\"u}hrt: 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) Fl{\"a}chenverteilte Modellierung von Grundwasserneubildung und Bodenstickstoffaustrag im Untersuchungsgebiet als Eingangsdaten f{\"u}r nachfolgende Grundwassersimulationen, und v) Untersuchung der Ausbreitung von Nitrat im Grundwasser und des Durchbruchs in die Oberfl{\"a}chengew{\"a}sser im Untersuchungsgebiet auf Basis einer 3D-Modellierung von Grundwasserstr{\"o}mung und reaktivem Stofftransport. Die Modellstudien zeigen, dass der Modellansatz geeignet ist, die Wechselwirkungen zwischen Stofftransport und \–umsatz und den hydraulisch-chemischen Gebietseigenschaften zu modellieren. Die Ausbreitung von Nitrat im Sediment wird wesentlich von der Verf{\"u}gbarkeit 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 Ber{\"u}cksichtigung von reaktivem Stofftransport f{\"u}hrt zu einer deutlichen Reduktion der Nitratkonzentrationen. Die Modellergebnisse zeigen, dass der Grundwasserzustrom die beobachtete Nitratbelastung im Grabensystem nicht erkl{\"a}ren kann, da der Großteil des Nitrates durch Denitrifikation verloren geht. Andere Quellen, wie direkte Eintr{\"a}ge oder Dr{\"a}nagenzufl{\"u}sse m{\"u}ssen ebenfalls in Betracht gezogen werden. Die Prognosef{\"a}higkeit des Modells f{\"u}r das Untersuchungsgebiet wird durch die Datenunsicherheiten und die Sch{\"a}tzung der Modellparameter eingeschr{\"a}nkt. Dennoch ist der Modellansatz eine wertvolle Hilfe bei der Identifizierung von belastungsrelevanten Teilfl{\"a}chen (Stoffquellen und -senken) sowie bei der Modellierung der Auswirkungen von Managementmaßnahmen oder Landnutzungsver{\"a}nderungen auf Grundlage von Szenario-Simulationen. Der Modellansatz unterst{\"u}tzt auch die Interpretation von Beobachtungsdaten, da so die lokalen Informationen in einen r{\"a}umlichen und zeitlichen Zusammenhang gestellt werden k{\"o}nnen.},
  language  = {en}
}
@article{TranterDeLuciaWolfgrammetal.2020,
  author    = {Tranter, Morgan Alan and De Lucia, Marco and Wolfgramm, Markus and K{\"u}hn, Michael},
  title     = {Barite scale formation and injectivity loss models for geothermal systems},
  series = {Water},
  volume    = {12},
  journal   = {Water},
  number    = {11},
  publisher = {MDPI},
  address   = {Basel},
  issn      = {2073-4441},
  doi       = {10.3390/w12113078},
  pages     = {24},
  year      = {2020},
  abstract  = {Barite scales in geothermal installations are a highly unwanted effect of circulating deep saline fluids. They build up in the reservoir if supersaturated fluids are re-injected, leading to irreversible loss of injectivity. A model is presented for calculating the total expected barite precipitation. To determine the related injectivity decline over time, the spatial precipitation distribution in the subsurface near the injection well is assessed by modelling barite growth kinetics in a radially diverging Darcy flow domain. Flow and reservoir properties as well as fluid chemistry are chosen to represent reservoirs subject to geothermal exploration located in the North German Basin (NGB) and the Upper Rhine Graben (URG) in Germany. Fluids encountered at similar depths are hotter in the URG, while they are more saline in the NGB. The associated scaling amount normalised to flow rate is similar for both regions. The predicted injectivity decline after 10 years, on the other hand, is far greater for the NGB (64\%) compared to the URG (24\%), due to the temperature- and salinity-dependent precipitation rate. The systems in the NGB are at higher risk. Finally, a lightweight score is developed for approximating the injectivity loss using the Damkohler number, flow rate and total barite scaling potential. This formula can be easily applied to geothermal installations without running complex reactive transport simulations.},
  language  = {en}
}
@article{TranterDeLuciaKuehn2021,
  author    = {Tranter, Morgan Alan and De Lucia, Marco and K{\"u}hn, Michael},
  title     = {Barite scaling potential modelled for fractured-porous geothermal reservoirs},
  series = {Minerals},
  volume    = {11},
  journal   = {Minerals},
  number    = {11},
  publisher = {MDPI},
  address   = {Basel},
  issn      = {2075-163X},
  doi       = {10.3390/min11111198},
  pages     = {22},
  year      = {2021},
  abstract  = {Barite scalings are a common cause of permanent formation damage to deep geothermal reservoirs. Well injectivity can be impaired because the ooling of saline fluids reduces the solubility of barite, and the continuous re-injection of supersaturated fluids forces barite to precipitate in the host rock. Stimulated reservoirs in the Upper Rhine Graben often have multiple relevant flow paths in the porous matrix and fracture zones, sometimes spanning multiple stratigraphical units to achieve the economically necessary injectivity. While the influence of barite scaling on injectivity has been investigated for purely porous media, the role of fractures within reservoirs consisting of both fractured and porous sections is still not well understood. Here, we present hydro-chemical simulations of a dual-layer geothermal reservoir to study the long-term impact of barite scale formation on well injectivity. Our results show that, compared to purely porous reservoirs, fractured porous reservoirs have a significantly reduced scaling risk by up to 50\%, depending on the flow rate ratio of fractures. Injectivity loss is doubled, however, if the amount of active fractures is increased by one order of magnitude, while the mean fracture aperture is decreased, provided the fractured aquifer dictates the injection rate. We conclude that fractured, and especially hydraulically stimulated, reservoirs are generally less affected by barite scaling and that large, but few, fractures are favourable. We present a scaling score for fractured-porous reservoirs, which is composed of easily derivable quantities such as the radial equilibrium length and precipitation potential. This score is suggested for use approximating the scaling potential and its impact on injectivity of a fractured-porous reservoir for geothermal exploitation.},
  language  = {en}
}
@phdthesis{Tranter2022,
  author    = {Tranter, Morgan Alan},
  title     = {Numerical quantification of barite reservoir scaling and the resulting injectivity loss in geothermal systems},
  doi       = {10.25932/publishup-56113},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-561139},
  school      = {Universit{\"a}t Potsdam},
  pages     = {131},
  year      = {2022},
  abstract  = {Due to the major role of greenhouse gas emissions in global climate change, the development of non-fossil energy technologies is essential. Deep geothermal energy represents such an alternative, which offers promising properties such as a high base load capability and a large untapped potential. The present work addresses barite precipitation within geothermal systems and the associated reduction in rock permeability, which is a major obstacle to maintaining high efficiency. In this context, hydro-geochemical models are essential to quantify and predict the effects of precipitation on the efficiency of a system. The objective of the present work is to quantify the induced injectivity loss using numerical and analytical reactive transport simulations. For the calculations, the fractured-porous reservoirs of the German geothermal regions North German Basin (NGB) and Upper Rhine Graben (URG) are considered. Similar depth-dependent precipitation potentials could be determined for both investigated regions (2.8-20.2 g/m3 fluid). However, the reservoir simulations indicate that the injectivity loss due to barite deposition in the NGB is significant (1.8\%-6.4\% per year) and the longevity of the system is affected as a result; this is especially true for deeper reservoirs (3000 m). In contrast, simulations of URG sites indicate a minor role of barite (< 0.1\%-1.2\% injectivity loss per year). The key differences between the investigated regions are reservoir thicknesses and the presence of fractures in the rock, as well as the ionic strength of the fluids. The URG generally has fractured-porous reservoirs with much higher thicknesses, resulting in a greater distribution of precipitates in the subsurface. Furthermore, ionic strengths are higher in the NGB, which accelerates barite precipitation, causing it to occur more concentrated around the wellbore. The more concentrated the precipitates occur around the wellbore, the higher the injectivity loss. In this work, a workflow was developed within which numerical and analytical models can be used to estimate and quantify the risk of barite precipitation within the reservoir of geothermal systems. A key element is a newly developed analytical scaling score that provides a reliable estimate of induced injectivity loss. The key advantage of the presented approach compared to fully coupled reservoir simulations is its simplicity, which makes it more accessible to plant operators and decision makers. Thus, in particular, the scaling score can find wide application within geothermal energy, e.g., in the search for potential plant sites and the estimation of long-term efficiency.},
  language  = {en}
}
@article{StedingKempkaKuehn2021,
  author    = {Steding, Svenja and Kempka, Thomas and K{\"u}hn, Michael},
  title     = {How insoluble inclusions and intersecting layers affect the leaching process within potash seams},
  series = {Applied Sciences : open access journal},
  volume    = {11},
  journal   = {Applied Sciences : open access journal},
  number    = {19},
  publisher = {MDPI},
  address   = {Basel},
  issn      = {2076-3417},
  doi       = {10.3390/app11199314},
  pages     = {21},
  year      = {2021},
  abstract  = {Potash seams are a valuable resource containing several economically interesting, but also highly soluble minerals. In the presence of water, uncontrolled leaching can occur, endangering subsurface mining operations. In the present study, the influence of insoluble inclusions and intersecting layers on leaching zone evolution was examined by means of a reactive transport model. For that purpose, a scenario analysis was carried out, considering different rock distributions within a carnallite-bearing potash seam. The results show that reaction-dominated systems are not affected by heterogeneities at all, whereas transport-dominated systems exhibit a faster advance in homogeneous rock compositions. In return, the ratio of permeated rock in vertical direction is higher in heterogeneous systems. Literature data indicate that most natural potash systems are transport-dominated. Accordingly, insoluble inclusions and intersecting layers can usually be seen as beneficial with regard to reducing hazard potential as long as the mechanical stability of leaching zones is maintained. Thereby, the distribution of insoluble areas is of minor impact unless an inclined, intersecting layer occurs that accelerates leaching zone growth in one direction. Moreover, it is found that the saturation dependency of dissolution rates increases the growth rate in the long term, and therefore must be considered in risk assessments.},
  language  = {en}
}
@phdthesis{Steding2022,
  author    = {Steding, Svenja},
  title     = {Geochemical and Hydraulic Modeling of Cavernous Structures in Potash Seams},
  doi       = {10.25932/publishup-54818},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-548182},
  school      = {Universit{\"a}t Potsdam},
  pages     = {IX, 104},
  year      = {2022},
  abstract  = {Salt deposits offer a variety of usage types. These include the mining of rock salt and potash salt as important raw materials, the storage of energy in man-made underground caverns, and the disposal of hazardous substances in former mines. The most serious risk with any of these usage types comes from the contact with groundwater or surface water. It causes an uncontrolled dissolution of salt rock, which in the worst case can result in the flooding or collapse of underground facilities. Especially along potash seams, cavernous structures can spread quickly, because potash salts show a much higher solubility than rock salt. However, as their chemical behavior is quite complex, previous models do not account for these highly soluble interlayers. Therefore, the objective of the present thesis is to describe the evolution of cavernous structures along potash seams in space and time in order to improve hazard mitigation during the utilization of salt deposits. The formation of cavernous structures represents an interplay of chemical and hydraulic processes. Hence, the first step is to systematically investigate the dissolution and precipitation reactions that occur when water and potash salt come into contact. For this purpose, a geochemical reaction model is used. The results show that the minerals are only partially dissolved, resulting in a porous sponge like structure. With the saturation of the solution increasing, various secondary minerals are formed, whose number and type depend on the original rock composition. Field data confirm a correlation between the degree of saturation and the distance from the center of the cavern, where solution is entering. Subsequently, the reaction model is coupled with a flow and transport code and supplemented by a novel approach called 'interchange'. The latter enables the exchange of solution and rock between areas of different porosity and mineralogy, and thus ultimately the growth of the cavernous structure. By means of several scenario analyses, cavern shape, growth rate and mineralogy are systematically investigated, taking also heterogeneous potash seams into account. The results show that basically four different cases can be distinguished, with mixed forms being a frequent occurrence in nature. The classification scheme is based on the dimensionless numbers P{\´e}clet and Damk{\"o}hler, and allows for a first assessment of the hazard potential. In future, the model can be applied to any field case, using measurement data for calibration. The presented research work provides a reactive transport model that is able to spatially and temporally characterize the propagation of cavernous structures along potash seams for the first time. Furthermore, it allows to determine thickness and composition of transition zones between cavern center and unaffected salt rock. The latter is particularly important in potash mining, so that natural cavernous structures can be located at an early stage and the risk of mine flooding can thus be reduced. The models may also contribute to an improved hazard prevention in the construction of storage caverns and the disposal of hazardous waste in salt deposits. Predictions regarding the characteristics and evolution of cavernous structures enable a better assessment of potential hazards, such as integrity or stability loss, as well as of suitable mitigation measures.},
  language  = {en}
}
@article{HennigStockmannKuehn2020,
  author    = {Hennig, Theresa and Stockmann, Madlen and K{\"u}hn, Michael},
  title     = {Simulation of diffusive uranium transport and sorption processes in the Opalinus Clay},
  series = {Applied geochemistry : journal of the International Association of Geochemistry and Cosmochemistry},
  volume    = {123},
  journal   = {Applied geochemistry : journal of the International Association of Geochemistry and Cosmochemistry},
  publisher = {Elsevier},
  address   = {Oxford},
  issn      = {0883-2927},
  doi       = {10.1016/j.apgeochem.2020.104777},
  pages     = {9},
  year      = {2020},
  abstract  = {Diffusive transport and sorption processes of uranium in the Swiss Opalinus Clay were investigated as a function of partial pressure of carbon dioxide pCO(2), varying mineralogy in the facies and associated changes in porewater composition. Simulations were conducted in one-dimensional diffusion models on the 100 m-scale for a time of one million years using a bottom-up approach based on mechanistic surface complexation models as well as cation exchange to quantify sorption. Speciation calculations have shown, uranium is mainly present as U(VI) and must therefore be considered as mobile for in-situ conditions. Uranium migrated up to 26 m in both, the sandy and the carbonate-rich facies, whereas in the shaly facies 16 m was the maximum. The main species was the anionic complex CaUO2(CO3)(3)(2-) . Hence, anion exclusion was taken into account and further reduced the migration distances by 30 \%. The concentrations of calcium and carbonates reflected by the set pCO(2) determine speciation and activity of uranium and consequently the sorption behaviour. Our simulation results allow for the first time to prioritize on the far-field scale the governing parameters for diffusion and sorption of uranium and hence outline the sensitivity of the system. Sorption processes are controlled in descending priority by the carbonate and calcium concentrations, pH, pe and the clay mineral content. Therefore, the variation in porewater composition resulting from the heterogeneity of the facies in the Opalinus Clay formation needs to be considered in the assessment of uranium migration in the far field of a potential repository.},
  language  = {en}
}
@article{HennigKuehn2021,
  author    = {Hennig, Theresa and K{\"u}hn, Michael},
  title     = {Surrogate model for multi-component diffusion of Uranium through Opalinus Clay on the host rock scale},
  series = {Applied Sciences : open access journal},
  volume    = {11},
  journal   = {Applied Sciences : open access journal},
  number    = {2},
  publisher = {MDPI},
  address   = {Basel},
  issn      = {2076-3417},
  doi       = {10.3390/app11020786},
  pages     = {21},
  year      = {2021},
  abstract  = {Multi-component (MC) diffusion simulations enable a process based and more precise approach to calculate transport and sorption compared to the commonly used single-component (SC) models following Fick's law. The MC approach takes into account the interaction of chemical species in the porewater with the diffuse double layer (DDL) adhering clay mineral surfaces. We studied the shaly, sandy and carbonate-rich facies of the Opalinus Clay. High clay contents dominate diffusion and sorption of uranium. The MC simulations show shorter diffusion lengths than the SC models due to anion exclusion from the DDL. This hampers diffusion of the predominant species CaUO2(CO3)32-. On the one side, species concentrations and ionic strengths of the porewater and on the other side surface charge of the clay minerals control the composition and behaviour of the DDL. For some instances, it amplifies the diffusion of uranium. We developed a workflow to transfer computationally intensive MC simulations to SC models via calibrated effective diffusion and distribution coefficients. Simulations for one million years depict maximum uranium diffusion lengths between 10 m and 35 m. With respect to the minimum requirement of a thickness of 100 m, the Opalinus Clay seems to be a suitable host rock for nuclear waste repositories.},
  language  = {en}
}
@article{HennigKuehn2021,
  author    = {Hennig, Theresa and K{\"u}hn, Michael},
  title     = {Potential uranium migration within the geochemical gradient of the opalinus clay system at the Mont Terri},
  series = {Minerals},
  volume    = {11},
  journal   = {Minerals},
  number    = {10},
  publisher = {MDPI},
  address   = {Basel},
  issn      = {2075-163X},
  doi       = {10.3390/min11101087},
  pages     = {22},
  year      = {2021},
  abstract  = {Transport properties of potential host rocks for nuclear waste disposal are typically determined in laboratory or in-situ experiments under geochemically controlled and constant conditions. Such a homogeneous assumption is no longer applicable on the host rock scale as can be seen from the pore water profiles of the potential host rock Opalinus Clay at Mont Terri (Switzerland). The embedding aquifers are the hydro-geological boundaries, that established gradients in the 210 m thick low permeable section through diffusive exchange over millions of years. Present-day pore water profiles were confirmed by a data-driven as well as by a conceptual scenario. Based on the modelled profiles, the influence of the geochemical gradient on uranium migration was quantified by comparing the distances after one million years with results of common homogeneous models. Considering the heterogeneous system, uranium migrated up to 24 m farther through the formation depending on the source term position within the gradient and on the partial pressure of carbon dioxide pCO2 of the system. Migration lengths were almost equal for single- and multicomponent diffusion. Differences can predominantly be attributed to changes in the sorption capacity, whereby pCO2 governs how strong uranium migration is affected by the geochemical gradient. Thus, the governing parameters for uranium migration in the Opalinus Clay can be ordered in descending priority: pCO2, geochemical gradients, mineralogical heterogeneity.</p>},
  language  = {en}
}