Open Access

Autoclaved aerated concrete (AAC) is a building material that combines heat insulation properties with sufficient mechanical strength for masonry construction. Compared to ordinary concrete, the matrix is highly porous (>50%) and hardened by a hydrothermal curing process at 150°C - 200°C. During this process, quartz sand and portlandite react to form first calcium silicate hydrates (C-(A)-S-H) with Ca/Si ratios <1.3 and then tobermorite. Especially tobermorite, which has a much larger crystallite size than C-(A)-S-H, provides improved mechanical strength. This reaction sequence is influenced by many parameters and additives of which calcium sulfate is probably the most important. Despite several attempts to investigate these hydrothermal reactions, the actual reaction mechanism involved when adding sulfate ions is not fully understood. It has been suggested that the addition of ca. 1.5 wt% significantly improves the mechanical properties due to the enhanced formation and arrangement of tobermorite in the porous matrix. Since the sulfate content in AAC waste is exceeding regulatory threshold for low-quality reuse in some countries, the aim of this study was to investigate in detail the reaction mechanisms involving sulfate addition. Such knowledge may open up the possibility to improve AAC production and to avoid the need for sulfate addition. To achieve this goal, this research work focused on investigating the hydrothermal curing process to determine the sequence of hydrothermal reactions and the spatial distribution of the phases formed. For this purpose, a new setup for in situ X-ray diffraction was specifically designed to study hydrothermal reactions and to conduct time intensive experiments on a normal laboratory diffractometer. In order to quantitatively evaluate the in situ measurements by Rietveld analysis using TOPAS, it was also necessary to develop atomistic structure models for C-(A)-S-H phases. This was made possible by adopting a supercell approach that was previously used to describe turbostratically stacked clay minerals. The structure models, derived from tobermorite, are placed in an otherwise empty supercell to simulate the C-(A)-S-H nanostructure. Adopting these methodological advances, it was possible to obtain absolute phase quantities from in situ data and to track the reaction kinetics of the hydrothermal curing process. These results were then combined with ex situ X-ray diffraction and scanning electron microscopy. Confirming previous studies, the major effect of sulfate ions was the formation and decomposition of hydroxylellestadite. It was further revealed that C-(A)-S-H formation was delayed during hydroxylellestadite formation, which is supposed to support the silicate ion diffusion and hence the tobermorite formation at a stage critical for improved hardening of AAC. This can be linked to the formation of lower amounts of capillary pores in the range of 1-5 µm, as observed by scanning electron microscopy, and therefore a lower concentration of inherent defects that resulted in the improved mechanical properties. This research work highlights how important the spatial distribution of crystallites is for the properties of a building material and how this distribution can be influenced by small alterations in reaction chemistry.

The deep geological underground represents an important georesource for the short- term storage of renewable energy and the long-term reduction of greenhouse gas emissions. To ensure the economic viability and safety of any subsurface storage project, detailed characterisation of the quality and integrity of the reservoir and its cap rock is required. This characterisation includes the accurate determination of the petrophysical properties, such as porosity and permeability, as well as the potential mineral reactions, such as the dissolution of reactive phases, which may occur during the lifespan of such a project. Clay minerals are common components of many reservoir systems and, depending on their type and structure, can have a significant impact on storage and transport properties. These processes are, however, currently not well understood. In order to address these issues, the main focus of this thesis is on mineralogical analyses using X-ray diffraction (XRD) and microstructural studies using focused ion beam scanning electron microscopy (FIB-SEM) together with micro X-ray computed tomography (µXCT) to gain a better understanding of the influence of clay minerals on reservoir and cap rock properties. A central part of this thesis focuses on the analysis of clay minerals and pore structures of the Bebertal Sandstone of the Parchim Formation (Early Permian, Upper Rotliegend), which is considered a natural analogue for the tight reservoir sandstones of the North German Basin. Two illite polytypes with a variety of characteristic structures have been identified in the Bebertal sandstone. Disordered 1Md illite forms the majority of the observed structures, which include omnipresent grain coatings, altered permeable feldspar grains and pore-filling meshwork structures. Trans-vacant 1M illite represents the second and youngest generation of authigenic illite and occurs as fibrous to lath-shaped particles that grew into open pore spaces and led to a significant reduction in porosity and permeability during late diagenesis. Based on these results, a model for the formation of illite polytypes in the aeolian layers of the Bebertal sandstone was developed that describes the temporal and spatial evolution of porosity and permeability during diagenesis. Information from this model was then used to improve the prediction of permeability of the Bebertal sandstone based on µXCT pore space models and direct numerical simulations. To achieve this, a micro-scale pore space model was created that allowed the simulation of permeability reduction by clay minerals by including nanoporous illite domains based on a novel morphological algorithm. By performing Navier-Stokes-Brinkman simulations, more accurate predictions of permeabilities with respect to experimentally determined values were obtained compared to conventional Navier-Stokes simulations. The detailed characterisation of the Bebertal sandstone has shown that natural reservoir rocks are usually complex heterogeneous systems with small-scale variations in texture, composition, porosity and permeability. Flow-through experiments on the Bebertal sandstone revealed that the coupled geochemical and hydrodynamic processes that occur during the dissolution of calcite could not be predicted by reactive transport models. Therefore, as part of this thesis, a novel approach for developing synthetic sandstones at low temperatures based on geopolymer binder was developed. It is shown that simpler and more homogeneous porous materials can be produced with porosity and permeability values in the range of natural sandstones. These can be used to better understand the dynamic and coupled processes relevant to the storage of renewable energy in reservoir rocks through improved experimental constraints. The final part of this thesis reports on a detailed clay mineral and pore space study of three shale formations and one mudstone that were identified as potential seals for the Mt. Simon sandstone reservoir in the Illinois Basin. During the Illinois Basin - Decatur Project, this reservoir was used for the sequestration of one megaton of supercritical carbon dioxide. In order to better assess the quality of the sealing units and to better understand the role of the intergranular clay mineral matrix as potential pathway for fluid migration, a multi-scale evaluation was conducted that included thin section analysis, quantitative evaluation of minerals by scanning electron microscopy (QEMSCAN), mercury intrusion capillary pressure (MICP) measurements, quantitative XRD and high-resolution FIB-SEM. The results allow for the classification of the studied formations into primary and secondary seals and emphasise the importance of three-dimensional clay-mineral-related pore structure characterisations in cap rock studies. XRD proved the most reliable method for the identification and quantification of clay minerals in the studied cap rocks and mudstones. In contrast, FIB-SEM and QEMSCAN provided the spacial constraints for reconstructing fluid flow pathways within the clay mineral matrix. Overall, this thesis highlights the importance of the precise identification of clay minerals in geological reservoirs and their cap rocks. It also illustrates the need for three-dimensional characterisation and modelling of the associated small pore structures for an improved understanding of the rocks diagenetic history as well as the prediction of the transport and storage properties of these crustal reservoir systems.

Underground hard coal mining operations irreversibly disrupt the pre-existing mechanical equilibrium of the geological media. The employment of high-recovery methods modifies the stress field of the sedimentary sequence, generating movement and faulting of the rock layers above and below mined seams. These new fracture zones do affect the original conditions of the hydrogeological system by modifying flow pathways and increasing the permeability of the rock sequence. Moreover, the surface area of rock exposed to air and water is increased, conditioning the water-rock interaction. Despite this rather clear conceptualization, flow and reactive transport processes in fractured overburdens are rarely modeled simultaneously. Discrete setups that consider fractures and porous matrix require extensive characterization of both media, which is impractical for regional case studies. As a result, most post-mining models explicitly ignore fracture structures by employing the equivalent porous approach or even both media with lumped parameter models. However, omitting either medium represents a delicate simplification, considering that mining-related fractures control the rate and direction of water flow within moderately permeable but relatively highly porous rock sequences. In this dissertation, the specific contribution of fractured and matrix continua to the transient discharge and water quality of a post-mining coal zone is quantified and evaluated. For this purpose, dual and multiple interacting continua models are employed to simulate fluid flow and reactive mass transport in fractured and variable water-saturated rock sequences. The effectiveness of the models is evaluated by simulating the origin, generation and transport of acid mine drainage (i.e., water with elevated concentrations of hydrogen, iron, sulfate and chloride) within the shallow overburden of the Ibbenbüren Westfield. Compared to other coal districts in Germany, this area is strongly delimited by the local geology and topography, resulting in a well-defined hydrogeological system to test the models. Petrographic and chemical analyses performed on core samples from the area show the strong influence of mining-derived fractures on the water-rock interaction within the Carboniferous sequence. The presence of oxidized pyrite along with amorphous iron hydroxide phases in weathering fronts on both sides of the fractures demonstrates the exchange of solutes and gases between the fractured and the porous matrix media. Based on the previous evidence, the TOUGHREACT software is employed to characterize flow and reactive transport processes in the Westfield. However, each of the two processes is simulated at separate stages to have more control in the adjustment of sensitive parameters for which little information is available. For the flow component, a dual continuum model, with Richard’s equations is used to characterize the unsaturated water flow in both fractured and matrix media. Under this approach, the model adequately reproduces the bimodal flow behavior of the discharges measured in the mine drainage for the years 2008 and 2017. Simulation results show how the fractured continuum generates intense discharge events during the winter months while the rock matrix controls smooth discharge limbs in summer, when water is slowly released back to the fractures. With the flow component calibrated, the second part of the study incorporates the geochemical processes into the model based on actual data from the rock samples. Their simulation requires extending the two-continuum setup to a multiple continua model with five nested block strings: one for the fractures and four for the rock matrix. This further subdivision prevents under-representations of kinetic reactions with short equilibrium length scales and numerical instabilities due to lack of chemical and flow gradients. As a result, the new multiple continua model provides good agreement with respect to long- and short-term concentrations and discharge trends measured in the mine drainage. The flow of oxygen and meteoric water through the fractured continuum leads to a high and steady release of hydrogen, iron and sulfate ions derived from pyrite oxidation in the matrix continua closest to the fractures. Moreover, high chloride concentrations result from the mixing and gradual release of relatively immobile solutes in the matrix as they interact with percolating water in the fracture. Both findings are equally congruent with the reactive pyrite oxidation and iron hydroxide precipitation fronts identified in the fractured core samples. In the end, the multiple continua models, the simulation procedure and the results of the benchmark and sensitivity analysis scenarios developed for the Westfield pave the way for the application of the approach in other mining zones. The first candidate emerges in the Ibbenbüren Eastfield, where a coupled elemental-isotopic approach included in this thesis has confirmed that water-conducting fracture zones are primary elements for solute generation and transport in the first 300 meters of the overburden. In the latter case, calibration and verification of the models can be complemented with measurements of δ34S in sulfates and δ18O, δ2H, and Tritium in water.

Seas and oceans are essential for the global ecosystem. Entire societies, economies and countless livelihoods rely on their good environmental status. Yet, pressures on marine environments are increasing. An extensive assessment and monitoring of marine habitats is a vital precondition for understanding these systems and their sustainable conservation. Remote sensing methods can temporally accelerate the mapping, improve the spatial resolution and support the interpretation of large areas. Hydroacoustic becomes the method of choice for areas deeper than the coastal zone as optical signals are limited by strong attenuation in the water column. Apart from depth measurements for the creation of bathymetric charts, the recording of backscatter strength is useful for the characterization of the seafloor surface. The direct influence of the inhabiting benthic community on the backscattered signal is rarely considered, although it can be utilized for the detection of benthic life. Information about habitat-specific backscatter responses or a hydroacoustic remote sensing catalog for benthic habitats is missing so far. The multibeam echosounder (MBES) has the advantage of recording both, bathymetry and backscatter strength simultaneously with related incidence angle. Further, recent technological developments allow to change between frequencies. Angular range curves supported the quantification of backscatter strength of different frequencies. Acoustic data sets were complemented by ground truthing in form of sedimentological and biological samples as well as video profiles. Study areas were located offshore the island of Sylt in the North Sea as well as in vicinity to Oder Bank and close to the coast offshore Hohe Düne/Rostock, both in the Baltic Sea. Investigated habitats included sand areas inhabited by tubeworms, loose mussel clusters on top of sand areas, seagrass meadows, coarse sand and gravel areas, and a reef covered by mussels. Multifrequency backscatter maps, combining frequencies between 200 kHz and 700 kHz, illustrate small-scale features at the seafloor not visible in monofrequent maps. Key habitats showed a specific backscatter response, which can partly be related to macrobenthic flora and fauna. Data sets recorded with a (partly calibrated) MBES in three different month (May, August, October) revealed that backscatter strength can further detect spatial as well as temporal habitat dynamics. Alterations in the sediment composition at the seafloor surface of the ecologically valuable coarse sand and gravel areas were caused by seasonal changes in local hydrodynamics. A newly developed 3D seismic lander has the ability to support hydroacoustic remote sensing as an additional, non-destructive ground truthing method utilizing a high frequency of 130 kHz to image the shallow subsurface. Buried objects, e.g., stones, shells, fruit gummy worms, as well as sediment disturbances could be detected and visualized in a laboratory experiment. The 3D seismic lander is likely to improve the investigation of volume scatter contribution to backscatter strength and is potentially applicable for the imaging of bioturbation.

The dissertation looks at bioeconomy innovation at different levels through the lens of economic geography. By progressing from the meta to the micro-scale, it tries to find answers to how the interrelated concepts of bioeconomy and innovation are embedded in these respective contexts while consecutively concretising bioeconomy and de-fuzzing it. To do that, it adopts a mixed-methods approach that starts general and ends specific, going from the meta-scale of literature over the macro-scale of three distinct areas in which bioeconomy is discussed to the meso-level of central actors of a European funding network before, lastly, considering case studies at the micro-scale. Throughout, the thesis aims to spatialise the bioeconomy by shedding light on the term and its drivers across multiple geographic layers. It thereby not only offers new insights into dimensions of innovation in the bioeconomy but also contributes to the discipline of economic geography by applying some of its essential theoretical ideas to an emerging political framework.