University, Diss., 2004--Bremen.

Techn. Universiẗat, Diss., 2004--Darmstadt.

Im Umfeld von Delitzsch befinden sich unter der etwa 100 m mächtigen Bedeckung aus tertiären Lockersedimenten mehrere magmatische Körper aus Karbonat. Im Jahr 2012 wurde durch die Deutsche Rohstoff AG bei Storkwitz eine 700 m tiefe Explorationsbohrung auf Seltene Erden Elemente abgeteuft. Im Rahmen eines Forschungsprojektes wurde der Frage nachgegangen, wie und woher die Seltenen Erden in das Gestein hineingelangten. Die Ergebnisse können Hinweise auf möglicherweise bisher unbekannte Anreicherungen von Seltenen Erden in anderen Nebengesteinen als den Karbonatiten geben. Die Veröffentlichung liegt nur in englischer Sprache vor. / The Storkwitz-Carbonatite is a Late Cretaceous intrusive complex, which is well-explored by a relatively large number of exploration bore holes both from the 1970ies, 1980ies and from one more recent bore hole, SES-1/2012. The carbonatite complex hosts a (currently) marginally economic mineralisation of rare earth elements (REE) and niobium, which is technically still difficult to recover. The upper part of the carbonatitic body is located some 100-120 m below the Pre-Cenozoic land surface, which in turn is overlain by approximately 100 m of glacial, fluvio-glacial, and fluviatile sediments. The aim of this study was to characterize the mineralisation in the upper part of the intrusion geochemically and mineralogically and to try to identify indications of a supergene overprint on the late magmatic to hydrothermal mineralisation. Fresh drill core samples from the exploration bore hole SES-1/2012 have revealed that the mineralisation is associated with a carbonatitic igneous breccia body and also with several alvikite veins. The breccia body is very heterogeneous, displays a variety of matrix colours and also a range of matrix-to-clast ratios.

University, Diss., 2004--Tübingen.

University, Diss., 2004--Bremen.

Even in times of renewable energy revolution fossil fuels will play a major role in energy supply, transportation, and chemical industry. Therefore, increasing demand for crude oil will still have to be met in the next decades by developing new oil re-serves. To cope with this challenge, companies and researchers are constantly seeking for new methods to increase the recovery factor of oil fields. For that reason, many enhanced oil recovery (EOR) methods have been developed and applied in the field. EOR methods alter the physico-chemical conditions inside the reservoir. One possibility to achieve this is to inject an aqueous solution containing special chemicals into the oil-bearing zone. Polymers, for example, increase the viscosity of the injected water and hence improve the displacement of the oil to the production well. The injection of surfactant solutions results in reduced capillary forces, which retain the oil in the pores of the reservoir. Some surfactants form viscoelastic solutions under certain conditions. The possibil-ity to apply those solutions for enhanced oil recovery has been investigated by some authors in the last years in low salinity brines. Reservoir brines, however, often contain high salt concentrations, which have detrimental effects on the properties of many chemical solutions applied for EOR operations. The Triphenoxymethane derivatives, which were the subject of study in this thesis, form viscoelastic solutions even in highly saline brines. The aim of this thesis was to investigate the efficiency and the mode-of-action of this new class of chemical EOR molecules with respect to oil mobilization in porous media.

With a size of ~10,000 km² the Salar de Uyuni is the largest salt lake in the world. It is located at a height of 3,653 m a.s.l. in the southern part of the Bolivian Altiplano, an endorheic high plateau separating the Eastern and Western cordillera of the Andes. The salt flat is characterized by an alternating sequence of evaporate layers mainly consisting of halite and lacustrine mud layers up to a depth of at least 220 m, whereby the stratification is ascribed to the alternation of dry and humid climatic phases during the Quaternary. With estimated 7 Mio tonnes in brine, the salt lake is considered the world’s largest Li deposit. Knowledge About genesis and distribution of Li is essential for the possible extraction of Li and other valuable elements from the brine in a commercial scale, which is the driving force for the Investigation of hydrochemical properties of the Salar de Uyuni. Practical work comprised the sampling of brines from drilled wells and along transects, salts from the surface, sampling of streams, rocks and sediments in the catchment, as well as chemical and isotopical analyses. The surface catchment, delineated with ArcGIS, has a size of 63,000 km² and is mainly characterized by volcanic deposits as ignimbrites, and unconsolidated sediments, salt deposits and lacustrine material in widespread flood plains. The pores of the upper salt crust, which shows a varying thickness of 2-11 m, are filled with a saturated NaCl brine rich in Mg, K, Li and B. The distribution of Li along the salt lake is inhomogeneous, with two regions of significantly higher concentrations up to 1.5 g/L in the southern part near the delta of the main inflow Río Grande and in the northern part, compared to an average of 0.3-0.4 g/L in brine. The age of brines from the upper salt crust was determined to 6,200 - 13,340 years, corresponding in age to the surrounding evaporates and showing a stable stratification with depth. However, a local mixing of the brine with freshwater feeding from groundwater Aquifers especially near the shore of the salar was observed by the analysis of δ2H and δ18O in the brines. The distribution of stable isotopes also shows the strong influence of evaporation, even smaller tributaries feeding the Río Grande are enriched in heavy isotopes of H and O. Element to bromine ratios in the brine showed that Li, K and Mg are not removed from solution by the formation of precipitates, but are rather released from clay minerals by ion exchange leading to their enrichment in the pore brine. Analyzed rocks, mostly of rhyolitic and dacitic type, show moderate lithium concentrations in the range of 4 to 37 mg/kg. Different types of digestion revealed that rock types occurring in the Salar de Uyuni catchment are a substantial supplier of lithium by the intensive physical and chemical weathering due to the specific environmental conditions. Increased Lithium concentrations in rock and sediment samples from the volcano flanks south of the salar indicate, that the southern catchment is the main supplier of lithium to the salt lake. The enrichment of lithium could also be observed by the analysis of superficial salts from the upper crust. Salt efflorescences are significantly enriched regarding Li, K, Mg and other Ions compared to the surface within the polygons. The enrichment of Li in brine occurs all-Season along shrinkage cracks at polygon borders, where brine rises up, water evaporates and NaCl precipitates, leaving a solution even more concentrated in Li and other solutes as Br, B, K and Mg. In conclusion, the accumulation of lithium in the brine of the Salar de Uyuni results from the combination of various site-specific circumstances, which are analyzed and discussed in the present thesis. / Mit einer Größe von ~10.000 km² ist der Salar de Uyuni der größte Salzsee der Welt. Er befindet sich auf einer Höhe von 3.653 m im Süden des bolivianischen Altiplano, einer abflusslosen Hochebene zwischen der Ost- und Westkordillere der Anden. Der Salzsee besteht bis zu einer Tiefe von mind. 220 m aus einer Wechselfolge evaporitischer Schichten (hauptsächlich halitisch) und lakustrinen Tonschichten, wobei die Schichtung auf den Wechsel von trockenen und feuchten klimatischen Phasen während des Quartärs zurückzuführen ist. Mit einer geschätzten Menge von 7 Mio. t gilt der Salzsee als die gegenwärtig größte Li-Ressource der Welt. Das Wissen über Genese und Verteilung von Li ist grundlegend für eine mögliche Gewinnung von Li und anderen Elementen in kommerziellem Maßstab, worin sich die Motivitation für die Untersuchung hydrochemischer Eigenschaften des Salar de Uyuni begründet. Praktische Tätigkeiten umfassten die Probenahme von Solen aus eigens gebohrten Brunnen und entlang von Transekten, die Entnahme von Oberflächensalzen, die Beprobung von Zuflüssen, Gesteinen und Sedimenten im Einzugsgebiet, sowie deren chemische und isotopische Analytik. Das oberflächliche, mittels ArcGIS ermittelte Einzugsgebiet, weist eine Größe von 63.000 km² auf und besteht hauptsächlich aus vulkanischen Gesteinen wie Ignimbriten und unverfestigten Ablagerungen, Salzausblühungen und lakustrinen Sedimenten in ausgeprägten Überschwemmungsebenen. Die Poren der obersten, zwischen 2 und 11 m mächtigen Salzschicht, sind mit einer an NaCl gesättigten Salzlösung, die reich an Mg, K, Li und B ist, gefüllt. Die inhomogene Verteilung von Li im Salzsee weist zwei Bereiche signifikant erhöhter Konzentrationen von bis zu 1,5 g/L auf, und zwar im südlichen Einmündungsbereich des Hauptzuflusses Río Grande und im Nordosten etwa 20 km von der Küste entfernt, verglichen mit einem durchschnittlichen Gehalt von 0,3-0,4 g/L in der Sole. Das Alter der Solen der obersten Salzkruste wurde auf 6.200 – 13.340 Jahre bestimmt, was dem Alter der umgebenden Evaporite entspricht und eine stabile Schichtung aufweist. Allerdings weist die Analytik von δ2H und δ18O auch auf eine lokale Vermischung der Sole mit Frischwasser aus ufernahen Aquiferen hin. Die Verteilung der stabilen Isotope δ²H und δ18O deutet auf einen signifikanten Einfluss der Verdunstung auf die Entwicklung der Porenlösung hin, denn auch kleinere Zuflüsse zum Salar sind angereichert an 2H und 18O. Das Verhältnis verschiedener Elemente zu Brom zeigt, dass Li, K und Mg weniger durch die Ausfällung von Salzen aus der Lösung entfernt, sondern eher durch Ionenaustausch aus Tonmineralen freigesetzt und folglich in der Sole angereichert werden. Die analysierten Gesteine, hauptsächlich rhyolitischen und dazitischen Typs, weisen moderate Lithiumkonzentrationen von 4 – 37 mg/kg auf. Die Anwendung verschiedener Aufschlüsse zeigte, dass die im Einzugsgebiet des Salar de Uyuni vorkommenden Gesteinstypen aufgrund der intensiven physikalischen und chemischen Verwitterung unter den spezifischen Umweltbedingungen eine wesentliche Quelle des Lithiums im Salzsee sind. Erhöhte Li-Konzentrationen in Gesteinen und Sedimenten der vulkanischen Flanken südlich des Salars deuten auf das südliche Einzugsgebiet als hauptsächlichen Zulieferer für Li hin. Die Anreicherung von Li wurde auch mittels der Untersuchung der Salze der obersten Kruste bestätigt. Im Vergleich zur Oberfläche innerhalb der Polygone sind die Salzausblühungen entlang der Polygonränder signifikant an Li, K, Mg und anderen Ionen angereichert. Die Anreicherung von Li geschieht ganzjährig entlang der Schrumpfungsrisse an Polygonrändern, indem die Sole durch kapillare Kräfte aufsteigt, Wasser verdunstet und NaCl ausfällt. Schließlich bleibt eine an Li und anderen Ionen wie Br, B, K und Mg noch stärker aufkonzentrierte Lösung zurück. Schlussfolgernd resultiert die Akkumulation von Lithium in der Porenlösung aus der Kombination zahlreicher standortspezifischer Faktoren, welche innerhalb der vorliegenden Arbeit untersucht und bewertet wurden.

Even in times of renewable energy revolution fossil fuels will play a major role in energy supply, transportation, and chemical industry. Therefore, increasing demand for crude oil will still have to be met in the next decades by developing new oil re-serves. To cope with this challenge, companies and researchers are constantly seeking for new methods to increase the recovery factor of oil fields. For that reason, many enhanced oil recovery (EOR) methods have been developed and applied in the field. EOR methods alter the physico-chemical conditions inside the reservoir. One possibility to achieve this is to inject an aqueous solution containing special chemicals into the oil-bearing zone. Polymers, for example, increase the viscosity of the injected water and hence improve the displacement of the oil to the production well. The injection of surfactant solutions results in reduced capillary forces, which retain the oil in the pores of the reservoir. Some surfactants form viscoelastic solutions under certain conditions. The possibil-ity to apply those solutions for enhanced oil recovery has been investigated by some authors in the last years in low salinity brines. Reservoir brines, however, often contain high salt concentrations, which have detrimental effects on the properties of many chemical solutions applied for EOR operations. The Triphenoxymethane derivatives, which were the subject of study in this thesis, form viscoelastic solutions even in highly saline brines. The aim of this thesis was to investigate the efficiency and the mode-of-action of this new class of chemical EOR molecules with respect to oil mobilization in porous media.

Driven by the need to use mineral resources more sustainably, and the increasing complexity of ore deposits still available for commercial exploitation, the acquisition of quantitative data on mineralogy and microfabric has become an important need in the execution of exploration and geometallurgical test programmes. Hyperspectral drill-core scanning has the potential to be an excellent tool for providing such data in a fast, non- destructive and reproducible manner. However, there is a distinct lack of integrated methodologies to make use of these data through-out the exploration and mining chain. This thesis presents a first framework for the use of hyperspectral drill-core scanning as a pillar in exploration and geometallurgical programmes. This is achieved through the development of methods for (1) the automated mapping of alteration minerals and assemblages, (2) the extraction of quantitative mineralogical data with high resolution over the drill-cores, (3) the evaluation of the suitability of hyperspectral sensors for the pre-concentration of ores and (4) the use of hyperspectral drill- core imaging as a basis for geometallurgical domain definition and the population of these domains with mineralogical and microfabric information.:Introduction Materials and methods Assessment of alteration mineralogy and vein types using hyperspectral data Hyperspectral imaging for quasi-quantitative mineralogical studies Hyperspectral sensors for ore beneficiation 3D integration of hyperspectral data for deposit modelling Concluding remarks References

Considering the ever-growing global demand for raw materials and the complexity of the geological deposits that are still to be found, high-quality extensive mineralogical information is required. Mineral exploration remains a risk-prone process, with empirical approaches prevailing over data-driven strategy. Amongst the many ways to innovate, hyperspectral imaging sensors for drill-core mineral mapping are one of the disruptive technologies. This potential could be multiplied by implementing machine learning. This dissertation introduces a workflow that allows the use of supervised learning to map minerals by means of ancillary data commonly acquired during exploration campaigns (i.e., mineralogy, geochemistry and core photography). The fusion of hyperspectral with such ancillary data allows not only to upscale to complete boreholes information acquired locally, but also to enhance the spatial resolution of the mineral maps. Thus, the proposed approaches provide digitally archived objective maps that serve as vectors for exploration and support geologists in their decision making.:List of Figures xviii List of Tables xix List of Acronyms xxi 1 Introduction 1 1.1 Mineral resources and the need for innovation . . . . . . . . . . . . . 2 1.2 Spectroscopy and hyperspectral imaging . . . . . . . . . . . . . . . . 5 1.2.1 Imaging spectroscopy ....................... 6 1.2.2 Spectroscopy of minerals ..................... 8 1.2.3 Mineral mapping.......................... 12 1.2.4 Mineral mapping in exploration ................. 15 1.2.5 Drill-core mineral mapping.................... 16 1.3 Machine learning .............................. 19 1.3.1 Supervised learning for drill-core hyperspectral data . . . . . 20 1.4 Motivation and approach ......................... 22 2 Hyperspectral mineral mapping using supervised learning and mineralogical data 25 Preface ....................................... 25 Abstract....................................... 26 2.1 Introduction ................................. 27 2.2 Data acquisition............................... 30 2.2.1 Hyperspectral data......................... 30 2.2.2 High-resolution mineralogica ldata . . . . . . . . . . . . . . . 31 2.3 Proposed system architecture ....................... 33 2.3.1 Re-sampling and co-registration ................. 33 2.3.2 Classification ............................ 35 2.4 Experimental results ............................ 36 2.4.1 Data description .......................... 36 2.4.2 Experimental setup......................... 37 2.4.3 Quantitative and qualitative assessment . . . . . . . . . . . . . 37 2.5 Discussion.................................. 40 2.6 Conclusion.................................. 42 3 Geochemical and hyperspectral data integration 45 Preface ....................................... 45 Abstract....................................... 46 3.1 Introduction ................................. 47 3.2 Basis for the integration of geochemical and hyperspectral data . . . 50 3.3 Proposed approach ............................. 51 3.3.1 Geochemical data labeling..................... 51 3.3.2 Superpixel segmentation ..................... 53 3.3.3 Classification ............................ 53 3.4 Experimental results ............................ 54 3.4.1 Data description .......................... 54 3.4.2 Data acquisition........................... 55 3.4.3 Experimental setup......................... 55 3.4.4 Assessment of the geochemical data labeling . . . . . . . . . . 58 3.4.5 Quantitative and Qualitative Assessment . . . . . . . . . . . . 58 3.5 Discussion.................................. 61 3.6 Conclusion.................................. 63 4 Improved spatial resolution for mineral mapping 65 Preface ....................................... 65 Abstract....................................... 66 4.1 Introduction ................................. 67 4.2 Methods: Resolution Enhancement for Mineral Mapping . . . . . . . 69 4.2.1 Hyperspectral Resolution Enhancement . . . . . . . . . . . . . 69 4.2.2 Mineral Mapping.......................... 71 4.2.3 Supervised Classification ..................... 71 4.3 Case Study.................................. 72 4.3.1 Data Acquisition .......................... 72 4.3.2 Resolution Enhancement Application . . . . . . . . . . . . . . 74 4.3.3 Evaluation of the Resolution Enhancement . . . . . . . . . . . 75 4.4 Results .................................... 76 4.4.1 Mineral Mapping.......................... 76 4.4.2 Supervised Classification ..................... 77 4.4.3 Validation .............................. 80 4.5 Discussion.................................. 82 4.6 Conclusions ................................. 84 5 Bibliography 92