In order to meet increasing indium demands, (bio)hydrometallurgical winning of low-grade sources will likely be required. The goal of this work in the scope of the Biohydrometallurgical Centre Freiberg, was to use geochemical modelling to improve indium leaching and extraction efficiency. Indium stability constants and chemical conditions of process relevant solutions were required. Electrochemical methods were used to determine the stability constants of indium complexes with nitrate, chloride, sulfate, and hydroxide ions, as well as with electrowinning additives. High pressure liquid chromatography techniques were adapted to quantify polysulfides (Sx2–) and metal ions in leaching and extraction solutions. This cumulative information was used in geochemical modelling. Predominance, Pourbaix, and speciation diagrams were produced to describe and explain the behaviour of multiple components in various process relevant solutions. / Um den steigenden Bedarf an Indium zu decken, ist eine (bio-)hydrometallurgische Gewinnung von ‚low-grade sources‘ erforderlich. Ziel dieser Arbeit im Rahmen des Biohydrometallurgischen Zentrums Freiberg war es, durch geochemische Modellierung die Indium-Laugungs- und Extraktionseffizienz zu verbessern. Dazu wurden Indium-Stabilitätskonstanten und chemische Bedingungen prozessrelevanter Lösungen benötigt. Mit elektrochemischen Methoden wurden die Stabilitätskonstanten von Indiumkomplexen mit Nitrat-, Chlorid-, Sulfat- und Hydroxidionen sowie mit Elektrogewinnungsadditiven bestimmt. Hochdruck-Flüssigkeitschromatographieverfahren wurden zur Quantifizierung von Polysulfiden (Sx2–) und Metallionen in Laugungs- und Extraktionslösungen angepasst. Alle experimentell bestimmten Parameter wurden in der geochemischen Modellierung verwendet. Prädominanz-, Pourbaix- und Speziationsdiagramme wurden erstellt, um das Verhalten mehrerer Komponenten in verschiedenen prozessrelevanten Lösungen zu beschreiben und zu erklären.

Indium gilt als eines der strategischen Metalle für die Technologiebranche. Durch das schnelle Wachstum bei Flachbildschirmen aller Art besteht seit Jahren eine stark wachsende Nachfrage nach Indium. Es wurde ein neuartiger Ansatz der Biolaugung gewählt und innerhalb des BHMZ getestet, Die aus der Biolaugung resultierende Lösung enthielt vereinfacht 1 mg·L-1 Indium sowie jeweils 1 g·L-1 Zink und Eisen. Durch systematische Untersuchung von zahlreichen hydrometallurgischen Methoden zur Metallabtrennung wurde eine auf Flüssig-Flüssig-Extraktion basierte Methode entworfen und erprobt. Der Prozess ermöglicht eine Indiumanreicherung bis zum Indiumhydroxid in einer Reinheit von 99,99 %. Die Chemikalienkosten für diesen Prozess belaufen sich gegenwärtig, bezogen auf den Labormaßstab, auf 189,40 €·kg-1 Indium. Diese liegen unter dem aktuellen Marktpreis von Indium. Die bisherigen Ergebnisse belegen, dass in der Realisierung dieses Verfahrens im technischen Maßstab erhebliches wirtschaftliches Potential steckt.

Different aspects of interaction of metals other than iron with metallophore mixtures were elucidated. Metal chelation besides iron and greater than with pure desferrioxamine B is documented by enhanced performance of soil mineral dissolution following application of diverse metallophore mixtures. New insights from genome to product of metallophores from Gordonia rubripertincta CWB2 under different cultivation conditions and under metal stress, particularly induced by rare earth elements are given. This evaluation led to increase by a factor of 13. Structure analyses showed that the strain produces citrate and different desferrioxamines. A robust RP-HPLC-based method quantified metal complexation. Further metal immobilization methods for metallophores for metal extraction from solutions with low concentrations were established. Moreover, catechol and hydroxamate metallophores from Arthrobacter oxydans ATW2 and Kocuria rosea ATW4 demonstrate the enhancement of Ge and rare earth element bioavailability, plant growth promotion and phytoextraction potential.:CONTENTS Abstract ..........................................................................................................1 CHAPTER 1 Introduction ......................................................................................5 CHAPTER 2 Mobilization of trace elements in soil extracts by bacterial siderophores in dependence of the pH-value..................................31 CHAPTER 3 Cultivation dependent formation of siderophores by Gordonia rubripertincta CWB2........................................................................41 CHAPTER 4 Data on metal-chelating, -immobilization and biosorption properties by Gordonia rubripertincta CWB2 in dependency on rare earth adaptation.......................................................................................67 CHAPTER 5 Analysis of desferrioxamine-like siderophores and their capability to selectively bind metals and metalloids: development of a robust analytical RP-HPLC method. ..........................................................97 CHAPTER 6 Secondary metabolites released by the rhizosphere bacteria Arthrobacter oxydans and Kocuria rosea enhance plant availability and soil–plant transfer of germanium (Ge) and rare earth elements (REEs) .........................................................................................120 CHAPTER 7 Conclusion remarks and further perspectives ...............................154 References .......................................................................................................162 Acknowledgement .........................................................................................185 Curriculum Vitae ..........................................................................................187 List of publications ..........................................................................................189 List of oral and poster presentations ..........................................................190 List of proceedings ..........................................................................................191 / En este trabajo se han dilucidado diferentes aspectos de la interacción de los metales con las mezclas de metalóforos desde distintos ángulos. La quelación de metales por debajo del hierro se pone de manifiesto en la mejora del rendimiento de la disolución de los minerales del suelo debido a la aplicación de diversas mezclas de metanóforos en comparación con la deferoxamina B pura. Se ofrecen nuevos conocimientos desde el genoma hasta el producto de los metanóforos de Gordonia rubripertincta CWB2 en diferentes condiciones de cultivo y bajo estrés por metales, especialmente inducido por elementos de tierras raras. Esta evaluación condujo a una sobreproducción de un factor de 13. El análisis estructural muestra que la cepa produce citrato y diferentes desferrioxaminas. Un método robusto basado en RP-HPLC cuantificó la complejación de metales. Se establecieron otros métodos de inmovilización de metales para la extracción de metales a partir de soluciones poco concentradas. Además, los metalóforos de catecol e hidroxamato de Arthrobacter oxydans ATW2 y Kocuria rosea ATW4 demuestran la mejora de la biodisponibilidad de GE y REE, la promoción del crecimiento vegetal y el potencial de fitoextracción.:CONTENTS Abstract ..........................................................................................................1 CHAPTER 1 Introduction ......................................................................................5 CHAPTER 2 Mobilization of trace elements in soil extracts by bacterial siderophores in dependence of the pH-value..................................31 CHAPTER 3 Cultivation dependent formation of siderophores by Gordonia rubripertincta CWB2........................................................................41 CHAPTER 4 Data on metal-chelating, -immobilization and biosorption properties by Gordonia rubripertincta CWB2 in dependency on rare earth adaptation.......................................................................................67 CHAPTER 5 Analysis of desferrioxamine-like siderophores and their capability to selectively bind metals and metalloids: development of a robust analytical RP-HPLC method. ..........................................................97 CHAPTER 6 Secondary metabolites released by the rhizosphere bacteria Arthrobacter oxydans and Kocuria rosea enhance plant availability and soil–plant transfer of germanium (Ge) and rare earth elements (REEs) .........................................................................................120 CHAPTER 7 Conclusion remarks and further perspectives ...............................154 References .......................................................................................................162 Acknowledgement .........................................................................................185 Curriculum Vitae ..........................................................................................187 List of publications ..........................................................................................189 List of oral and poster presentations ..........................................................190 List of proceedings ..........................................................................................191 / Es wurden verschiedene Aspekte der Wechselwirkung von anderen Metallen als Eisen mit Metallophormischungen untersucht. Die Chelatbildung mit anderen Metallen als Eisen, die größer ist als bei reinem Desferrioxamin B, wird durch eine verbesserte Leistung bei der Auflösung von Bodenmineralien nach Anwendung verschiedener Metallophormischungen dokumentiert. Es werden neue Erkenntnisse vom Genom bis zum Produkt von Metallophoren aus Gordonia rubripertincta CWB2 unter verschiedenen Anbaubedingungen und unter Metallstress, insbesondere induziert durch Seltene Erden, gegeben. Diese Auswertung führte zu einer Steigerung um den Faktor 13. Strukturanalysen zeigten, dass der Stamm Citrat und verschiedene Desferrioxamine produziert. Eine robuste RP-HPLC-basierte Methode quantifizierte die Metallkomplexierung. Weitere Methoden zur Metallimmobilisierung von Metallophoren für die Metallextraktion aus Lösungen mit niedrigen Konzentrationen wurden etabliert. Darüber hinaus zeigen Catechol- und Hydroxamat-Metallophore aus Arthrobacter oxydans ATW2 und Kocuria rosea ATW4 die Verbesserung der Bioverfügbarkeit von Ge und Seltenen Erden, die Förderung des Pflanzenwachstums und das Phytoextraktionspotenzial.:CONTENTS Abstract ..........................................................................................................1 CHAPTER 1 Introduction ......................................................................................5 CHAPTER 2 Mobilization of trace elements in soil extracts by bacterial siderophores in dependence of the pH-value..................................31 CHAPTER 3 Cultivation dependent formation of siderophores by Gordonia rubripertincta CWB2........................................................................41 CHAPTER 4 Data on metal-chelating, -immobilization and biosorption properties by Gordonia rubripertincta CWB2 in dependency on rare earth adaptation.......................................................................................67 CHAPTER 5 Analysis of desferrioxamine-like siderophores and their capability to selectively bind metals and metalloids: development of a robust analytical RP-HPLC method. ..........................................................97 CHAPTER 6 Secondary metabolites released by the rhizosphere bacteria Arthrobacter oxydans and Kocuria rosea enhance plant availability and soil–plant transfer of germanium (Ge) and rare earth elements (REEs) .........................................................................................120 CHAPTER 7 Conclusion remarks and further perspectives ...............................154 References .......................................................................................................162 Acknowledgement .........................................................................................185 Curriculum Vitae ..........................................................................................187 List of publications ..........................................................................................189 List of oral and poster presentations ..........................................................190 List of proceedings ..........................................................................................191

The aim of the EU BIOMOre Project is to investigate the potential to extract copper from Sandstone formations in the North-Sudetic Trough which lies along the border between Poland and Germany. A new mining concept called bioleaching shall be applied in thin and very low permeable copper mineralization zones (order of 0.2 mD). Briefly, bioleaching process is the injection of a lixiviant (sulphur acid containing ferric iron) and then extraction of a pregnant leach solution through boreholes at the ground surface. This concept requires another special technique which is called hydraulic stimulation. Cracks along a wellbore are generated by pumping large quantity of fluid under high pressure into a cased section of rock during a hydraulic stimulation. This work at hand focuses on the geotechnical methods and scientific-engineering approaches used for extracting copper from very thin mineralization zones. The geological setting with faults and in situ stress state of the exploration zone is generated using measurements, visualised by 3D CAD model (RHINO), and computed via the Discrete Element code 3DEC. The preliminary drilling (stacked dual lateral wellbore) and stimulation design (plug-and-perf completion) are selected based on comprehensive literature survey and industry-based consultancy. In order to calibrate the calculated stress state in 3D, candidate sites for the hypothetical drilling-stimulation are detected using 2D GIS map (QGIS) at CAD model (RHINO). Trend of calculated stresses is in good agreement with the measured ones (σH > σv > σh). The final decision of selecting a drilling-stimulation site is made by using both GIS map and 3D CAD model. A hypothetical drilling-stimulation can be performed up to the depth of 1564 m in the Rotliegend & Grauliegend Sandstone with shale, which is overlain by (Zechstein) Limestone. During a possible stimulation, limestone’s integrity as a caprock and as a stress barrier is of great importance in addition to connect two lateral wellbores for facilitating flow of lixiviant. The preliminary geometrical design of stimulation is set with the cluster spacing (distance between fractures) of 20 m. Subsequent to final cost estimation of selected preliminary drilling-stimulation design, it is decided to use pinpoint (1,200,000 Euro) instead of plug-and-perf completion (2,345,300 Euro) since it is more economical. A possible drilling operation is anticipated to cost approximately 9,000,000 Euro. The 3D in situ stress model is calibrated before transferring of stress state into the sub-model which is used to optimise the selected stimulation design. The results of the last (DEM) sub-model are employed to reduce costs, to enhance the connection between branches of wellbores for bioleaching and to hinder possible penetration of fractures into the caprock. The preliminary geometrical design of stimulation is then modified based on these calculation results while increasing the cluster spacing from 20 m to 40 m. This is performed due to high stress-shadows (alteration of the stresses between fractures in a stimulation) encountered at the preliminary calculations. Results showed that, after the 80 seconds injection duration of water with 0.16 m3/sec into the sandstone, two wellbore laterals are expected to be connected by three generated cracks. They exhibit average aperture and transmissivity of 4.1 mm and 5.8 . 10-8 m2/sec, respectively. Furthermore, fracture initiation pressure ranges between 30 – 35 MPa at the drilling depth. The conclusions can be drawn that through the assessment of 3D CAD, GIS, and numerical DEM modelling methods, approximately 49% of cost reduction can be achieved by employing pinpoint instead of plug-and-perf completion. That is an important proof of the systematically approach for a stimulation planning wherein all necessary phases such as in situ stress estimation, modelling and cost assessment should have been considered. This work can be considered as a milestone for studies of stimulation designs which has been newly initiated in the EU-Region as a promising method for efficiency considering unconventional ore extraction. Moreover, this dissertation revealed again the emerging importance of integrated geotechnical information systems analogous to BIM (Building Information Systems).:LIST OF FIGURES LIST OF TABLES NOMENCLATURE ABSTRACT ZUSAMMENFASSUNG ACKNOWLEDGEMENTS 1. OUTLINE AND OBJECTIVE OF THE DISSERTATION 2. STATE OF THE ART 2.1. INTRODUCTION TO STIMULATION TECHNOLOGIES, EQUIPMENT AND DESIGNS 2.1.1. Technical instruments and frac-materials 2.1.2. Wellbore completion designs 2.1.3. Location and orientation of a wellbore 2.1.4. Fracture placement designs 2.1.5. Summary and conclusions 2.2. MEASUREMENT AND MODELLING OF UNDERGROUND STRESS FIELD 3. DETERMINATION AND MODELLING OF IN SITU STRESS FIELD IN THE NORTH SUDETIC TROUGH 3.1. GEOLOGICAL SETTING OF THE MODELLED REGION 3.2. SIMULATION OF THE IN SITU STRESS FIELD 3.2.1. Determination of the stress regime by measurements 3.2.2. Stepwise procedure of the stress field modelling 3D CAD assisted structural model of geological setting 3D DEM model for stress field simulations 2D GIS maps used for detection of drilling-stimulation sites 4. DRILLING AND WELLBORE DESIGN CALCULATIONS WITH COST ESTIMATION 4.1. DESIGN CALCULATIONS AND TECHNICAL REQUIREMENTS OF DRILLING AND WELLBORE 4.2. ECONOMICAL EVALUATION OF THE SELECTED DRILLING AND WELLBORE DESIGN 5. MODELLING OF THE HYDRAULIC STIMULATION AT THE SELECTED DRILLING SITE IN SANDSTONE 5.1. FINAL CALIBRATION OF THE 3D STRESS FIELD MODELS 5.2. DISCRETE ELEMENT MODELLING OF THE STIMULATION DESIGN AT THE SELECTED DRILLING SITE 5.3. DESIGN OPTIMIZATION STUDY OF THE STIMULATION MODEL AND FINAL COST ESTIMATION 6. SUMMARY AND CONCLUSIONS REFERENCES APPENDIX-A APPENDIX-B APPENDIX-C

These are the abstracts of the oral presentations of the 6th PhD conference held on 10. June 2022 in Freiberg.