Lithium Cesium Tantalum (LCT) pegmatites are important resources for rare metals like Cesium, Lithium or Tantalum, whose demand increased markedly during the past decade. At present, Cs is known to occur in economic quantities only from the two LCT pegmatite deposits at Bikita located in Zimbabwe and Tanco in Canada. Host for this Cs mineralisation is the extreme rare zeolite group mineral pollucite. However, at Bikita and Tanco, pollucite forms huge massive, lensoid shaped and almost monomineralic pollucite mineralisations that occur within the upper portions of the pegmatite. In addition, both pegmatite deposits have a comparable regional geological background as they are hosted within greenstone belts and yield a Neoarchean age of about 2,600 Ma. Furthermore, at present the genesis of these massive pollucite mineralisations was not yet investigated in detail. Major portions of Western Australia consist of Meso- to Neoarchean crustal units (e.g., Yilgarn Craton, Pilbara Craton) that are known to host a large number of LCT pegmatite systems. Among them are the LCT pegmatite deposits Greenbushes (Li, Ta) and Wodgina (Ta, Sn). In addition, small amounts of pollucite were recovered from one single diamond drill core at the Londonderry pegmatite field. Despite that, no systematic investigations and/or exploration studies were conducted for the mode of occurrence of Cs and especially that of pollucite in Western Australia. In the course of the present study nineteen individual pegmatites and pegmatite fields located on the Yilgarn Craton, Pilbara Craton and Kimberley province have been visited and inspected for the occurrence of the Cs mineral pollucite. However, no pollucite could be detected in any of the investigated pegmatites. Four of the inspected LCT-pegmatite systems, namely the Londonderry pegmatite field, the Mount Deans pegmatite field, the Cattlin Creek LCT pegmatite deposit (Yilgarn Craton) and the Wodgina LCT pegmatite deposit (Pilbara Craton) was sampled and investigated in detail. In addition, samples from the Bikita pegmatite field (Zimbabwe Craton) were included into the present study in order to compare the Western Australian pegmatites with a massive pollucite mineralisation bearing LCT pegmatite system. This thesis presents new petrographical, mineralogical, mineralchemical, geochemical, geochronological, fluid inclusion and stable and radiogenic isotope data. The careful interpretation of this data enhances the understanding of the LCT pegmatite systems in Western Australia and Zimbabwe. All of the four investigated LCT pegmatite systems in Western Australia, crop out in similar geological settings, exhibit comparable internal structures, geochemistry and mineralogy to that of the Bikita pegmatite field in Zimbabwe. Furthermore, in all LCT pegmatite systems evidences for late stage hydrothermal processes (e.g., replacement of feldspars) and associated Cs enrichment (e.g., Cs enriched rims on mica, beryl and tourmaline) is documented. With the exception of the Wodgina LCT pegmatite deposit, that yield a Mesoarchean crystallisation age (approx. 2,850 Ma), all other LCT pegmatite systems gave comparable Neoarchean ages of 2,630 Ma to 2,600 Ma. The almost identical ages of the LCT pegmatite systems of the Yilgarn and Zimbabwe cratons suggests, that the process of LCT pegmatite formation at the end of the Neoarchean was active worldwide. Nevertheless, essential distinguishing feature of the Bikita pegmatite field is the presence of massive pollucite mineralisations that resulted from a process that is not part of the general development of LCT pegmatites and is associated with the extreme enrichment of Cs. The new findings of the present study obtained from the Bikita pegmatite field and the Western Australian LCT pegmatite systems significantly improve the knowledge of Cs behaviour in LCT pegmatite systems. Therefore, it is now possible to suggest a genetical model for the formation of massive pollucite mineralisations within LCT pegmatite systems. LCT pegmatites are generally granitic in composition and are interpreted to represent highly fractionated and geochemically specialised derivates from granitic melts. Massive pollucite mineralisation bearing LCT pegmatites evolve from large and voluminous pegmatite melts that intrude as single body along structures within an extensional tectonic setting. After emplacement, initial crystallisation will develop the border and wall zone of the pegmatites, while due to fractionated crystallisation immobile elements (i.e., Cs, Rb) become enriched within the remaining melt and associated hydrothermal fluids. Following this initial crystallisation, a relatively small portion (0.5–1 vol.%) of immiscible melt or fluid will separate during cooling. This immiscible partial melt/fluid is enriched in Al2O3 and Na2O, as well as depleted in SiO2 and will crystallise as analcime. In addition, this melt might allready contains up to 1–2 wt.% Cs2O. However, due to the effects of fluxing components (e.g., H2O, F, B) this analcime melt becomes undercooled which prevents crystallisation of the analcime as intergranular grains. Since this analcime melt exhibits a lower relative gravity when compared to the remaining pegmatite melt the less dense analcime melt will start to ascent gravitationally and accumulate within the upper portion of the pegmatite sheet. At the same time, the remaining melt will start to crystallise separately and form the inner portions of the pegmatite. This crystallisation is characterised by still ongoing fractionation and enrichment of incompatible elements (i.e., Cs, Rb) within the last crystallising minerals (e.g., lepidolite) or concentration of these incompatible elements within exsolving hydrothermal fluids. As analcime and pollucite form a continuous solid solution series, the analcime melt is able to incorporate any available Cs from the melt and/or associated hydrothermal fluids and crystallise as Cs-analcime in the upper portion of the pegmatite sheet. Continuing hydrothermal activity and ongoing substitution of Cs will then start to shift the composition from Cs-analcime composition towards Na-pollucite composition. In addition, if analcime is cooled below 400 °C it is subjected to a negative thermal expansion of about 1 vol.%. This contraction results in the formation of a prominent network of cracks that is filled by late stage minerals (e.g., lepidolite, quartz, feldspar and petalite). Certainly, prior to filling, this network of cracks enhances the available conduits for late stage hydrothermal fluids and the Cs substitution mechanism within the massive pollucite mineralisation. Furthermore, during cooling of the pegmatite, prominent late stage mineral replacement reactions (e.g., replacement of K-feldspar by lepidolite, cleavelandite, and quartz) as well as subsolidus self organisation processes in feldspars take place. These processes are suggested to release additional incompatible elements (e.g., Cs, Rb) into late stage hydrothermal fluids. As feldspar forms large portions of pegmatite a considerable amount of Cs is released and transported via the hydrothermal fluids towards the massive pollucite mineralisation in the upper portion of the pegmatite. Consequently, the initial analcime can accumulate enough Cs in order to shift its composition from the Cs-analcime member (>2 wt.% Cs2O) towards the Na-pollucite member (23–43 wt.% Cs2O) of the solid solution series. The timing of this late stage Cs enrichment is interpreted to be quasi contemporaneous or immediately after the complete crystallisation of the pegmatite melt. However, much younger hydrothermal events that overprint the pegmatite are also interpreted to cause similar results. Hence, it has been demonstrated that the combination of this magmatic and hydrothermal processes is capable to generate an extreme enrichment in Cs in order to explain the formation of massive pollucite mineralisations within LCT pegmatite systems. This genetic model can now be applied to evaluate the potential for occurrences of massive pollucite mineralisations within LCT pegmatite systems in Western Australia and worldwide.:Contents Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii Zusammenfassung . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v Versicherung . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix Contents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi 1. Introduction 1 1.1. Motivation and Scope of the Thesis . . . . . . . . . . . . . . . . . . . . . . . . 1 1.2. Structure of the Thesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 2. Fundamentals 7 2.1. The Alkali Metal Cesium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 2.1.1. Distribution of Cesium . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 2.1.2. Mineralogy of Cesium . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 2.1.3. Geochemical Behaviour of Cesium . . . . . . . . . . . . . . . . . . . . 13 2.1.4. Economy of Cesium . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15 2.2. Pollucite – (Cs,Na)2Al2Si4O12×H2O . . . . . . . . . . . . . . . . . . . . . . . . 16 2.2.1. Crystal Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16 2.2.2. Analcime–Pollucite–Series . . . . . . . . . . . . . . . . . . . . . . . . . 17 2.2.3. Formation of Pollucite . . . . . . . . . . . . . . . . . . . . . . . . . . . 17 2.2.4. Pollucite Occurences . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 2.3. Pegmatites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34 2.3.1. General Characteristics of Pegmatites . . . . . . . . . . . . . . . . . . 34 2.3.2. Controls on Pegmatite Formation and Evolution . . . . . . . . . . . . . 40 2.3.3. Pegmatite Age Distribution and Continental Crust Formation . . . . . . 43 3. Geological Settings of Archean Cratons 47 3.1. Zimbabwe Craton . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47 3.1.1. Tectonostratigraphic Subdivision . . . . . . . . . . . . . . . . . . . . . 48 3.1.2. Tectonometamorphic Evolution of the Northern Limpopo Thrust Zone . 49 3.1.3. Pegmatites within the Zimbabwe Craton . . . . . . . . . . . . . . . . . 52 3.1.4. Masvingo Greenstone Belt . . . . . . . . . . . . . . . . . . . . . . . . . 53 3.1.5. Geological Setting of the Bikita Pegmatite District . . . . . . . . . . . . 58 3.2. Yilgarn Craton . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62 3.2.1. Tectonostratigraphic Framework and Geological Development . . . . . 62 3.2.2. Tectonic Models for the Development . . . . . . . . . . . . . . . . . . . 70 3.2.3. Pegmatites within the Yilgarn Craton . . . . . . . . . . . . . . . . . . . 76 3.2.4. Geological setting of the Londonderry Pegmatite Field . . . . . . . . . . 76 3.2.5. Geological Setting of the Mount Deans Pegmatite Field . . . . . . . . . 85 3.2.6. Geological Setting of the Cattlin Creek Pegmatite Deposit . . . . . . . . 91 3.3. Pilbara Craton . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99 3.3.1. Tectonostratigraphic Framework and Geological Development . . . . . 99 3.3.2. Tectonic Model for the Development . . . . . . . . . . . . . . . . . . . 101 3.3.3. Pegmatites within the Pilbara Craton . . . . . . . . . . . . . . . . . . . 105 3.3.4. Geological Setting of the Wodgina Pegmatite District . . . . . . . . . . 106 4. Fieldwork and Sampling of Selected Pegmatites and Pegmatite Fields 115 4.1. Bikita Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115 4.2. Londonderry Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115 4.2.1. Londonderry Feldspar Quarry Pegmatite . . . . . . . . . . . . . . . . . 115 4.2.2. Lepidolite Hill Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . 117 4.2.3. Tantalite Hill Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . . 118 4.3. Mount Deans Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . . . . . 118 4.3.1. Type I – Flat Lying Pegmatites . . . . . . . . . . . . . . . . . . . . . . . 118 4.3.2. Type II – Steeply Dipping Pegmatites . . . . . . . . . . . . . . . . . . . 120 4.4. Cattlin Creek Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120 4.5. Wodgina LCT-Pegmatite Deposit . . . . . . . . . . . . . . . . . . . . . . . . . . 121 4.5.1. Mount Tinstone Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . 123 4.5.2. Mount Cassiterite Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . 123 5. Petrography and Mineralogy 139 5.1. Quantitative Mineralogy by Means of Mineral Liberation Analysis . . . . . . . . 141 5.2. Mineralogical and Petrographical Characteristics of Individual Mineral Groups . 141 5.2.1. Feldspar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141 5.2.2. Quartz . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144 5.2.3. Mica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146 5.2.4. Pollucite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147 5.2.5. Petalite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149 5.2.6. Spodumene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149 5.2.7. Beryl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154 5.2.8. Tourmaline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155 5.2.9. Apatite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157 5.2.10. Ta-, Nb- and Sn-oxides . . . . . . . . . . . . . . . . . . . . . . . . . . 157 5.3. Reconstruction of the General Crystallisation Sequence . . . . . . . . . . . . . 162 6. Geochemistry 165 6.1. Major Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165 6.2. Selected Minor and Trace Elements . . . . . . . . . . . . . . . . . . . . . . . . 174 6.3. Fractionation Indicators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175 6.4. Rare Earth Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185 7. Geochronology 193 7.1. 40Ar/39Ar-Method on Mica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193 7.1.1. Bikita Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . . . . . 194 7.1.2. Mount Deans Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . 195 7.1.3. Londonderry Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . 195 7.1.4. Cattlin Creek Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . 195 7.1.5. Wodgina Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198 7.2. Th-U-Total Pb Monazite Dating . . . . . . . . . . . . . . . . . . . . . . . . . . . 201 7.2.1. Monazite Ages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201 7.3. U/Pb Dating of Selected Ta-, Nb- and Sn-Oxide Minerals . . . . . . . . . . . . 203 7.3.1. Bikita Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . . . . . 203 7.3.2. Londonderry Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . 203 7.3.3. Mount Deans Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . 206 7.3.4. Cattlin Creek Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . 206 7.3.5. Wodgina Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207 8. Fluid Inclusion Study 211 8.1. Bikita Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211 8.2. Wodgina Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211 8.3. Carbon Isotope Analysis on Fluid Inclusion Gas of Selected Mineral Phases . . 212 9. Stable and Radiogenic Isotopes 217 9.1. Whole Rock Sm/Nd-Isotopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217 9.1.1. New Whole Rock Sm/Nd Data . . . . . . . . . . . . . . . . . . . . . . 217 9.2. Lithium Isotope Analysis on Selected Mineral Phases . . . . . . . . . . . . . . . 220 9.2.1. New Lithium Isotope Data . . . . . . . . . . . . . . . . . . . . . . . . . 220 10.Discussion 227 10.1. Regional Geological and Tectonomagmatic Development . . . . . . . . . . . . 227 10.1.1. Constraints from Field Evidence . . . . . . . . . . . . . . . . . . . . . . 227 10.1.2. Petrographical and Mineralogical Constraints . . . . . . . . . . . . . . 229 10.1.3. Geochemical Constraints . . . . . . . . . . . . . . . . . . . . . . . . . 230 10.1.4. Isotopic Constraints . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232 10.1.5. Constraints from Fluid Inclusion Data . . . . . . . . . . . . . . . . . . . 233 10.1.6. Geochronological Constrains . . . . . . . . . . . . . . . . . . . . . . . 233 10.2. Massive Pollucite Mineralisations . . . . . . . . . . . . . . . . . . . . . . . . . . 243 10.2.1. Unique Characteristics of Massive Pollucite Mineralisations . . . . . . . 243 10.2.2. New Concepts for the Formation of Massive Pollucite Mineralisations . . 252 10.3. Genetic Model for the Formation of Massive Pollucite Mineralisations within LCT Pegmatite Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264 11.Summary and Conclusions 267 References 273 Lists of Abbreviations 309 General Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309 Mineral Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310 List of Figures 311 List of Tables 315 Appendix 317 A. Legend for Topographic Maps 319 B. Sample List 323 C. Methodology 331 C.1. Quantitative Mineralogy by Means of Mineral Liberation Analysis . . . . . . . . 331 C.2. Geochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331 C.3. 40Ar/39Ar-Method on Mica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335 C.4. Th-U-Total Pb Monazite Dating . . . . . . . . . . . . . . . . . . . . . . . . . . . 335 C.5. U/Pb Dating of Selected Ta-, Nb- and Sn-Oxide Minerals . . . . . . . . . . . . 336 C.6. Fluid Inclusion Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337 C.7. Whole Rock Sm/Nd-Isotopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338 C.8. Lithium Isotope Analysis on Selected Mineral Phases . . . . . . . . . . . . . . . 338 D. Data – Mineral Liberation Analysis 341 E. Data – Geochemistry 345 F. Data – Geochronology 349 G. Data – Stable and Radiogenic Isotopes 353 / Lithium-Caesium-Tantal-(LCT) Pegmatite repräsentieren eine bedeutende Quelle für seltene Metalle, deren Bedarf im letzten Jahrzehnt beträchtlich angestiegen ist. Im Falle von Caesium sind zurzeit weltweit nur zwei LCT-Pegmatitlagerstätten bekannt, die abbauwürdige Vorräte an Cs enthalten. Dies sind die LCT-Pegmatitlagerstätten Bikita in Simbabwe und Tanco in Kanada. Das Wirtsmineral für diese Cs-Mineralisation ist das extrem selten auftretende Zeolith-Gruppen-Mineral Pollucit. In den Lagerstätten Bikita und Tanco bildet Pollucit dagegen massive, linsenförmige und fast monomineralische Pollucitmineralisationen, die in den oberen Bereichen der Pegmatitkörper anstehen. Zusätzlich befinden sich beide Lagerstätten in geologisch vergleichbaren Einheiten. Die Nebengesteine sind Grünsteingürtel die ein neoarchaisches Alter von ca. 2,600 Ma aufweisen. Die Bildung derartiger massiver Pollucitmineralisationen ist bis jetzt noch nicht detailliert untersucht worden. Große Bereiche von Westaustralien werden von meso- bis neoarchaischen Krusteneinheiten (z.B. Yilgarn Kraton, Pilbara Kraton) aufgebaut, von denen auch eine große Anzahl an LCT-Pegmatitsystemen bekannt sind. Darunter befinden sich unter anderem die LCT-Pegmatitlagerstätten Greenbushes (Li, Ta) und Wodgina (Ta, Sn). Zusätzlich wurden kleine Mengen an Pollucit in einer einzigen Kernbohrung im Londonderry Pegmatitfeld angetroffen. Ungeachtet dessen, wurden in Westaustralien bis jetzt keine systematischen Untersuchungen und/oder Explorationskampagnen auf Vorkommen von Cs und speziell der von Pollucit durchgeführt. Im Verlauf dieser Studie wurden insgesamt neunzehn verschiedene Pegmatitvorkommen und Pegmatitfelder des Yilgarn Kratons, Pilbara Kratons und der Kimberley Provinz auf das Vorkommen des Minerals Pollucit untersucht. Allerdings konnte in keinem der untersuchten LCT-Pegmatitsystemen Pollucit nachgewiesen werden. Von vier der untersuchten LCT-Pegmatitsystemen, dem Londonderry Pegmatitfeld, dem Mount Deans Pegmatitfeld, der Cattlin Creek LCT-Pegmatitlagerstätte (Yilgarn Kraton) und der Wodgina LCT-Pegmatitlagerstätte (Pilbara Kraton) wurden detailliert Proben entnommen und weitergehend untersucht. Zusätzlich wurden die massiven Pollucitmineralisationen im Bikita Pegmatitfeld beprobt und in die detailierten Untersuchungen einbezogen. Der Probensatz aus dem Bikita Pegmatitfeld dient als Referenzmaterial mit dem die Pegmatitproben aus Westaustralien verglichen werden. Die vorliegende Arbeit fasst die wesentlichen Ergebnisse der petrographischen, mineralogischen, mineralchemischen, geochemischen und geochronologischen Untersuchungen sowie der Flüssigkeitseinschlussuntersuchungen und stabilen und radiogenen Isotopenzusammensetzungen zusammen. Alle vier der in Westaustralien untersuchten LCT-Pegmatitsysteme kommen in geologisch ähnlichen Rahmengesteinen vor, weisen einen vergleichbaren internen Aufbau, geochemische Zusammensetzung und Mineralogie zu dem des Bikita Pegmatitfeldes in Simbabwe auf. Weiterhin konnten in allen LCT-Pegmatitsystemen Hinweise für späte hydrothermale Prozesse (z.B. Verdrängung von Feldspat) nachgewiesen werden, die einhergehend mit einer Anreicherung von Cs verbunden sind (z.B. Cs-angereicherte Säume um Glimmer, Beryll und Turmalin). Mit der Ausnahme der Wodgina LCT-Pegmatitlagerstätte, in der ein mesoarchaisches Kristallisationsalter (ca. 2,850 Ma) nachgewiesen wurde, lieferten die Altersdatierungen in den anderen LCT-Pegmatitsystemen übereinstimmende neoarchaische Alter von 2,630 Ma bis 2,600 Ma. Diese fast identischen Alter der LCT-Pegmatitsysteme des Yilgarn und Zimbabwe Kratons suggerieren, dass die Prozesse, die zur LCT-Pegmatitbildung am Ende des Neoarchaikums führten, weltweit aktiv waren. Ungeachtet dessen stellt das Vorhandensein von massiver Pollucitmineralisation das Alleinstellungsmerkmal des Bikita Pegmatitfeldes dar, welche sich infolge eines Prozesses gebildet haben der nicht Bestandteil der üblichen LCT-Pegmatitentwicklung ist und sich durch eine extreme Anreicherung an Cs unterscheidet. Die neuen Ergebnisse die in dieser Studie von den Bikita Pegmatitfeld und den Westaustralischen LCT-Pegmatitsystemen gewonnen wurden, verbessern das Verständnis des Verhaltens von Cs in LCT-Pegmatitsystemen deutlich. Somit ist es nun möglich, ein genetisches Modell für die Bildung von massiven Pollucitmineralisationen in LCT-Pegmatitsystemen vorzustellen. LCT-Pegmatite weisen im Allgemeinen eine granitische Zusammensetzung auf und werden als Kristallisat von hoch fraktionierten und geochemisch spezialisierten granitischen Restschmelzen interpretiert. Die Bildung von massiven Pollucitmineralisationen ist nur aus großen und voluminösen Pegmatitschmelzen, die als einzelner Körper entlang von Störungen in extensionalen Stressregimen intrudieren möglich. Nach Platznahme der Schmelze bildet die beginnende Kristallisation zunächst die Kontakt- und Randzone des Pegmatits, wobei infolge von fraktionierter Kristallisation die immobilen Elemente (v.a. Cs, Rb) in der verbleibenden Restschmelze angereichert werden. Im Anschluss an diese erste Kristallisation entmischt sich nach Abkühlung eine sehr kleine Menge (0.5–1 vol.%) Schmelze und/oder Fluid von der Restschmelze. Diese nicht mischbare Teilschmelze/-fluid ist angereichert an Al2O3 und Na2O sowie verarmt an SiO2 und kristallisiert als Analcim. Zusätzlich kann diese Schmelze bereits mit 1–2 wt.% Cs2O angereichert sein. Aufgrund der Auswirkung von Flussmitteln (z.B. H2O, F, B) wird allerdings der Schmelzpunkt dieser Analcimschmelze herabgesetzt und so die Kristallisation des Analcims als intergranulare Körner verhindert. Da diese Analcimschmelze im Vergleich zu der restlichen Schmelze eine geringere relative Dichte besitzt, beginnt sie gravitativ aufzusteigen und sich in den oberen Bereichen des Pegmatitkörpers zu akkumulieren. Währenddessen beginnt die restliche Schmelze separat zu kristallisieren und die inneren Bereiche des Pegmatits zu bilden. Diese Kristallisation ist einhergehend mit fortschreitender Fraktionierung und der Anreicherung von inkompatiblen Elementen (v.a. Cs, Rb) in den sich als letztes bildenden Mineralphasen (z.B. Lepidolit) oder der Konzentration der inkompatiblen Element in die sich entmischenden hydrothermalen Fluiden. Da Analcim und Pollucit eine lückenlose Mischungsreihe bilden, ist die Analcimschmelze in der Lage, alles verfügbare Cs von der Restschmelze und/oder assoziierten hydrothermalen Fluiden an sich zu binden und als Cs-Analcim im oberen Bereich des Pegmatitkörpers zu kristallisieren. Fortschreitende hydrothermale Aktivität und Substitution von Cs verschiebt dann die Zusammensetzung des Analcims von der Cs-Analcim- zu Na-Pollucitzusammensetzung. Zusätzlich erfährt der Analcim bei Abkühlung unter 400 °C eine negative thermische Expansion von ca. 1 vol.%. Diese Kontraktion führt zu der Bildung des markanten Rissnetzwerkes das durch späte Mineralphasen (z.B. Lepidolit, Quarz, Feldspat und Petalit) gefüllt wird. Vor der Mineralisation allerdings, erhöht dieses Netzwerk an Rissen die verfügbaren Wegsamkeiten für die späten hydrothermalen Fluide und begünstigt somit den Cs-Substitutionsmechanismus in der massiven Pollucitmineralisation. Weiterhin kommt es bei der Abkühlung des Pegmatits zu späten Mineralverdrängungsreaktionen (z.B. Verdrängung von K-Feldspat durch Lepidolit, Cleavelandit und Quarz), sowie zu Subsolidus-Selbstordnungsprozessen in Feldspäten. Diese Prozesse werden weiterhin interpretiert inkompatible Elemente (z.B. Cs, Rb) in die späten hydrothermalen Fluide freizusetzen. Da Feldspäte große Teile der Pegmatite bilden, kann somit eine beträchtliche Menge an Cs freigeben werden und durch die späten hydrothermalen Fluide in die massive Pollucitmineralisation in den oberen Bereichen des Pegmatitkörpers transportiert werden. Infolgedessen ist es möglich, dass genügend Cs frei gesetzt werden kann, um die Zusammensetzung innerhalb der Mischkristallreihe von Cs-Analcim (>2 wt.% Cs2O) zu Na-Pollucit (23–43 wt.% Cs2O) zu verschieben. Die zeitliche Einordnung dieser späten Cs-Anreicherung wird als quasi zeitgleich oder im direkten Anschluss an die vollständige Kristallisation der Pegmatitschmelze interpretiert. Es kann allerdings nicht vernachlässigt werden, dass auch jüngere hydrothermale Ereignisse, die den Pegmatitkörper nachträglich überprägen, ähnliche hydrothermale Prozesse hervorrufen können. Somit konnte gezeigt werden, dass es durch Kombination dieser magmatischen und hydrothermalen Prozessen möglich ist, genügend Cs anzureichern, um die Bildung von massiven Pollucitmineralisationen in LCT-Pegmatitsystemen zu ermöglichen. Dieses genetische Modell kann nun dazu genutzt werden, um das Potential von Vorkommen von massiven Pollucitmineralisationen in LCT-Pegmatitsystemen in Westaustralien und weltweit besser einzuschätzen.:Contents Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii Zusammenfassung . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v Versicherung . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix Contents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi 1. Introduction 1 1.1. Motivation and Scope of the Thesis . . . . . . . . . . . . . . . . . . . . . . . . 1 1.2. Structure of the Thesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 2. Fundamentals 7 2.1. The Alkali Metal Cesium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 2.1.1. Distribution of Cesium . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 2.1.2. Mineralogy of Cesium . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 2.1.3. Geochemical Behaviour of Cesium . . . . . . . . . . . . . . . . . . . . 13 2.1.4. Economy of Cesium . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15 2.2. Pollucite – (Cs,Na)2Al2Si4O12×H2O . . . . . . . . . . . . . . . . . . . . . . . . 16 2.2.1. Crystal Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16 2.2.2. Analcime–Pollucite–Series . . . . . . . . . . . . . . . . . . . . . . . . . 17 2.2.3. Formation of Pollucite . . . . . . . . . . . . . . . . . . . . . . . . . . . 17 2.2.4. Pollucite Occurences . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 2.3. Pegmatites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34 2.3.1. General Characteristics of Pegmatites . . . . . . . . . . . . . . . . . . 34 2.3.2. Controls on Pegmatite Formation and Evolution . . . . . . . . . . . . . 40 2.3.3. Pegmatite Age Distribution and Continental Crust Formation . . . . . . 43 3. Geological Settings of Archean Cratons 47 3.1. Zimbabwe Craton . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47 3.1.1. Tectonostratigraphic Subdivision . . . . . . . . . . . . . . . . . . . . . 48 3.1.2. Tectonometamorphic Evolution of the Northern Limpopo Thrust Zone . 49 3.1.3. Pegmatites within the Zimbabwe Craton . . . . . . . . . . . . . . . . . 52 3.1.4. Masvingo Greenstone Belt . . . . . . . . . . . . . . . . . . . . . . . . . 53 3.1.5. Geological Setting of the Bikita Pegmatite District . . . . . . . . . . . . 58 3.2. Yilgarn Craton . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62 3.2.1. Tectonostratigraphic Framework and Geological Development . . . . . 62 3.2.2. Tectonic Models for the Development . . . . . . . . . . . . . . . . . . . 70 3.2.3. Pegmatites within the Yilgarn Craton . . . . . . . . . . . . . . . . . . . 76 3.2.4. Geological setting of the Londonderry Pegmatite Field . . . . . . . . . . 76 3.2.5. Geological Setting of the Mount Deans Pegmatite Field . . . . . . . . . 85 3.2.6. Geological Setting of the Cattlin Creek Pegmatite Deposit . . . . . . . . 91 3.3. Pilbara Craton . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99 3.3.1. Tectonostratigraphic Framework and Geological Development . . . . . 99 3.3.2. Tectonic Model for the Development . . . . . . . . . . . . . . . . . . . 101 3.3.3. Pegmatites within the Pilbara Craton . . . . . . . . . . . . . . . . . . . 105 3.3.4. Geological Setting of the Wodgina Pegmatite District . . . . . . . . . . 106 4. Fieldwork and Sampling of Selected Pegmatites and Pegmatite Fields 115 4.1. Bikita Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115 4.2. Londonderry Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115 4.2.1. Londonderry Feldspar Quarry Pegmatite . . . . . . . . . . . . . . . . . 115 4.2.2. Lepidolite Hill Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . 117 4.2.3. Tantalite Hill Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . . 118 4.3. Mount Deans Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . . . . . 118 4.3.1. Type I – Flat Lying Pegmatites . . . . . . . . . . . . . . . . . . . . . . . 118 4.3.2. Type II – Steeply Dipping Pegmatites . . . . . . . . . . . . . . . . . . . 120 4.4. Cattlin Creek Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120 4.5. Wodgina LCT-Pegmatite Deposit . . . . . . . . . . . . . . . . . . . . . . . . . . 121 4.5.1. Mount Tinstone Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . 123 4.5.2. Mount Cassiterite Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . 123 5. Petrography and Mineralogy 139 5.1. Quantitative Mineralogy by Means of Mineral Liberation Analysis . . . . . . . . 141 5.2. Mineralogical and Petrographical Characteristics of Individual Mineral Groups . 141 5.2.1. Feldspar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141 5.2.2. Quartz . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144 5.2.3. Mica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146 5.2.4. Pollucite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147 5.2.5. Petalite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149 5.2.6. Spodumene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149 5.2.7. Beryl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154 5.2.8. Tourmaline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155 5.2.9. Apatite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157 5.2.10. Ta-, Nb- and Sn-oxides . . . . . . . . . . . . . . . . . . . . . . . . . . 157 5.3. Reconstruction of the General Crystallisation Sequence . . . . . . . . . . . . . 162 6. Geochemistry 165 6.1. Major Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165 6.2. Selected Minor and Trace Elements . . . . . . . . . . . . . . . . . . . . . . . . 174 6.3. Fractionation Indicators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175 6.4. Rare Earth Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185 7. Geochronology 193 7.1. 40Ar/39Ar-Method on Mica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193 7.1.1. Bikita Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . . . . . 194 7.1.2. Mount Deans Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . 195 7.1.3. Londonderry Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . 195 7.1.4. Cattlin Creek Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . 195 7.1.5. Wodgina Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198 7.2. Th-U-Total Pb Monazite Dating . . . . . . . . . . . . . . . . . . . . . . . . . . . 201 7.2.1. Monazite Ages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201 7.3. U/Pb Dating of Selected Ta-, Nb- and Sn-Oxide Minerals . . . . . . . . . . . . 203 7.3.1. Bikita Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . . . . . 203 7.3.2. Londonderry Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . 203 7.3.3. Mount Deans Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . 206 7.3.4. Cattlin Creek Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . 206 7.3.5. Wodgina Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207 8. Fluid Inclusion Study 211 8.1. Bikita Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211 8.2. Wodgina Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211 8.3. Carbon Isotope Analysis on Fluid Inclusion Gas of Selected Mineral Phases . . 212 9. Stable and Radiogenic Isotopes 217 9.1. Whole Rock Sm/Nd-Isotopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217 9.1.1. New Whole Rock Sm/Nd Data . . . . . . . . . . . . . . . . . . . . . . 217 9.2. Lithium Isotope Analysis on Selected Mineral Phases . . . . . . . . . . . . . . . 220 9.2.1. New Lithium Isotope Data . . . . . . . . . . . . . . . . . . . . . . . . . 220 10.Discussion 227 10.1. Regional Geological and Tectonomagmatic Development . . . . . . . . . . . . 227 10.1.1. Constraints from Field Evidence . . . . . . . . . . . . . . . . . . . . . . 227 10.1.2. Petrographical and Mineralogical Constraints . . . . . . . . . . . . . . 229 10.1.3. Geochemical Constraints . . . . . . . . . . . . . . . . . . . . . . . . . 230 10.1.4. Isotopic Constraints . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232 10.1.5. Constraints from Fluid Inclusion Data . . . . . . . . . . . . . . . . . . . 233 10.1.6. Geochronological Constrains . . . . . . . . . . . . . . . . . . . . . . . 233 10.2. Massive Pollucite Mineralisations . . . . . . . . . . . . . . . . . . . . . . . . . . 243 10.2.1. Unique Characteristics of Massive Pollucite Mineralisations . . . . . . . 243 10.2.2. New Concepts for the Formation of Massive Pollucite Mineralisations . . 252 10.3. Genetic Model for the Formation of Massive Pollucite Mineralisations within LCT Pegmatite Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264 11.Summary and Conclusions 267 References 273 Lists of Abbreviations 309 General Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309 Mineral Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310 List of Figures 311 List of Tables 315 Appendix 317 A. Legend for Topographic Maps 319 B. Sample List 323 C. Methodology 331 C.1. Quantitative Mineralogy by Means of Mineral Liberation Analysis . . . . . . . . 331 C.2. Geochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331 C.3. 40Ar/39Ar-Method on Mica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335 C.4. Th-U-Total Pb Monazite Dating . . . . . . . . . . . . . . . . . . . . . . . . . . . 335 C.5. U/Pb Dating of Selected Ta-, Nb- and Sn-Oxide Minerals . . . . . . . . . . . . 336 C.6. Fluid Inclusion Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337 C.7. Whole Rock Sm/Nd-Isotopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338 C.8. Lithium Isotope Analysis on Selected Mineral Phases . . . . . . . . . . . . . . . 338 D. Data – Mineral Liberation Analysis 341 E. Data – Geochemistry 345 F. Data – Geochronology 349 G. Data – Stable and Radiogenic Isotopes 353

Im Osterzgebirge sowie im nordöstlich daran angrenzenden Elbtalschiefergebirge wurde mit Unterbrechungen über mehrere Jahrhunderte Bergbau auf Eisen betrieben. Für die Besiedlung, den Bergbau auf andere Metalle, die Landwirtschaft und das Handwerk in der Region hatte der Eisenerzbergbau eine gewisse Bedeutung. Im Gegensatz zum Silber- und Buntmetallbergbau ist über den Eisenerzbergbau allerdings nur relativ wenig bekannt. Das Ziel dieser Diplomarbeit bestand deshalb darin, eine zusammenfassende geologisch-geographische Darstellung, die sowohl den historischen Eisenerzbergbau im Osterzgebirge als auch den historischen Eisenerzbergbau im Elbtalschiefergebirge beinhaltet, zu erarbeiten. Um ein hohes Maß an Vollständigkeit zu gewährleisten, wurden die Erkenntnisse aus Archiven, Bibliotheken und Sammlungen zusammengetragen. Überdies wurde auch auf das Fachwissen von Heimatvereinen, Bergbaumuseen und Hobbyhistorikern zurückgegriffen. Ferner wird im Rahmen dieser Arbeit untersucht, welche Typen von Eisenerzlagerstätten es im Osterzgebirge und im Elbtalschiefergebirge gab, wie diese entstanden sind, um welche Mineralisation und um welche Art von Eisenerztypen es sich dabei handelt. Mit den gegenwärtig zur Verfügung stehenden Methoden der Analytik (REM-EDX) werden zudem die Mineralparagenese und die chemische Zusammensetzung von historischen und neuen Eisenerzproben aus dem Osterz- und Elbtalschiefergebirge untersucht. Ferner wird den Fragestellungen nachgegangen, wann diese Eisenerzlagerstätten erschlossen wurden, über welchen Zeitraum sie unter Abbau standen und wie viel Eisenerz aus den jeweiligen Gruben gefördert wurde. Hierfür erfolgte eine detaillierte Dokumentation der wichtigsten ehemaligen Eisenerzlagerstätten mit den dazugehörigen Zeugnissen des historischen Eisenerzbergbaus. Darauf aufbauend werden die Bedeutung des Eisenerzbergbaus und des daran angeschlossenen Eisenhüttenwesens für die wirtschaftliche und kulturelle Entwicklung des Gebietes untersucht. Des Weiteren werden die regionalen Beziehungen zu anderen Bergbau- und Wirtschaftszweigen aufgezeigt. Der Prozess des Aufbrechens der regionalen Wirtschaftsstrukturen im Zuge der Industrialisierung wird eingehend erläutert. Und die Gründe für den Niedergang des Eisenerzbergbaus und Eisenhüttenwesens werden ebenfalls genannt. Danach erfolgt eine Betrachtung darüber, welche bergbauhistorischen Zeugnisse heute im Gelände noch auffindbar bzw. welche Nachfolgenutzungen an den Standorten des historischen Eisenerzbergbaus und des Eisenhüttenwesens gegenwärtig vorhanden sind. Abschließend wird erläutert welche Schlussfolgerungen für die Nutzung des geotouristischen Potenzials sich daraus ergeben.

Im Osterzgebirge sowie im nordöstlich daran angrenzenden Elbtalschiefergebirge wurde mit Unterbrechungen über mehrere Jahrhunderte Bergbau auf Eisen betrieben. Für die Besiedlung, den Bergbau auf andere Metalle, die Landwirtschaft und das Handwerk in der Region hatte der Eisenerzbergbau eine gewisse Bedeutung. Im Gegensatz zum Silber- und Buntmetallbergbau ist über den Eisenerzbergbau allerdings nur relativ wenig bekannt. Das Ziel dieser Diplomarbeit bestand deshalb darin, eine zusammenfassende geologisch-geographische Darstellung, die sowohl den historischen Eisenerzbergbau im Osterzgebirge als auch den historischen Eisenerzbergbau im Elbtalschiefergebirge beinhaltet, zu erarbeiten. Um ein hohes Maß an Vollständigkeit zu gewährleisten, wurden die Erkenntnisse aus Archiven, Bibliotheken und Sammlungen zusammengetragen. Überdies wurde auch auf das Fachwissen von Heimatvereinen, Bergbaumuseen und Hobbyhistorikern zurückgegriffen. Ferner wird im Rahmen dieser Arbeit untersucht, welche Typen von Eisenerzlagerstätten es im Osterzgebirge und im Elbtalschiefergebirge gab, wie diese entstanden sind, um welche Mineralisation und um welche Art von Eisenerztypen es sich dabei handelt. Mit den gegenwärtig zur Verfügung stehenden Methoden der Analytik (REM-EDX) werden zudem die Mineralparagenese und die chemische Zusammensetzung von historischen und neuen Eisenerzproben aus dem Osterz- und Elbtalschiefergebirge untersucht. Ferner wird den Fragestellungen nachgegangen, wann diese Eisenerzlagerstätten erschlossen wurden, über welchen Zeitraum sie unter Abbau standen und wie viel Eisenerz aus den jeweiligen Gruben gefördert wurde. Hierfür erfolgte eine detaillierte Dokumentation der wichtigsten ehemaligen Eisenerzlagerstätten mit den dazugehörigen Zeugnissen des historischen Eisenerzbergbaus. Darauf aufbauend werden die Bedeutung des Eisenerzbergbaus und des daran angeschlossenen Eisenhüttenwesens für die wirtschaftliche und kulturelle Entwicklung des Gebietes untersucht. Des Weiteren werden die regionalen Beziehungen zu anderen Bergbau- und Wirtschaftszweigen aufgezeigt. Der Prozess des Aufbrechens der regionalen Wirtschaftsstrukturen im Zuge der Industrialisierung wird eingehend erläutert. Und die Gründe für den Niedergang des Eisenerzbergbaus und Eisenhüttenwesens werden ebenfalls genannt. Danach erfolgt eine Betrachtung darüber, welche bergbauhistorischen Zeugnisse heute im Gelände noch auffindbar bzw. welche Nachfolgenutzungen an den Standorten des historischen Eisenerzbergbaus und des Eisenhüttenwesens gegenwärtig vorhanden sind. Abschließend wird erläutert welche Schlussfolgerungen für die Nutzung des geotouristischen Potenzials sich daraus ergeben.

Within the framework of this research, the complex geological history of the Pan African-Volta basin has been systematically reconstructed. Based on a broad review of literature and new data, 5 stages of geological-tectonic development have been identified. For the first time a systematic review of the mineral potential of the Pan-African Volta Basin was executed. Known and potentially existing mineralization have been related to the geotectonic history and metallogenetic conclusions have been drawn. Based on the findings of this research, the folded thrust belt located at the eastern rim of the Volta basin has been identified as the most prospective area for the ultramafic rocks with chromite, nickel mineralization and PGEs, hydrothermal gold and banded iron formation (BIF) but this will require further work.

The fate of the carbon and nitrogen in dairy farm effluent (DFE) applied onto soil was investigated through laboratory experiments and field lysimeter studies. They resulted in the development and testing of a complex carbon (C) and nitrogen (N) simulation model (CaNS-Eff) of the soil-plant-microbial system. To minimise the risk of contamination of surface waters, regulatory authorities in New Zealand promote irrigation onto land as the preferred treatment method for DFE. The allowable annual loading rates for DFE, as defined in statutory regional plans are based on annual N balance calculations, comparing N inputs to outputs from the farming system. Little information is available, however, to assess the effects that these loading rates have on the receiving environment. It is this need, to understand the fate of land-applied DFE and develop a tool to describe the process, that is addressed in this research. The microbially mediated net N mineralisation from DFE takes a central role in the turnover of DFE, as the total N in DFE is dominated by organic N. In a laboratory experiment, where DFE was applied at the standard farm loading rate of 68 kg N ha⁻¹, the net C mineralisation from the DFE was finished 13 days after application and represented 30% of the applied C, with no net N mineralisation being measured by Day 113. The soluble fraction of DFE appeared to have a microbial availability similar to that of glucose. The low and gradually changing respiration rate measured from DFE indicated a semi-continuous substrate supply to the microbial biomass, reflecting the complex nature and broad range of C compounds in DFE. The repeated application of DFE will gradually enhance the mineralisable fraction of the total soil organic N and in the long term increase net N mineralisation. To address the lack of data on the fate of faecal-N in DFE, a ¹⁵N-labelled faecal component of DFE was applied under two different water treatments onto intact soil cores with pasture growing on them. At the end of 255 days, approximately 2% of the applied faecal ¹⁵N had been leached, 11 % was in plant material, 11 % was still as effluent on the surface, and 40% remained in the soil (39% as organic N). Unmeasured gaseous losses and physical losses from the soil surface of the cores supposedly account for the remaining ¹⁵N (approximately 36%). Separate analysis of the total and ammonium nitrogen contents and ¹⁵N enrichments of the DFE and filtered sub-samples (0.5 mm, 0.2µm) showed that the faecal-N fraction was not labelled homogeneously. Due to this heterogeneity, which was exacerbated by the filtration of DFE on the soil surface, it was difficult to calculate the turnover of the total faecal-N fraction based on ¹⁵N results. By making a simplifying assumption about the enrichment of the ¹⁵N in the DFE that infiltrated the soil, the contribution from DFE-N to all plant available N fractions including soil inorganic N was estimated to have been approximately 11 % of the applied DFE-N. An initial two-year study investigating the feasibility of manipulating soil water conditions through controlled drainage to enhance denitrification from irrigated DFE was extended a further two years for this thesis project. The resulting four-year data set provided the opportunity to evaluate the sustainability of DFE application onto land, an extended data set against which to test the adequacy of CaNS-Eff, and to identify the key processes in the fate of DFE irrigated onto soil under field conditions. In the final year of DFE irrigation, 1554 kg N ha⁻¹ of DFE-N was applied onto the lysimeters, with the main removal mechanism being pasture uptake (700 kg N ha⁻¹ yr⁻¹ removed). An average of 193 kg N ha⁻¹ yr⁻¹ was leached, with 80% of this being organic N. The nitrate leaching decreased with increasing soil moisture conditions through controlled drainage. At the high DFE loading rate used, the total soil C and N, pH and the microbial biomass increased at different rates over the four years. The long-term sustainability of the application of DFE can only be maintained when the supply of inorganic N is matched by the demand of the pasture. The complex simulation model (CaNS-Eff) of the soil-plant-microbial system was developed to describe the transport and transformations of C and N components in effluents applied onto the soil. The model addresses the shortcomings in existing models and simulates the transport, adsorption and filtration of both dissolved and particulate components of an effluent. The soil matrix is divided into mobile and immobile flow domains with convective flow of solutes occurring in the mobile fraction only. Diffusion is considered to occur between the micropore and mesopore domains both between and within a soil layer, allowing dissolved material to move into the immobile zone. To select an appropriate sub-model to simulate the water fluxes within CaNS-Eff, the measured drainage volumes and water table heights from the lysimeters were compared to simulated values over four years. Two different modelling approaches were compared, a simpler water balance model, DRAINMOD, and a solution to Richards' equation, SWIM. Both models provided excellent estimation of the total amount of drainage and water table height. The greatest errors in drainage volume were associated with rain events over the summer and autumn, when antecedent soil conditions were driest. When soil water and interlayer fluxes are required at small time steps such as during infiltration under DFE-irrigation, SWIM's more mechanistic approach offered more flexibility and consequently was the sub-model selected to use within CaNS-Eff. Measured bromide leaching from the lysimeters showed that on average 18% of the bromide from an irrigation event bypassed the soil matrix and was leached in the initial drainage event. This bypass mechanism accounted for the high amount of organic N leached under DFE-irrigation onto these soils and a description of this bypass process needed to be included in CaNS-Eff. Between 80 and 90% of the N and C leached from the lysimeters was particulate (> 0.2 µm in size), demonstrating the need to describe transport of particulate material in CaNS-Eff. The filtration behaviour of four soil horizons was measured by characterising the size of C material in a DFE, applying this DFE onto intact soil cores, and collecting and analyzing the resulting leachate using the same size characterisation. After two water flushes, an average of 34% of the applied DFE-C was leached through the top 0-50 mm soil cores, with a corresponding amount of 27% being leached from the 50-150 mm soil cores. Most of the C leaching occurred during the initial DFE application onto the soil. To simulate the transport and leaching of particulate C, a sub-model was developed and parameterised that describes the movement of the effluent in terms of filtering and trapping the C within a soil horizon and then washing it out with subsequent flow events. The microbial availability of the various organic fractions within the soil system are described in CaNS-Eff by availability spectra of multiple first-order decay functions. The simulation of microbial dynamics is based on actual consumption of available C for three microbial biomass populations: heterotrophs, nitrifiers and denitrifiers. The respiration level of a population is controlled by the amount of C that is available to that population. This respiration rate can vary between low level maintenance requirements, when very little substrate is available, and higher levels when excess substrate is available to an actively growing population. The plant component is described as both above and below-ground fractions of a rye grass-clover pasture. The parameter set used in CaNS-Eff to simulate the fate of DFE irrigated onto the conventionally drained lysimeter treatments over three years with a subsequent 10 months non-irrigation period was derived from own laboratory studies, field measurements, experimental literature data and published model studies. As no systematic calibration exercise was undertaken to optimise these parameters, the parameter set should be considered as "initial best estimates" and not as a calibrated data set on which a full validation of CaNS-Eff could be based. Over the 42 months of simulation, the cumulative drainage from CaNS-Eff for the conventionally drained DFE lysimeter was always within the 95% CI of the measured value. On the basis of individual drainage bulking periods, CaNS-Eff was able to explain 92% of the variation in the measured drainage volumes. On an event basis the accuracy of the simulated water filled pore space (WFPS) was better than that of the drainage volume, with an average of 70% of the simulated WFPS values being within the 95% CI for the soil layers investigated, compared to 44% for the drainage volumes. Overall the hydrological component of CaNS-Eff, which is based on the SWIM model, could be considered as satisfactory for the purposes of predicting the soil water status and drainage volume from the conventionally drained lysimeter treatment for this study. The simulated cumulative nitrate leaching of 4.7 g NO₃-N m⁻² over the 42 months of lysimeter operation was in good agreement to the measured amount of 3.0 (± 2.7) g NO₃-N m⁻². Similarly, the total simulated ammonium leaching of 2.7g NH₄- N m⁻² was very close to the measured amount of 2.5 (± 1.35) g NH₄- N m⁻² , however the dynamics were not as close to the measured values as with the nitrate leaching. The simulated amount of organic N leached was approximately double that measured, and most of the difference originated from the simulated de-adsorption of the dissolved fraction of organic N during the l0-month period after the final DFE irrigation. The 305 g C m⁻² of simulated particulate C leached was close to the measured amount of 224 g C m⁻² over the 31 months of simulation. The dissolved C fraction was substantially over-predicted. There was good agreement in the non-adsorbed and particulate fractions of the leached C and N in DFE. However, the isothermic behaviour of the adsorbed pools indicated that a non-reversible component needed to be introduced or that the dynamics of the de-adsorption needed to be improved. Taking into account that the parameters were not calibrated but only "initial best estimates", the agreement in the dynamics and the absolute amounts between the measured and simulated values of leached C and N demonstrated that CaNS-Eff contains an adequate description of the leaching processes following DFE irrigation onto the soil. The simulated pasture N production was in reasonable agreement with the measured data. The simulated dynamics and amounts of microbial biomass in the topsoil layers were in good agreement with the measured data. This is an important result as the soil microbial biomass is the key transformation station for organic materials. Excepting the topsoil layer, the simulated total C and N dynamics were close to the measured values. The model predicted an accumulation of C and N in the topsoil layer as expected, but not measured. Although no measurements were available to compare the dynamics and amounts of the soil NO₃-N and NH₄-N, the simulated values appear realistic for an effluent treatment site and are consistent with measured pasture data. Considering the large amount of total N and C applied onto the lysimeters over the 42 months of operation (4 t ha⁻¹ of N and 42 t ha⁻¹0f C), the various forms of C and N in dissolved and particulate DFE as well as in returned pasture, and that the parameters used in the test have not been calibrated, the simulated values from CaNS-Eff compared satisfactorily to the measured data.

No description available.

No description available.

The introduced mineral deposit model (MDM) is the product of a trans-disciplinary study, based on Complexity and General Systems Theory. Both investigate the abstract organization of phenomena, independent of their substance, type, or spatial or temporal scale of existence. The focus of the research has been on giant, hydrothermal mineral deposits. They constitute <0.001% of the total number of deposits yet contain 70-85% of the world's metal resources. Giants are the definitive exploration targets. They are more profitable to exploit and less susceptible to fluctuations of the market. Consensus has it that the same processes that generate small deposits also form giants but those processes are simply longer, vaster, and larger. Heat is the dominant factor in the genesis of giant mineral deposits. A paleothermal map shows where the vast heat required to generate a giant has been concentrated in a large space, and even allows us to deduce the duration of the process. To generate a paleothermal map acceptable to the scientific community requires reproducibility. Experimentation with various approaches to pattern recognition of geochemical data showed that the AUTOCLUST algorithm not only gave reproducibility but also gave the most consistent, most meaningful results. It automatically extracts boundaries based on Voronoi and Delaunay tessellations. The user does not specify parameters; however, the modeller does have tools to explore the data. This approach is near ideal in that it removes much of the human-generated bias. This algorithm reveals the radial, spatial distribution, of gold deposits in the Lachlan Fold Belt of southeastern Australia at two distinct scales – repeating patterns every ~80 km and ~230 km. Both scales of patterning are reflected in the geology. The ~80 km patterns are nested within the ~230 km patterns revealing a self-similar, geometrical relationship. It is proposed that these patterns originate from Rayleigh-Bénard convection in the mantle. At the Rayleigh Number appropriate for the mantle, the stable planform is the spoke pattern, where hot mantle material is moving upward near the centre of the pattern and outward along the radial arms. Discontinuities in the mantle, Rayleigh-Bénard convection in the mantle, and the spatial distribution of giant mineral deposits, are correlative. The discontinuities in the Earth are acting as platforms from which Rayleigh-Bénard convection can originate. Shallow discontinuities give rise to plumelets, which manifest at the crust as repeating patterns ranging, from ~100 to ~1,000 km in diameter. Deeper discontinuities give rise to plumes, which become apparent at the crust as repeating patterns ranging from >1,000 to ~4,000 km in diameter. The deepest discontinuities give rise to the superplumes, which become detectable at the crust as repeating patterns ranging from >4,000 to >10,000 km in diameter. Rayleigh-Bénard convection concentrates the reservoir of heat in the mantle into specific locations in the crust; thereby providing the vast heat requirements for the processes that generate giant, hydrothermal mineral deposits. The radial spatial distribution patterns observed for gold deposits are also present for base metal deposits. At the supergiant Broken Hill deposit in far western New South Wales, Australia, the higher temperature Broken Hill-type deposits occur in a radial pattern while the lower temperature deposits occur in concentric patterns. The supergiant Broken Hill deposit occurs at the very centre of the pattern. If the supergiant Broken Hill Deposit was buried beneath alluvium, water or younger rocks, it would now be possible to predict its location with accuracy measured in tens of square kilometres. This predictive accuracy is desired by every exploration manager of every exploration company. The giant deposits at Broken Hill, Olympic Dam, and Mount Isa all occur on the edge of an annulus. There are at least two ways of creating an annulus on the Earth's surface. One is through Rayleigh-Bénard convection and the other is through meteor impact. It is likely that only 'large' meteors (those >10 km in diameter) would have any permanent impact on the mantle. Lesser meteors would leave only a superficial scar that would be eroded away. The permanent scars in the mantle act as ‘accidental templates’ consisting of concentric and possibly radial fractures that impose those structures on any rocks that were subsequently laid down or emplaced over the mantle. In southeastern Australia, the proposed Deniliquin Impact structure has been an 'accidental template' providing a 'line-of-least-resistance' for the ascent of the ~2,000 km diameter, offshore, Cape Howe Plume. The western and northwestern radial arms of this plume have created the very geometry of the Lachlan Fold Belt, as well as giving rise to the spatial distribution of the granitic rocks in that belt and ultimately to the gold deposits. The interplay between the templating of the mantle by meteor impacts and the ascent of plumelets, plumes or superplumes from various discontinuities in the mantle is quite possibly the reason that mineral deposits occur where they do.

The introduced mineral deposit model (MDM) is the product of a trans-disciplinary study, based on Complexity and General Systems Theory. Both investigate the abstract organization of phenomena, independent of their substance, type, or spatial or temporal scale of existence. The focus of the research has been on giant, hydrothermal mineral deposits. They constitute <0.001% of the total number of deposits yet contain 70-85% of the world's metal resources. Giants are the definitive exploration targets. They are more profitable to exploit and less susceptible to fluctuations of the market. Consensus has it that the same processes that generate small deposits also form giants but those processes are simply longer, vaster, and larger. Heat is the dominant factor in the genesis of giant mineral deposits. A paleothermal map shows where the vast heat required to generate a giant has been concentrated in a large space, and even allows us to deduce the duration of the process. To generate a paleothermal map acceptable to the scientific community requires reproducibility. Experimentation with various approaches to pattern recognition of geochemical data showed that the AUTOCLUST algorithm not only gave reproducibility but also gave the most consistent, most meaningful results. It automatically extracts boundaries based on Voronoi and Delaunay tessellations. The user does not specify parameters; however, the modeller does have tools to explore the data. This approach is near ideal in that it removes much of the human-generated bias. This algorithm reveals the radial, spatial distribution, of gold deposits in the Lachlan Fold Belt of southeastern Australia at two distinct scales – repeating patterns every ~80 km and ~230 km. Both scales of patterning are reflected in the geology. The ~80 km patterns are nested within the ~230 km patterns revealing a self-similar, geometrical relationship. It is proposed that these patterns originate from Rayleigh-Bénard convection in the mantle. At the Rayleigh Number appropriate for the mantle, the stable planform is the spoke pattern, where hot mantle material is moving upward near the centre of the pattern and outward along the radial arms. Discontinuities in the mantle, Rayleigh-Bénard convection in the mantle, and the spatial distribution of giant mineral deposits, are correlative. The discontinuities in the Earth are acting as platforms from which Rayleigh-Bénard convection can originate. Shallow discontinuities give rise to plumelets, which manifest at the crust as repeating patterns ranging, from ~100 to ~1,000 km in diameter. Deeper discontinuities give rise to plumes, which become apparent at the crust as repeating patterns ranging from >1,000 to ~4,000 km in diameter. The deepest discontinuities give rise to the superplumes, which become detectable at the crust as repeating patterns ranging from >4,000 to >10,000 km in diameter. Rayleigh-Bénard convection concentrates the reservoir of heat in the mantle into specific locations in the crust; thereby providing the vast heat requirements for the processes that generate giant, hydrothermal mineral deposits. The radial spatial distribution patterns observed for gold deposits are also present for base metal deposits. At the supergiant Broken Hill deposit in far western New South Wales, Australia, the higher temperature Broken Hill-type deposits occur in a radial pattern while the lower temperature deposits occur in concentric patterns. The supergiant Broken Hill deposit occurs at the very centre of the pattern. If the supergiant Broken Hill Deposit was buried beneath alluvium, water or younger rocks, it would now be possible to predict its location with accuracy measured in tens of square kilometres. This predictive accuracy is desired by every exploration manager of every exploration company. The giant deposits at Broken Hill, Olympic Dam, and Mount Isa all occur on the edge of an annulus. There are at least two ways of creating an annulus on the Earth's surface. One is through Rayleigh-Bénard convection and the other is through meteor impact. It is likely that only 'large' meteors (those >10 km in diameter) would have any permanent impact on the mantle. Lesser meteors would leave only a superficial scar that would be eroded away. The permanent scars in the mantle act as ‘accidental templates’ consisting of concentric and possibly radial fractures that impose those structures on any rocks that were subsequently laid down or emplaced over the mantle. In southeastern Australia, the proposed Deniliquin Impact structure has been an 'accidental template' providing a 'line-of-least-resistance' for the ascent of the ~2,000 km diameter, offshore, Cape Howe Plume. The western and northwestern radial arms of this plume have created the very geometry of the Lachlan Fold Belt, as well as giving rise to the spatial distribution of the granitic rocks in that belt and ultimately to the gold deposits. The interplay between the templating of the mantle by meteor impacts and the ascent of plumelets, plumes or superplumes from various discontinuities in the mantle is quite possibly the reason that mineral deposits occur where they do.

The introduced mineral deposit model (MDM) is the product of a trans-disciplinary study, based on Complexity and General Systems Theory. Both investigate the abstract organization of phenomena, independent of their substance, type, or spatial or temporal scale of existence. The focus of the research has been on giant, hydrothermal mineral deposits. They constitute <0.001% of the total number of deposits yet contain 70-85% of the world's metal resources. Giants are the definitive exploration targets. They are more profitable to exploit and less susceptible to fluctuations of the market. Consensus has it that the same processes that generate small deposits also form giants but those processes are simply longer, vaster, and larger. Heat is the dominant factor in the genesis of giant mineral deposits. A paleothermal map shows where the vast heat required to generate a giant has been concentrated in a large space, and even allows us to deduce the duration of the process. To generate a paleothermal map acceptable to the scientific community requires reproducibility. Experimentation with various approaches to pattern recognition of geochemical data showed that the AUTOCLUST algorithm not only gave reproducibility but also gave the most consistent, most meaningful results. It automatically extracts boundaries based on Voronoi and Delaunay tessellations. The user does not specify parameters; however, the modeller does have tools to explore the data. This approach is near ideal in that it removes much of the human-generated bias. This algorithm reveals the radial, spatial distribution, of gold deposits in the Lachlan Fold Belt of southeastern Australia at two distinct scales – repeating patterns every ~80 km and ~230 km. Both scales of patterning are reflected in the geology. The ~80 km patterns are nested within the ~230 km patterns revealing a self-similar, geometrical relationship. It is proposed that these patterns originate from Rayleigh-Bénard convection in the mantle. At the Rayleigh Number appropriate for the mantle, the stable planform is the spoke pattern, where hot mantle material is moving upward near the centre of the pattern and outward along the radial arms. Discontinuities in the mantle, Rayleigh-Bénard convection in the mantle, and the spatial distribution of giant mineral deposits, are correlative. The discontinuities in the Earth are acting as platforms from which Rayleigh-Bénard convection can originate. Shallow discontinuities give rise to plumelets, which manifest at the crust as repeating patterns ranging, from ~100 to ~1,000 km in diameter. Deeper discontinuities give rise to plumes, which become apparent at the crust as repeating patterns ranging from >1,000 to ~4,000 km in diameter. The deepest discontinuities give rise to the superplumes, which become detectable at the crust as repeating patterns ranging from >4,000 to >10,000 km in diameter. Rayleigh-Bénard convection concentrates the reservoir of heat in the mantle into specific locations in the crust; thereby providing the vast heat requirements for the processes that generate giant, hydrothermal mineral deposits. The radial spatial distribution patterns observed for gold deposits are also present for base metal deposits. At the supergiant Broken Hill deposit in far western New South Wales, Australia, the higher temperature Broken Hill-type deposits occur in a radial pattern while the lower temperature deposits occur in concentric patterns. The supergiant Broken Hill deposit occurs at the very centre of the pattern. If the supergiant Broken Hill Deposit was buried beneath alluvium, water or younger rocks, it would now be possible to predict its location with accuracy measured in tens of square kilometres. This predictive accuracy is desired by every exploration manager of every exploration company. The giant deposits at Broken Hill, Olympic Dam, and Mount Isa all occur on the edge of an annulus. There are at least two ways of creating an annulus on the Earth's surface. One is through Rayleigh-Bénard convection and the other is through meteor impact. It is likely that only 'large' meteors (those >10 km in diameter) would have any permanent impact on the mantle. Lesser meteors would leave only a superficial scar that would be eroded away. The permanent scars in the mantle act as ‘accidental templates’ consisting of concentric and possibly radial fractures that impose those structures on any rocks that were subsequently laid down or emplaced over the mantle. In southeastern Australia, the proposed Deniliquin Impact structure has been an 'accidental template' providing a 'line-of-least-resistance' for the ascent of the ~2,000 km diameter, offshore, Cape Howe Plume. The western and northwestern radial arms of this plume have created the very geometry of the Lachlan Fold Belt, as well as giving rise to the spatial distribution of the granitic rocks in that belt and ultimately to the gold deposits. The interplay between the templating of the mantle by meteor impacts and the ascent of plumelets, plumes or superplumes from various discontinuities in the mantle is quite possibly the reason that mineral deposits occur where they do.