Tungsten transport and deposition in magmatic-hydrothermal environments : the example of Panasqueira (Portugal) Eleonora Carocci To cite this version: Eleonora Carocci. Tungsten transport and deposition in magmatic-hydrothermal environments : the example of Panasqueira (Portugal). Earth Sciences. Université de Lorraine, 2019. English. NNT : 2019LORR0315. tel-02880627 HAL Id: tel-02880627 https://hal.univ-lorraine.fr/tel-02880627 Submitted on 25 Jun 2020 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. 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Contact : [email protected] LIENS Code de la Propriété Intellectuelle. articles L 122. 4 Code de la Propriété Intellectuelle. articles L 335.2- L 335.10 http://www.cfcopies.com/V2/leg/leg_droi.php http://www.culture.gouv.fr/culture/infos-pratiques/droits/protection.htm logos Ecole Doctorale SIReNa (Science et ingénierie des Ressources Naturelles) Thèse Présentée et soutenue publiquement pour l’obtention du titre de Docteur de l’Université de Lorraine (Nancy) Mention : « Géosciences » par Eleonora CAROCCI Transport et dépôt du tungstène dans les environnements magmatiques-hydrothermaux : exemple de Panasqueira (Portugal) Tungsten transport and deposition in magmatic-hydrothermal environments: the example of Panasqueira (Portugal) 13 décembre 2019 Membres du jury : Rapporteurs : Mr Johann G. RAITH Professeur, Montanuniversität Leoben, Austria Mr Jean-Louis HAZEMANN Directeur de Recherche CNRS, Institut NEEL, Grenoble, France Examinateurs : Mme Mercedes FUERTES FUENTE Professeur, Université de Oviedo, Espagne Mme Cécile FABRE Maître de Conférences, Université de Lorraine, Nancy, France Mr Michel CATHELINEAU Directeur de Recherche, Université de Lorraine, Nancy, France, directeur de thèse Mr Laurent TRUCHE Professeur, Université Grenoble Alpes, Grenoble, France, co- directeur de thèse Membres invités : Mr Christian MARIGNAC Professeur Emérite, Université de Lorraine, Nancy, France Mr Filipe PINTO Ingenieur géologue, BERALT TIN and WOLFRAM, Barroca Grande, Portugal 1 2 « Le cose sono unite da legami invisibili. Non puoi cogliere un fiore senza turbare una stella. » Galileo Galilei 3 CONTENTS: Résumé Étendu 12 Abstract 18 Introduction 22 1. STATE OF ART 24 1.1 Genetic Model of Deposits Associated with Veins-Stockworks 25 1.2 W-Sn- (Cu) Panasqueira Deposit 27 1.3 Common Types of Fluids Characterizing Transport and Deposition of W: Fluid Inclusions Data 30 2. SET OF ISSUES AND SUBJECT OF THE THESIS 33 3. OBJECTIVES AND EXPECTED RESULTS 34 4. MATERIALS AND METHODS 36 4.1 Geological Part- Data Collection 36 4.2 Geochemical Collection Data 39 Major elements conditions 39 Trace, Rare Earth elements 39 Dating 39 Fluid Inclusions 40 4.3 Experimental Part- Dataset 41 5. MANUSCRIPT ORGANIZATION 48 Part One 49 First Depositional Stage 49 Paragenetic succession at Panasqueira 50 General characteristics of the paragenetic succession 50 At the pillar scale 50 Later stages 51 At the sample scale 51 Revised Panasqueira paragenetic chart 53 4 Li-Fe-muscovite 54 Arsenopyrite 56 Topaz 58 Phosphates 61 Siderite 62 CHAPTER ONE 63 INCIPIENT DEPOSITION STAGE OF WOLFRAMITE: W-RUTILE AND TOURMALINE CHEMISTRY AS PROXIES FOR EARLY FLUIDS AT PANASQUEIRA (PORTUGAL) 63 Abstract 63 Introduction 64 Regional background 65 Geological setting and previous work 68 Samples and methods 70 Results 72 Petrography of the tourmalinized wallrocks 72 Tourmaline textures 73 Rutile textures 78 Tourmaline chemical composition 79 Rutile chemical composition: 88 Dating 88 Discussion 91 Age of the early hydrothermal stage 91 Tourmaline evidence for the involvement of two fluids 92 The boron problem and the feasibility of a magmatic source of fluids 95 Metasedimentary source(s) of the fluids: the contribution of REE data 96 Contrasted compositions of F1 and F2 end-members 97 Rutile evidence for short term fluid dynamics and mixing 98 Proposed conceptual model 98 Conclusions 101 5 CHAPTER TWO 112 RUTILE FROM PANASQUEIRA (CENTRAL PORTUGAL): AN EXCELLENT PATHFINDER FOR WOLFRAMITE DEPOSITION 112 Abstract 112 1. Introduction 113 2. Geological Setting 114 3. Material and Methods 115 4. Results 115 4.1. Petrography 115 4.2. Rutile Chemical Composition 118 5. Interpretation 120 5.1. Crystal Chemistry 120 5.2. Compositional Zoning: Sector Zoning 122 5.3. Compositional Zoning: Oscillatory Zoning 126 6. Discussion 129 6.1. Oscillatory Zoning: External or Internal Control? 129 6.2. Open or Closed System Evolution? 130 6.3. Oscillatory Zoning as a Consequence of Seismic Activity? 131 6.4. Nature of the Fluid(s) 131 7. Conclusions 132 Part Two 141 Panasqueira Chemical Fluid Evolution 141 CHAPTER THREE 142 FLUID EVOLUTION IN THE PANASQUEIRA DEPOSIT: THE ROLE OF EXHUMATION AND MULITPLE FLUID PULSES IN THE TRANSPORT AND DEPOSITION OF W-Sn-Cu 142 Abstract 142 1 Introduction 143 2 Methods 146 6 Paragenetic associations 146 Fluid inclusions 147 3 Paragenetic succession at Panasqueira 148 General characteristics of the paragenetic succession 148 Revised Panasqueira paragenetic chart 156 4 Fluid inclusions results 166 Fluid characterization 166 5 Bulk chemical evolution 183 6 P-T estimation 188 Thermal gradients and proximity to magma intrusions: the convective fluid system 189 Long-lived hydrothermal systems likely related to multiple intrusions 189 7 Conclusions 192 Part Three 197 Experimental Part On W-Beahviour 197 CHAPTER FOUR 198 TUNGSTEN (VI) SPECIATION IN HYDROTHERMAL SOLUTION UP TO 400°C AS REVEALED BY IN- SITU RAMAN SPECTROSCOPY 198 Abstract 198 1 Introduction 199 2 Methods 200 2.1 Experiments 200 2.2 Spectroscopic cell and Raman data acquisition 201 2.3 Fitting procedure of Raman spectra 202 3 Results 206 3.1 Effect of temperature and pH on W speciation 206 3.2. Stability and reversible formation of W-species 208 3.3. Effect of carbonate and chloride 209 4 Discussion 211 7 4.1. Identification of W-species 211 4.2. Tungsten speciation 214 4.3. Geological implications 216 5. Conclusion 216 Part Four 222 Discussion Upon a Possible Panasqueira Model and Open Questions 222 4.1 IMPLICATIONS FROM THE PARAGENETIC SUCCESSION: GEOCHEMICAL INTERPRETATION, PROBLEMS TO BE SOLVED 223 4.2 NATURE AND ORIGIN OF THE FLUIDS 224 A- Fluid origin 224 Predominance of Pseudo-Metamorphic Fluids 224 Introduction of Magmatic Fluids in the System 225 B- Fluid Migration and Exhumation 225 C- Quartz vein formation 226 4.3 METAL SOURCES (W and other RM) 227 A- Granite source of fluids and metals? A connected question: the role of “greisen” and “greisenization” 227 The G1, G2, G3, G4 Granites 229 Greisenization versus Episyenitization 234 Protolithionite (-) and the Silicification Events 235 HYPOTHESIS UPON CONCEALED RMG BODIES 237 B- Metamorphic Source of Metals 238 Magmatic-metamorphic variant: 238 4.4 THE TIME CHART AT PANASQUEIRA 239 4.5 MECHANISMS OF WOLFRAMITE PRECIPITATION 242 A- The Transport of W in Solution, State of the Art 242 B- The New Data on Complexation 243 C- The Potential Mechanisms for W-Species Destabilization 244 8 4.6 APPLICATION TO PANASQUEIRA CASE 247 A- Previous Works 247 B- Constraints Issued from the Present Work/Critics of Previous Works 247 CONSTRAINTS FROM THE PARAGENETIC SUCCESSION: INCONSISTENCY OF THE LECUMBERRI-SANCHEZ ET AL. (2017) MODEL 247 CONSTRAINTS FROM THE TOURMALINE STUDY 247 THE MAIN STAGE OF WOLFRAMITE DEPOSITION: CONSTRAINTS FROM FI DATA 248 Part Five 250 Conclusions 250 250 CONCLUSION 251 THE PANASQUEIRA METALLOGENIC (MINERAL) SYSTEM : THE EVIDENCE FOR A PROTRACTED CRUSTAL-SCALE SYSTEM 251 5.1 Proposition of a Conceptual Model for the Early Stages (I-II) 251 5.3. A long-lived crustal scale system 257 Appendix 263 APPENDIX PART ONE: CHAPTER ONE 264 Table A1: Operating conditions for the LA-ICP-MS equipment 264 Appendix A2: Ar-Ar dating of muscovite (methodology) 265 Appendix A0: 266 1. Problems in measuring Tur compositions by EPMA 266 2. Reality and extent of a Si apfu bias in SEM-EDS analyses 266 3. SEM-EPMA comparison 267 4. Internal consistency of SEM-EDS analyses 270 5. The case for F 271 6. Conclusion 272 Appendix A3-Table A3: Major element analyses of the early tourmaline from Panasqueira 273 Appendix A4- Table A4: Major element analyses of the early tourmaline from Panasqueira 273 9 Appendix A6- Table A6: LA-ICP-MS U-Pb data for the Panasqueira Rutile - All errrors are listed at 1 sigma 273 Appendix A7- Table A7: 40Ar/39Ar dating of a muscovite selvage from Panasqueria 273 Appendix A8: 273 Boron mass balance calculations 273 Volume of magmatic water required for boron transportation 274 Possible water yield by the granite system 274 Appendix A9: Oscillatory zoning: a (micro)seismic connection? 276 APPENDIX PART ONE: CHAPTER TWO 278 Supplementary Data: Table S1 278 APPENDIX PART THREE: CHAPTER FOUR 278 Annex 2: Table 1, k calibration, Table 3, Table 4 278 Annex 1: Table 5, Table 6, Table 7 278 Acknowledgments 280 10 11 Résumé Étendu L’importance accordée aux métaux rares a augmenté considérablement au cours des les trois dernières décennies, en raison de la demande croissante provenant de l’industrie, de la technologie et des économies émergentes. Parmi ces métaux rares, le tungstène (W) a a été l’objet d’attention puisqu’il est utilisé dans des produits couvrant une large gamme d’objectifs dans l’industrie de haute technologie.