UNIVERSITY OF COIMBRA FACULTY OF SCIENCES AND TECHNOLOGY Department of Earth Sciences EVALUATION OF THE POTENTIAL IN CRITICAL METALS IN THE FINE TAILINGS DAMS OF THE PANASQUEIRA MINE (BARROCA GRANDE, PORTUGAL) - TUNGSTEN AND OTHER CRMs CASES - Francisco Cunha Soares Veiga Simão MASTER IN GEOSCIENCES – Specialisation in Geological Resources September, 2017 UNIVERSITY OF COIMBRA FACULTY OF SCIENCES AND TECHNOLOGY Department of Earth Sciences EVALUATION OF THE POTENTIAL IN CRITICAL METALS IN THE FINE TAILINGS DAMS OF THE PANASQUEIRA MINE (BARROCA GRANDE, PORTUGAL) - TUNGSTEN AND OTHER CRMs CASES - Francisco Cunha Soares Veiga Simão MASTER IN GEOSCIENCES Specialisation in Geological Resources Scientific Advisors: Doctor Alcides Pereira, Faculty of Sciences and Technology, University of Coimbra Doctor Elsa Gomes, Faculty of Sciences and Technology, University of Coimbra September, 2017 TABLE OF CONTENTS ACKNOWLEDGMENTS I RESUMO III ABSTRACT V LIST OF FIGURES VII LIST OF CHARTS IX LIST OF TABLES XI LIST OF ACRONYMS XIII LIST OF ABBREVIATIONS, CHEMICAL SYMBOLS AND FORMULAS, AND UNITS XVII CHAPTER 1. INTRODUCTION 1 1.1. RATIONALE 1 1.2. MAIN AND SPECIFIC GOALS 2 1.3. STATE OF THE ART 2 CHAPTER 2. EUROPEAN UNION AND PORTUGUESE POLICIES ON RAW MATERIALS 5 2.1. RAW MATERIALS INITIATIVE 6 2.2. INTERNATIONAL DIPLOMACY ON RAW MATERIALS 18 2.3. RAW MATERIALS INITIATIVE DEVELOPMENT 18 2.3.1. THE EUROPEAN INNOVATION PARTNERSHIP ON RAW MATERIALS 19 2.3.2. EUROPEAN INSTITUTE OF INNOVATION & TECHNOLOGY 22 2.4. CIRCULAR ECONOMY 22 2.4.1. CONCEPTS AND PRINCIPLES 22 2.4.2. EUROPEAN UNION POLICIES ON CIRCULAR ECONOMY 24 2.4.3. CRITICAL RAW MATERIALS IN THE EUROPEAN UNION’S CIRCULAR ECONOMY 26 2.5. PORTUGUESE POLICIES ON THE RAW MATERIALS 30 2.5.1. NATIONAL LEGISLATION 30 2.5.2. NATIONAL POLICIES ON RAW MATERIALS 31 2.5.3. CRITICAL RAW MATERIALS IN PORTUGAL 31 CHAPTER 3. METAL CHARACTERISATION – TUNGSTEN CASE 33 3.1. PHYSICAL AND CHEMICAL PROPERTIES 33 3.2. DISTRIBUTION AND ABUNDANCE IN THE EARTH’S CRUST 34 3.3. MINERALOGY 34 3.4. DEPOSIT TYPES 36 3.4.1. MAJOR DEPOSIT CLASSES 37 3.5. EXTRACTION METHODS AND PROCESSING 39 3.5.1. EXTRACTION 39 3.5.2. PROCESSING 40 3.6. SPECIFICATIONS AND USES 42 3.6.1. SPECIFICATIONS 42 3.6.2. USES 44 3.7. RECYCLING AND SUBSTITUTION 47 3.7.1. RECYCLING 47 3.7.2. SUBSTITUTION 48 3.8. WORLD AND EUROPEAN RESOURCES, RESERVES, AND PRODUCTION 49 3.8.1. WORLD 49 3.8.2. EUROPEAN 51 3.9. SUPPLY CHAIN 53 3.10. FUTURE SUPPLIES 53 3.11. WORLD TRADE 54 3.12. PRICES 55 CHAPTER 4. STUDY AREA FRAMEWORK 57 4.1. GEOGRAPHICAL LOCATION 57 4.2. GEOLOGICAL FRAMEWORK 59 4.2.1. REGIONAL SETTINGS 59 4.2.2. LOCAL SETTINGS 63 4.2.3. MINE SETTINGS 64 CHAPTER 5. PANASQUEIRA MINE 73 5.1. HISTORICAL REVIEW 73 5.2. MINING METHODS 74 5.3. ORE PROCESSING AND RECOVERY METHODS 77 5.3.1. RUN-OF-MINE (ROM) CIRCUIT 77 5.3.2. CRUSHING, WASHING AND SCREENING (CWS) CIRCUIT 77 5.3.3. HEAVY MEDIA SEPARATION (HMS) CIRCUIT 77 5.3.4. SAND CIRCUIT 77 5.3.5. SLIME CIRCUIT 78 5.3.6. FINAL CONCENTRATION CIRCUIT 78 5.3.7. COPPER (CU) CIRCUIT 79 5.3.8. TIN (SN) CIRCUIT 79 5.4. MAIN TYPES OF LANDFILL MINING 80 5.5. FINE TAILINGS DISPOSAL AREAS 81 5.5.1. RIO SITE 81 5.5.2. BARROCA GRANDE SITE 82 CHAPTER 6. MATERIALS, METHODOLOGIES, AND TECHNIQUES 87 6.1. SELECTION OF THE SAMPLING SITE AND SAMPLING 87 6.2. SAMPLE PREPARATION 90 6.2.1. HOMOGENISING AND QUARTERING 91 6.2.2. DRYING 92 6.2.3. MILLING 92 6.2.4. SIEVING 93 6.2.5. MINERAL CONCENTRATE 94 6.2.6. PRESSED PELLETS 95 6.3. LASER DIFFRACTION PARTICLE SIZE ANALYSIS 96 6.3.1. BECKMAN COULTER 96 6.4. X-RAY DIFFRACTION ANALYSIS 97 6.4.1. PHILIPS 97 6.5. SCANNING ELECTRON MICROSCOPY ANALYSIS 98 6.5.1. ZEISS 98 6.6. X-RAY FLUORESCENCE ANALYSIS 99 6.6.1. THERMO FISHER 99 6.6.2. PANALYTICAL 102 CHAPTER 7. RESULTS AND DISCUSSION OF RESULTS 103 7.1. GRANULOMETRICAL DATA 103 7.1.1. LASER DIFFRACTION PARTICLE SIZE ANALYSIS 103 7.2. CHEMICAL-MINERALOGICAL DATA 108 7.2.1. X-RAY DIFFRACTION ANALYSIS 108 7.2.2. SCANNING ELECTRON MICROSCOPY ANALYSIS 113 7.3. CHEMICAL DATA 118 7.3.1. X-RAY FLUORESCENCE ANALYSIS 118 CHAPTER 8. FINAL REMARKS 131 8.1. CONCLUSION 131 8.2. FUTURE WORKS 132 REFERENCES 133 APPENDICES 141 APPENDIX I - SUPPLY RISK OF THE METALLIC AND SEMI-METALLIC CRMs FOR THE EU 141 APPENDIX II - CRMs IN PORTUGAL 143 APPENDIX III - PROFILE OF THE BOREHOLE LOGGING SAMPLES 145 APPENDIX IV – RESULTS XRF THERMO FISHER (TESTALLGEO OPERATION MODE) 147 APPENDIX V – RESULTS XRF THERMO FISHER (MINING Cu/Zn OPERATION MODE) 149 APPENDIX VI – RESULTS XRF PANALYTICAL (OMNIAN OPERATION MODE) 151 APPENDIX VII – RESULTS XRF PANALYTICAL (PRO-TRACE OPERATION MODE) 153 APPENDIX VIII – RESULTS XRD ANALYSIS SURFACE AND BOREHOLE SAMPLES 155 APPENDIX IX – RESULTS SEM ANALYSIS SAMPLE S10 157 APPENDIX X – RESULTS SEM ANALYSIS SAMPLE B1.S5.4.2 159 APPENDIX XI – RESULTS SEM ANALYSIS SAMPLE B2.S2.3.2 163 ACKNOWLEDGMENTS The accomplishment of this Master's dissertation depended on the support and guidance of several people and institutions that must be credited for some of the positive contribution this work can bring to this scientific area. Therefore, I would like to acknowledge the following individuals for their guidance and encouragement, and the following companies for their contributions in making this work successful: My gratitude goes to the Department of Earth Sciences, Faculty of Sciences and Technology at the University of Coimbra, namely to Doctor Alcides Pereira and Doctor Elsa Gomes, my two scientific advisors, for their useful help and guidance throughout this dissertation. I would also like to extend my gratitude to Doctor Pedro Proença and Doctor Marina Pinto for their useful help and advice. To Doctor Fernando Pita, from the Laboratory of Ore Treatment; Doctor Manuela da Vinha, from the Laboratory of Sample Preparation and Mineral Separation; Doctor Lídia Catarino, from the Laboratory of Geotechnics; Doctor Pedro Dinis and Doctor Bárbara Costa, from the Laboratory of Sedimentology; and Carlos Maia, from the Laboratory of Geochemistry and X-Ray, whose help and advice with the practical work I am also thankful for. To Doctor Paula Morais, from the Department of Life Sciences, Faculty of Sciences and Technology at the University of Coimbra and coordinator of the transnational project ERAMIN2/2015 “BIOCriticalMetals”, I express my gratitude for her helpful contribution, which allowed the practical work used in this dissertation to take place. To Doctor José Paixão and Doctor Pedro Sidónio from the Trace Analysis and Imaging Laboratory, Department of Physics, Faculty of Sciences and Technology at the University of Coimbra, I express my sincere thankfulness for their helpful contribution. To Doctor Cristina Vila, from the Department of Mining Engineering, Faculty of Engineering at the University of Porto, and Doctor Mário Machado Leite, from the National Laboratory of Energy and Geology of Portugal, I am grateful for the shared data information provided. To Doctor Santiago Cuesta-Lopez, from the International Research Center in Critical Raw Materials for Advanced Industrial Technologies at the University of Burgos, I am thankful for the opportunity to participate in the High Level Conference “European Regions in the Critical Raw Materials Strategy and the Circular Economy Policy”, which gave me the first notion of the importance of the critical raw materials for the European Union. To the Laboratory of Wear, Testing & Materials at the Pedro Nunes Institute, namely Engineer João Dias and Engineer Nélson Duarte, I express my thankfulness for their contribution. To Space Layer Technologies at the Pedro Nunes Institute, namely Paulo Caridade and Filipe Matos, I am grateful for their availability and contribution towards this dissertation. I To Sojitz Beralt Tin & Wolfram (Portugal), S.A., namely Engineer Paulo Ferraz, Engineer Manuel Pacheco, Engineer Donzília Gonçalves and Filipe Pinto, I express my sincere gratitude for the technical information and permission to collect the samples, which were vital for the completion of this dissertation. To Empresa de Desenvolvimento Mineiro, S.A., namely Engineer Mário Guedes, I am thankful for the availability of the equipment for some of the proposed analyses. To the Institute for Research and Technological Development in Construction, Energy, Environment and Sustainability, namely Doctor António Tadeu and Doctor João Almeida, I express my gratitude for their availability and contribution. I would like to gratefully thank the former Panasqueira miner and my friend, Jorge Abrantes, for his guidance in the field work at the so-called “Couto Mineiro” of the Panasqueira mine. I would also like to express my appreciation to all the professors and colleagues from the Universities of Coimbra, Oviedo and Svalbard that, in some way, were involved in my academic learning process. A particular thank you goes to my colleagues and friends André Pacheco, Bruno Teixeira, Flávio Almeida, Pablo Martinez, Pedro Neves and Rodrigo Leal, for their support and friendship throughout this academic journey. A special gratitude goes to Katie, for all the emotional support and help throughout our journey. My last acknowledgement goes to my family, for the unconditional support and guidance throughout the years, and for always reminding me that the future is built today. II RESUMO No âmbito da Estratégia Europa 2020, a Comissão Europeia identificou dois constrangimentos que têm condicionado a competitividade e o crescimento da economia europeia: a elevada dependência de importação de produtos acabados e a insegurança no fornecimento de matérias-primas.