Compositional and structural characterisation of Ni - phyllosilicates in hydrous silicate type Ni - laterite deposits Cristina Villanova de Benavent ADVERTIMENT . La consulta d’aquesta tesi queda condicionada a l’acceptació de les següents condicions d'ús: La difusió d’aquesta tesi per mitjà del servei TDX ( www.tdx.cat ) i a través del Dipòsit Digital de la UB ( diposit.ub.edu ) ha estat autoritzada pels titulars dels drets de propietat intel·lectual únicament per a usos privats emmarcats en activitats d’investigació i docència. No s’autoritza la seva repro ducció amb finalitats de lucre ni la seva difusió i posada a disposició des d’un lloc aliè al servei TDX ni al Dipòsit Digital de la UB . No s’autoritza la presentació del seu contingut en una finestra o marc aliè a TDX o al Dipòsit Digital de la UB (framin g). Aquesta reserva de drets afecta tant al resum de presentació de la tesi com als seus continguts. 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DEPARTAMENT DE CRISTAL·LOGRAFIA, MINERALOGIA I DIPÒSITS MINERALS FACULTAT DE GEOLOGIA Compositional and structural characterisation of Ni- phyllosilicates in hydrous silicate type Ni-laterite deposits PhD Thesis Cristina Villanova de Benavent October 2015 UNIVERSITAT DE BARCELONA DEPARTAMENT DE CRISTAL·LOGRAFIA, MINERALOGIA I DIPÒSITS MINERALS FACULTAT DE GEOLOGIA Compositional and structural characterisation of Ni-phyllosilicates in hydrous silicate type Ni-laterite deposits Tesi doctoral presentada per Cristina Villanova de Benavent Memòria presentada per optar al títol de doctora per la Universitat de Barcelona amb Menció Internacional Tesi realitzada dins del Programa de Doctorat de Ciències de la Terra per la Universitat de Barcelona, sota la direcció del Dr. Joaquín A. Proenza i el Dr. Salvador Galí La Doctoranda Els Directors Cristina Villanova de Joaquín Antonio Salvador Galí i Medina Benavent Proenza Fernández Barcelona, octubre de 2015 ACKNOWLEDGEMENTS First of all, I would like to extend my most sincere thanks to my PhD advisors, Joaquín A. Proenza and Salvador Galí. Their limitless patience, dedication and interest have been a very positive influence during the development of this thesis. Special thanks are given to Joan Carles Melgarejo, who introduced me to the fascinating world of Mineralogy and who trusted me ten years ago to start a first research work. This thesis was possible thanks to the hospitality and generosity of the staff in Falcondo Glencore Xstrata Nickel (formerly Falconbridge Dominicana C por A), in particular of Francisco Longo, for the field trip logistics, the inestimable help during sample collection, and field work in general. I am also grateful to the Emeritus Professor John F. Lewis for his vast knowledge on the geology of Hispaniola, without whom this thesis would not have been possible. The investigation of Ni-phyllosilicates was conducted thanks to (by order of appearance in Chapter 3: Materials & Methods): Xavier Alcobé and Maria Barba (XRD, CCiT-UB), Maite Garcia-Vallès and Mercedes Aguilar (DTA-TG, UB), Dolors Barso, Montserrat Sibila, Fadoua Zoura Oumada, Vicenç Planella (thin section facility, UB), Jesús Montes Rueda (thin section facility, UGr), Eva Prats, Javier García-Veigas and Anna Domínguez (SEM and FESEM, CCiT-UB), Xavier Llovet (EMP, CCiT-UB), Josep Roqué-Rosell and Fèlix Mata (TEM sample preparation, CCiT-UB), Isabel Nieto, José Damián Montes (TEM sample preparation, UGr), Claudia Magrini (TEM sample preparation, UniSi), Joaquim Portillo, Aránzazu Villuendas, Joan Mendoza (TEM, CCiT-UB), Fernando Nieto and María del Mar Abad (TEM, UGr), Cecilia Viti and Enrico Mugnaioli (TEM, UniSi), Tariq Jawhari (micro- Raman spectroscopy, CCiT-UB), Elena Bailo (micro-Raman spectroscopy, WITec), Josep Roqué-Rosell (X-ray absorption spectroscopy by synchrotron radiation, Diamond Light Source and Lawrence Berkeley Laboratory), Jordi Bellés (flow-through experimental setup, IDAEA-CSIC), Rafael Bartrolí (ICP-AES, IDAEA-CSIC). I would also like to acknowledge all the coauthors who made accurate scientific revisions of my texts and from whom I learnt some of the secrets of scientific writing: Esperança Tauler, Josep Roqué-Rosell and Cristina Domènech (UB), Fernando Nieto and Antonio García-Casco (UGr), Cecilia Viti (UniSi), Josep Mª Soler and Jordi Cama (IDAEA-CSIC). The successive anonymous reviewers (and M. Alain Baronnet), who made constructive comments and observations that helped to improve my papers, are also sincerely acknowledged. It is worth noting that the fruitful conversations with Frederick J. Wicks at the IMA2014 Meeting and with Michel Cathelineau at the SGA2015 Meeting contributed to this thesis as well and deserve to be mentioned here. In addition, I would like to thank the help extended by some colleagues who provided me rare and/or old papers that completed the list of references for this thesis: Montgarri Castillo i Oliver (Liversidge, 1874; Maksimović,1973), Sergey Silantsyev (Rukavishnikova, 1956; Vitovskaya & Berkhin, 1968, 1970), Alexander Schopf (Spangenberg, 1938; 1949), Mathieu Chassé (Caillère, 1965). I thank also Alicja Lacinska, for providing me samples LIZ-1 and LIZ-2, Àngels Canals for sample TLC and Esperança Tauler for sample SEP (see Chapter 6). The administrative help of the secretaries of the Departament de Cristal·lografia, Mineralogia i Dipòsits Minerals (UB) is also gratefully acknowledged, for their patience and ability to solve any kind of issue. And last but not least, I thank the unconditional support from my parents, Antonio and Guillermina, who always encouraged me to do whatever I wanted in life and to pursue my dreams; from Hèctor, with remarkable patience and kindness; and from my entire family as well. I sincerely thank the scientific and personal support from friends and colleagues, in particular Montgarri Castillo i Oliver, Thomas Aiglsperger, who were excellent office mates; but also Esperança Tauler, Cristina Domènech, Marc Campeny, Sandra Amores, Lídia Butjosa, Amaia Castellano, Lisard Torró, Mariona Tarragó, Raül Benages, Juan Hernández (UB), Pura Alfonso, Abigaíl Jiménez (UPC), Fernando Nieto, Fernando Gervilla, Antonio García-Casco, Idael Blanco, Juan Cárdenas (UGr), Darío Chinchilla, Lorena Ortega, Ricardo Castroviejo (UCM); and specially Cecilia Viti and Enrico Mugnaioli who warmly welcomed me in the Università degli Studi di Siena, and Enrico Capezzuoli, Rocco Novellino, Cristina Fornacelli, Andrea Brogi, Massimiliano Ciacci, Alessio Casagli, Marco Meccheri, Luca Foresi, Ivan Martini, Elisa Ambrosetti, Giovanna Giorgetti, Barbara Terrosi (UniSi), with whom I spent some unforgettable moments during these five years. This PhD thesis was economically possible thanks to the funding provided by the FPU pre- doctoral and the “Estancias Breves” scholarships given by the Spanish Ministry of Education, the Spanish projects CGL2009-10924, CGL2012-36263 (co-financed by Fondo Europeo de Desarrollo Regional: FEDER), CGL2011-30153 and CGL2012-32169, the Catalan projects SGR 2009-444 and SGR 2014-1661. In addition, the grants given by the Society of Geology Applied to Mineral Deposits (SGA) to attend the 2011, 2013 and 2015 Biennial Meetings; by the International Union of Crystallography to attend the 2013 Meeting of the Spanish Mineralogical Society (SEM), the grants given by the SEM and the International Mineralogical Association (IMA) to attend the 2014 IMA Meeting, and the “Borsa de viatges” travel grants given by the Facultat de Geologia (Universitat de Barcelona) are sincerely acknowledged. ABSTRACT Ni-bearing Mg-phyllosilicates (commonly known as garnierites) are significant ore minerals in many Ni-laterite deposits worldwide. However, the characterisation of these mineral phases is complex, as well as their classification and nomenclature, due