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Periodico Di Mineralogia and the Support of Sapienza Università Di Roma, It Would Have Been Very Difficult to Organize This Meeting and This Volume September, 2015 1-208 September, 2015 1-208 PERIODICO di MINERALOGIA PERIODICO di MINERALOGIA established in 1930 established in 1930 ISSN 0369-8963 An International Journal of September, 2015 MINERALOGY, CRYSTALLOGRAPHY, GEOCHEMISTRY, ORE DEPOSITS, PETROLOGY, VOLCANOLOGY and applied topics on Environment, Archaeometry and Cultural Heritage A MINERALOGI Proceedings of the 8 th European Conference on Mineralogy and Spectroscopy PERIODICO di Rome, Italy, September 9-11, 2015 Edited by Giovanni B. Andreozzi and Ferdinando Bosi 9788868123857_436 _ TF B _ 3 1-208 Edizioni Nuova Cultura PERIODICO di MINERALOGIA established in 1930 http://www.periodicodimineralogia.it [email protected] September, 2015 ECMS 2015 Proceedings of the 8th European Conference on Mineralogy and Spectroscopy Property of Università degli Studi di Roma “La Sapienza” Piazzale Aldo Moro 5, I-00185 Roma, Italy Edizioni Nuova Cultura Copyright © 2015 Edizioni Nuova Cultura - Roma, Italy ISSN PRINT: 0369-8963 ISSN ON LINE: 2239-1002 All rights reserved including translation into other languages. This journal, or some part of it, cannot be reproduced in any form without permission. Director ANTONIO GIANFAGNA Dipartimento di Scienze della Terra, Università degli Studi di Roma “La Sapienza” Piazzale Aldo Moro 5, I-00185 Roma, Italy Tel. +39 0649914921; Fax +39 064454729; e-mail: [email protected] - [email protected] Authorization by Tribunale di Roma n. 313/2000 This journal is printed with funds by Università degli Studi di Roma “La Sapienza” ECMS 2015 8th European Conference on Mineralogy and Spectroscopy Preface Rome is proud to host the eighth edition of the European Conference on Mineralogy and Spectroscopy (ECMS 2015). This is a welcome back, after the starting point of this conference cycle in Rome (1988) and following editions held in Berlin (1995), Kiev (1996), Paris (2001), Vienna (2004), Stockholm (2007) and Potsdam (2011). The Rome 2015 conference will hopefully reflect the philosophy of previous conferences and provide a common forum to present new ideas, concepts and results related to mineral spectroscopy. It will also offer an opportunity for students and young scientists to meet and interact with established, well-known scientists. The conference deals with mineralogy, spectroscopy and related fields of science, bringing together both theoretically and experimentally oriented scientists and providing an opportunity to share ideas and learn from one another. The ECMS 2015 is housed in the headquarters of the National Research Council, and consists of three days of oral presentations and two days of poster sessions. Keynote lectures will be presented by Frank C. Hawthorne, Laurence Galoisy, Robert D. Shannon, Giancarlo Della Ventura, Bjorn Winkler and Catherine McCammon. This volume is the joint effort of all conference participants largely coming from Europe, but also from America, Asia and Australia. It contains 100 contributions, many of which present experimental results and applications based on new or well- established analytical techniques, while others highlight theoretical and computational approaches to our better understanding of short-range and long-range structures of minerals and materials. We are very grateful for the constant support of Francesco Di Benedetto (publicity chair), Sabrina Nazzareni (treasurer) and our scientific advisory board: Danilo Bersani, Giuseppe Cruciani, Michele Dondi, Ulf Hålenius, Monika Koch-Müller, Roberta Oberti, Henrik Skogby and Sergio Speziale. Without the generous sponsoring from the Società Italiana di Mineralogia e Petrologia (SIMP), Italian National Research Council (CNR) and Periodico di Mineralogia and the support of Sapienza Università di Roma, it would have been very difficult to organize this meeting and this volume. We also appreciate the sponsorship and scholarship grant from the European Mineralogical Union (EMU) and the International Union of Crystallography (IUCr), and contributions from private companies (Bruker, Geologica, Gemmoraman, Masterstones, PANalytical). Thanking all participants for coming in the Eternal City, we wish you all a stimulating, informative and enjoyable conference and offer a sincere welcome to the ECMS 2015. Giovanni B. Andreozzi and Ferdinando Bosi Co-chairmen On behalf of the Organizing Committee Keynote Lectures Periodico di Mineralogia, ECMS 2015, 1-2 Short-range order in rock-forming and accessory minerals: a review of the present state of affairs and some suggestions as to what to do next Frank C. Hawthorne Department of Geological Sciences, University of Manitoba, Winnipeg, R3T2N2, Canada Corresponding author: [email protected] Short-range order involves local clusters of atoms that occur either more or less frequently than predicted by a random distribution. Where solid solutions involve coupled replacement of ions by ions of different charge, the valence-sum rule of bond-valence theory constrains the relative positions of the substituent ions. This constraint produces short-range order as the rela- tive arrangements of the ions is not random. The ubiquity of polyvalent substitutions in miner- als means that short-range order is the rule rather than the exception in many rock-forming and accessory minerals. I will briefly review those groups of minerals in which short-range order is a common feature: amphiboles (e.g., Hawthorne and Della Ventura, 2007), tourmalines (e.g., Bosi, 2011), micas (e.g., Sanz et al., 2015), spinels (e.g., Bosi et al., 2012) etc., and will discuss the difficulties in deriving short-range arrangements of atoms experimentally. Hydrogen is a key probe of short-range order in hydroxyl minerals, and careful work can determine much of the short-range order present in these minerals. Anhydrous minerals are more difficult to deal with, as the spectroscopic techniques sensitive to short-range order are not as comprehensive in their sensitivity as infrared spectroscopy in the OH-stretching region. [1] Bond-valence theory has been used in a qualitative way to predict short-range order in a few minerals. A more quantitative approach may be possible using a priori bond-valence cal- culations, and I will examine this possibility here. [2] One of the major problems in rigorously considering short-range order in crystal structures is the propagation of this order throughout the structure: how do we get a handle on what happens as short range becomes medium range? Current ways of looking at these issues always involve mean-field approaches; are the deriva- tion of “real” solid-solution structures possible? If we are to improve our understanding of short-range order and develop more realistic thermodynamic models for solid solutions, we need to address these issues. 2 Periodico di Mineralogia, ECMS 2015, 1-2 F.C. Hawthorne References Bosi, F. (2011) - Stereochemical constraints in tourmaline: from a short-range structure to a long-range structure. Canadian Mineralogist, 49, 17-27. Bosi, F., Halenius, U., D’Ippolito, V. and Andreozzi, G.B. (2012) - Blue spinel crystals in the MgAl2O4-CoAl2O4 series: Part II. Cation ordering over short-range and long-range scales. American Mineralogist, 97, 1834-1840. Hawthorne, F.C. and Della Ventura, G. (2007) - Short-range order in amphiboles. In: Amphi- boles: Crystal Chemistry, Occurrence and Health Issues (Hawthorne, F.C., Oberti, R., Della Ventura, G., Mottana, A., eds.) Reviews in Mineralogy and Geochemistry 67, Mineralogi- cal Society of America and Geochemical Society, Washington D.C., 173-222. Sanz, J., Sobrados, I. and Robert, J-.L. (2015) - Influence of hydration on 23Na, 27Al, and 29Si MAS-NMR spectra of sodium saponites and sodium micas. American Mineralogist, 100, 1076-1083. Periodico di Mineralogia, ECMS 2015, 3-4 Structural control of the color of minerals and glasses using spectroscopic tools Laurence Galoisy Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie (IMPMC) - Sorbonne Universités – UPMC UMR CNRS 7590 - IRD UMR 206 – MNHN - 4 place Jussieu F-75005 Paris, France Corresponding author: [email protected] Color is one of the most important properties in minerals and glasses. Light absorption by transition elements, either as major part of the mineral chemistry or as impurities, is one of the most important coloring mechanisms. To induce coloration, transition elements should be lo- cated in specific surroundings in minerals and glasses. This local environment depends on the structure and composition of the materials and on the prevailing thermodynamic conditions during their formations. Different colorations in the same mineral group may arise from ions with the same oxidation state and substituted site: for instance, Cr3+ in octahedral sites may give rise to purple, red or green colors depending on the mineral structure and composition. Naturally multi-faceted garnets form wide solid-solutions with each other and captivate people with their incomparable range of colors (from green to orange and red) which are large- ly controlled by the crystal chemistry of substituted transition elements (Galoisy, 2013). The variations of colors and hues of garnets are related to the presence of coloring elements such as Fe, Mn, Cr, V, Ti substituted in the structure of garnet minerals between various end-members A3B2(SiO4). Spectroscopic techniques (UV-Visible-Near IR spectroscopy, Electron Paramagnet- ic Resonance and X-ray Absorption Spectroscopy) demonstrate how the nature and concentra- tion of these cations explain the
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