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(Co, Mn, Ni)(OH)2], in the VERMION MT (GREECE) and ITS GENETIC SIGNIFICANCE for the MINERAL GROUP of HYDROXIDES

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(Co, Mn, Ni)(OH)2], in the VERMION MT (GREECE) and ITS GENETIC SIGNIFICANCE for the MINERAL GROUP of HYDROXIDES In: Chemical Mineralogy, Smelting and Metallization ISBN 978-1-60692-853-0 Editor: E. D. McLaughlin and L. A. Breaux, pp. © 2009 Nova Science Publishers, Inc. Chemical Mineralogy, Smelting and Metallization Click to enlarge Editors: Eugene D. McLaughlin and Levan A. Breaux Book Description: Mineralogy is an earth science focused around the chemistry, crystal structure, and physical properties of minerals. This book presents new research on mineralogy, including a review on the chemical mineralogy of ornamental rock waste and water treatment plant waste, which are produced worldwide in large scales and are a concerning issue for industry and environmentalists alike. This book also presents new research on smelting, a process that liberates the metallic element of an ore from its compound and separates it from the waste part of the charge. The environmental impact of smelting activities is discussed, as well as the combination of smelting with gasification for treatment of solid waste and the production of alternative fuel. 2 Maria Economou-Eliopoulos and Demetrios G. Eliopoulos Chapter 1, pages 1-18 A NEW SOLID SOLUTION, [(Co, Mn, Ni)(OH)2], IN THE VERMION MT (GREECE) AND ITS GENETIC SIGNIFICANCE FOR THE MINERAL GROUP OF HYDROXIDES Maria Economou-Eliopoulos∗1 and Demetrios G. Eliopoulos2 1University of Athens, Department of Geology and Geoenvironment, Section of Economic, Geology and Geochemistry, Panepistimiopolis, GR-15784, Athens, Greece 2Institute of Geology and Mineral Exploration (IGME), Entrance C’, 1, Sp. Louis St., Olympic Village, Acharnae, P.C. 13677 Athens, Greece ABSTRACT Nickel hydroxide and Ni1-xCox(OH)2 compounds known as active materials are of a great experimental interest, since research of the mixed hydroxide contributes to a better understanding on the thermal behaviour of nanoparticles of nickel hydroxide compounds. Among natural mineral of the group of hydroxides [X(OH)2] pyrochroite [Mn(OH)2] and theophastite [Ni(OH)2] have been discovered in Pajsberg mine, Sweden (1864) and the Vermion Mt, Greece (1981), respectively, whilst the Co(OH)2 is known only as a synthetic compound. The new mineral with the Co(OH)2 composition (CoO 80.61, H2O 19.39) was discovered in the Vermion Mt, recently. It was found within small (1×2 m), strongly schistose Ni-laterite occurrences, hosted in dismembered, serpentinized harzburgites, close to their contacts with overlying limestones, located along a strong shear zone. The solid-solution (Co, Mn, Ni) (OH)2 phases, with a green colour and compositional variation from Co-dominated [(Co0.59Mn0.24Ni0.17)Σ1.00(OH)2] to Mn-rich [(Mn0.51Ni0.26Co0.23)Σ1.00(OH)2] members appear as concentrated layers, composed by very fine platy and fibrous crystals. The mineral dominated by cobalt, exhibit a Mn- enrichment towards peripheral parts, suggesting an earlier deposition of the former compared to the latter. The XRD and SEM/EDS investigation showed that there are similarities between theophastite and the new mineral Co(OH)2 in (a) their habit and the small crystal size, (b) their conchoidal fracture, and (c) their powder XRD patterns, suggesting that the replacement of Ni2+ by mostly Co2+ and to a lesser extend Mn2+ have no influence on the crystal structure, and that they have a common origin in space, subsequently of the strong late tectonic evolution, which obscures earlier deformation events. ∗ E-mail: [email protected] A New Solid Solution, [(Co, Mn, Ni)(OH)2], in the Vermion Mt (Greece)… 3 Associated minerals are: theophrastite, Co,Ni-bearing pyrochroite, magnetite, Al-rich chromite, millerite, garnet (Cr-bearing grossularite), vezuvianite and clinochlore and Ni- serpentine. The formation of Ni-serpentine at the expense of Ni-poor serpentine via supergene alteration is consistent with the thermodynamic data. The distribution of Ni among secondary minerals seems to be consistent with their values of the crystal field stabilization energy (CFSE), solubility and the activation energy derived from the Arrhenius equations for Ni sorption on clay mineral. The scarcity of the (Ni, Co, Mn)-hydroxides, their extremely tiny crystal size, the existence of high degree of purity rarely and their concentrating development, mostly on silicate minerals, are the most salient features. These features may be related with the formation processes of the transition metals (Ni, Co, Mn) hydroxides, probably under alkaline (in the pH region 7 to 8) conditions, due to neighbouring limestones and low temperature (< 200 oC). INTRODUCTION Nickel hydroxide and Ni1-xCox(OH)2 compounds are known to be active materials used in the cathodes of rechargeable batteries and research on this subject is a great interest. Recently, investigators have focussed on the thermal behaviour of nickel hydroxide [Ni(OH)2] and of nickel cobalt hydroxide [Ni1-xCox(OH)2] particles arising from synthetic colloidal solutions, since the study of the mixed hydroxide contributes to a better understanding on the thermal behaviour of nanoparticles of nickel hydroxide compounds. (Boyer et al., 2004; Vidotti et al., 2007). The group of hydroxides [X(OH)2] include pyrochroite [Mn(OH)2] which was discovered in Pajsberg mine, Filipstad, Sweden, in 1864 (Palache, 1935), theophrastite [Ni(OH)2] discovered in the Vermion Mountain, Greece (Marcopoulos and Economou, 1981), whilst Co(OH)2 is known only as a synthetic compound. Recently, a (Co, Mn, Ni)-hydroxide with a wide compositional range, were discovered in the Vermion Mountain, Greece, in a spatial association with theophrastite. These minerals are hosted in serpentinized harzburgites, within small (1×2m), strongly schistose Ni-laterite occurrences, located along a strong shear zone. Mineralogical and chemical characteristic features of the new hydroxide mineral, Co(OH)2, and associated minerals presented in this study provide constraints on their origin. GLOBAL OCCURRENCES OF Ni(OH)2 AND (Ni, CO, Mn)(OH)2 Nickel is a transition element that is widespread as both siderophile (associated with iron) and chalcophile (associated with sulphur), and it is mined throughout the world from two types of ore deposits (a) laterites where the principal ore minerals are Ni-bearing iron oxides and hydrous nickel silicates and (b) magmatic sulphide deposits where the principal ore mineral is pentlandite [(Ni,Fe)9S8]. Generally cobalt is mined as cobaltite, CoAsS, linnaeite, Co3S4, carrollite, Cu(Co,Ni)2S4, (cobaltian) pyrite, FeS2, and Co-bearing manganese and iron oxides and clays. 4 Maria Economou-Eliopoulos and Demetrios G. Eliopoulos Cobalt deposits fall into a number of categories (Golightly, 1981; Brand et al., 1998; Gleeson et al., 2004). Despite the significant Mn, Zn and Co contents (whole ore analysis) of some Ni-laterite deposits of the Balkan peninsula, Mn, Zn and Co enrichment in chromite is restricted to certain allochthonous deposits (Economou-Eliopoulos, 2003). The occurrence of the nickel hydroxides [Ni(OH)2] and [Co(OH)2] in nature is extremely rare. The natural occurrence of nickel hydroxide was firstly reported by Williams (1960) but no mineral name was given to the compound. Theophrastite, Ni(OH)2 was discovered in the Vermion Mt, 50 km west of Thessaloniki, Macedonia, Greece, which is very close to pure Ni(OH)2, similar in properties to synthetic Ni(OH)2 (Macropoulos and Economou, 1981). Subsequently it was described on chromitite specimens from the Hagdale Quarry, Unst, Shetland Islands, Scotland. It is Mg-bearing and occurs associated with a very poorly crystalline Ni-containing mixed hydroxide of the pyroaurite type and/or zaratite. X-ray powder diffraction data show a shift in d spacing toward brucite compared with pure Ni(OH)2 (Livingstone and Bish, 1982). Theophrastite located in the nickel ores of the Lord Brassey mine (Heazlewood ophiolitic ultramafic complex), Tasmania, Australia, is not pure Ni(OH)2, but a mixed with poorly crystalline pyroaurite and it is associated with zaratite within veins cutting massive magnetite- chromite ore hosted in serpentinite (Henry and Birch 1992). The primary mineralization consists of nickel sulfides (pentlandite and heazlewoodite) with minor Ni-Fe alloy (awaruite) intergrown with grains of magnetite and various silicates (Williams, 1958). o o The new mineral Co(OH)2 was discovered in the Vermion Mt (40 26’ Ν, 22 10’ Ε), in a spatial association with pure Ni(OH)2. It occurs within small, strongly schistose Ni-laterite occurrences, dominated by magnetite, located along a strong shear zone, which define a trend parallel to the general NW-SE displacement direction of ophiolites in the Balkan peninsula (Eliopoulos and Economou-Eliopoulos, 2000). Laterite ore is hosted in dismembered, serpentinized harzburgites, close to their contacts with overlying limestones, in the Vermion Mountains and has been affected by intense tectonic activity, which has created over thrusting, foliation and lineation of minerals. The compact Ni-laterite ore is characterized by lack of pisolitic–oolitic texture, with magnetite being the major mineral. ANALYTICAL METHODS Polished sections prepared from the Ni-laterite ore occurrences of the Vermion area were examined by reflected light microscopy and scanning electron microscope. Quantitative analyses were carried out at the University of Athens, Department of Geology, using a JEOL JSM 5600 scanning electron microscope, equipped with automated OXFORD ISIS 300 energy dispersive analysis system. Analytical conditions were 20 kV accelerating voltage, 0.5 nA beam current, <2 µm beam diameter and 50 second count times. The following X-ray lines were used: Standards used were pure metals for the elements Ni, Co and Mn, and pyrite for S and Fe. The H2O was calculated to obtain 2 (OH) pfu. A New Solid Solution, [(Co, Mn, Ni)(OH)2], in the Vermion Mt (Greece)… 5 Trace element concentrations in whole ore were determined by ICP/MS analysis at Activation Laboratories, Ltd, Canada, after an alkaline peroxide fusion. Platinum, Pd and Au were determined by ICP/MS analysis after preconcentration using the lead fire assay technique from large (30 g) samples, at Activation Laboratories, Ltd, Canada.
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