Exotic accessory minerals in layered chromities of the Campo Formoso complex (Brazil)

The Campo Formoso stratiform intrusive complex, in Bahia State, Brazil, considered to be of Paleoproterozoic age, consists of a tabular body of ultramafic rocks about 40 km long and 100-1100 m wide. Thick horizons of chromitite are exploited and the deposits are the richest in Brazil. The complex was intruded by the Campo Formoso calc-alkaline batholith, emplaced by the result of the Transamazonian collision-related orogeny. The peridotite was firstly thoroughly serpentinized, then affected by a renewed cycle of hydrothermal alteration as the batholith cooled, leading in the roof zone to emerald mineralization around roof pendants. An even later influx of fluid led to the formation of talc, silica and carbonates, such that the ultramafic rocks were locally converted to listwanite. The chromitite sequences are highly unusual in containing rather exotic minerals, such as monazite-(La), monazite-(Ce), apatite, galena, bismuthinite, antimony, and three unknown minerals of stoichiometry PbSb2, Pb6Sb and PbSb4, all associated with the clinochlore. The latter phases may have formed during hydrothermal activity in the system Pb-Sb. The presence of these exotic minerals in chromitite, which makes this occurrence unique in the world, strongly support the hypothesis that the La, Ce, P, Pb, Bi and Sb were metasomatically added to the Campo Formoso chromitite horizons by hydrothermal fluids emanating from the nearby Campo Formoso calc-alkaline batholith as it cooled

Crystal-chemistry of sulfates from the Apuan Alps, Tuscany, Italy. VIII. New data on khademite, Al(SO 4)F(H 2 O) 5

Khademite, ideally Al(SO4)F(H2O)5, from the Monte Arsiccio mine, Apuan Alps, Tuscany, Italy, has been characterised through quantitative electron microprobe analysis, micro-Raman spectroscopy and single-crystal X-ray diffraction. Khademite occurs as colourless to whitish tabular crystals, up to 5 mm. Electron microprobe analysis (in wt.%, average of 20 spot analyses) gave: SO3 35.43, Al2O3 21.27, F 6.92, H2Ocalc 39.73, sum 103.35, -O = F 2.92, total 100.43. On the basis of 10 anions per formula unit, assuming the occurrence of 5 H2O groups and 1 (F+OH) atom per formula unit, its chemical formula can be written as Al0.96S1.02O4[F0.84(OH)0.16]Σ1.00·5H2O. The Raman spectrum of khademite is characterised by the occurrence of vibrational modes of SO4 groups and by broad and strong bands due to the O-H stretching modes. Khademite is orthorhombic, space group Pcab, with unit-cell parameters a = 11.1713(2), b = 13.0432(3), c = 10.8815(2) Å, V = 1585.54(5) Å3 and Z = 8. The crystal structure refinement converged to R1 = 0.0293 on the basis of 2359 unique reflections with Fo > 4σ(Fo) and 152 refined parameters. The crystal structure of khademite is characterised by the alternation, along b, of two distinct kinds of {010} layers, one formed by [001] rows of isolated Al-centred octahedra, connected to each other through H bonds, and the other showing isolated SO4 groups. Along b, oxygen atoms belonging to SO4 groups act as acceptor of H bonds from H2O groups coordinating Al atoms. The new data improved the description of the H bonds in khademite and led us to discuss about the possible existence of its (OH)-analogue, rostite. In addition, Raman spectroscopic data were collected on the same crystal used for the crystal-chemical characterisation, allowing a comparison with previous results

The Stillwater Complex chromitites : the response of chromite crystal chemistry to magma injection

Nineteen chromite crystals from the A, B, E, G, H, J and K chromitite layers of the Peridotite Zone of the Stillwater Complex (Montana, USA) have been studied by means of X-ray single crystal diffraction and microprobe analyses. The results show that samples from the basal A layer are quite different from the others showing very high oxygen positional parameter u (0.2633-0.2635) and Ti- contents (0.059-0.067apfu). Mg# values are within the range 0.21-0.23 while for the other chromites it is in the range 0.45-0.47. Moreover, for the other samples, according to the structural parameters, two groups have been identified. The first one comprises samples of layers B, E and G, the second includes H, J and K layer samples. It is supposed that high Fe2+ and Ti contents of A layer samples are due to the post-crystallization reaction with interstitial liquid. This fact allowed a very slow cooling rate as evidenced by the high u values. The fractionation of evolved magma from within the intrusion and pulse of a new magma bringing more chromium into the chamber lead to Cr- and Fe3+ -rich compositions and consequently to the increase of the cell edges. The decrease of u values seems to be related to the Cr+Fe3+ and/or Al contents

Dutrowite, Na(Fe2.52+Ti0.5)Al6(Si6O18)(BO3)3(OH)3O, a new mineral from the Apuan Alps (Tuscany, Italy). The first member of the tourmaline supergroup with Ti as a species-forming chemical constituent

The new tourmaline supergroup mineral dutrowite, Na(Fe2.52+Ti0.5)Al6(Si6O18)(BO3)3(OH)3O, has been discovered in an outcrop of a Permian metarhyolite near the hamlet of Fornovolasco, Apuan Alps, Tuscany, Italy. It occurs as chemically homogeneous domains, up to 0.5 mm, brown in colour, with a light-brown streak and a vitreous lustre, within anhedral to subhedral prismatic crystals, up to 1 mm in size, closely associated with Fe-rich oxy-dravite. Dutrowite is trigonal, space group R3m, with aCombining double low line15.9864(8), cCombining double low line7.2187(4) Å, VCombining double low line1597.68(18) Å3, and ZCombining double low line3. The crystal structure was refined to R1Combining double low line0.0257 for 1095 unique reflections with Fo>4σ (Fo) and 94 refined parameters. Electron microprobe analysis, coupled with Mössbauer spectroscopy, resulted in the empirical structural formula X(Na0.81Ca0.20K0.01)ς1.02 Y(Fe1.252+Mg0.76Ti0.56Al0.42)ς3.00 Z(Al4.71Fe0.273+V0.023+Mg0.82Fe0.182+)ς6.00 T[(Si5.82Al0.18)ς6.00O18] (BO3)3O(3)(OH)3O(1)[O0.59(OH)0.41]ς1.00, which was recast in the empirical ordered formula, required for classification purposes: X(Na0.81Ca0.20K0.01)ς1.02 Y(Fe1.432+Mg1.00Ti0.56)ς3.00 Z(Al5.13Fe0.273+V0.023+Mg0.58)ς6.00 T[(Si5.82Al0.18)ς6.00O18] (BO3)3V(OH)3 W[O0.59(OH)0.41]ς1.00. Dutrowite is an oxy-species belonging to the alkali group of the tourmaline supergroup. Titanium is hosted in octahedral coordination, and its incorporation is probably due to the substitution 2Al3+ Combining double low line Ti4+ + (Fe,Mg)2+. Its occurrence seems to be related to late-stage high-T/low-P replacement of "biotite"during the late-magmatic/hydrothermal evolution of the Permian metarhyolite

Exotic accessory minerals in layered chromitites of the Campo Formoso complex (Brazil)

The Campo Formoso stratiform intrusive complex, in Bahia State, Brazil, considered to be of Paleoproterozoic age, consists of a tabular body of ultramafic rocks about 40 km long and 100-1100 m wide. Thick horizons of chromitite are exploited and the deposits are the richest in Brazil. The complex was intruded by the Campo Formoso calc-alkaline batholith, emplaced by the result of the Transamazonian collision-related orogeny. The peridotite was firstly thoroughly serpentinized, then affected by a renewed cycle of hydrothermal alteration as the batholith cooled, leading in the roof zone to emerald mineralization around roof pendants. An even later influx of fluid led to the formation of talc, silica and carbonates, such that the ultramafic rocks were locally converted to listwanite. The chromitite sequences are highly unusual in containing rather exotic minerals, such as monazite-(La), monazite-(Ce), apatite, galena, bismuthinite, antimony, and three unknown minerals of stoichiometry PbSb2, Pb Sb and PbSb4, all associated with the clinochlore. The latter phases may have formed during hydrothermal activity in the system Pb-Sb. The presence of these exotic minerals in chromitite, which makes this occurrence unique in the world, strongly support the hypothesis that the La, Ce, P, Pb, Bi and Sb were metasomatically added to the Campo Formoso chromitite horizons by hydrothermal fluids emanating from the nearby Campo Formoso calc-alkaline batholith as it cooled

The podiform chromitites in the Dagküplü and Kavak mines, Eskisehir ophiolite (NW-Turkey) : genetic implications of mineralogical and geochemical data

Mantle tectonites from Eskisehir (NW-Turkey) include high-Cr chromitites with limited variation of Cr#, ranging from 65 to 82. Mg# ratios are between 54 and 72 and chromite grains contain up to 3.71 wt% Fe2O3 and 0.30 wt% TiO2. PGE contents are variable and range from 109 to 533 pbb. Chondrite-normalized PGE patterns are flat from Os to Rh and negatively sloping from Rh to Pd. Total PGE contents and low Pd/Ir ratios (from 0.07 to 0.41) of chromitites are consistent with typical ophiolitic chromitites. Chromite grains contain a great number of solid inclusions. They comprise mainly of highly magnesian (Mg# 95-98) mafic silicates (olivine, amphibole and clinopyroxene) and base-metal sulfide inclusions of millerite (NiS), godlevskite (Ni7S6), bornite (C5FeS4) with minor Ni arsenides of maucherite (Ni11As8) and orcelite (Ni5-xAs2), and unnamed Cu2FeS3 phases. Heazlewoodite, awaruite, pyrite, and rare putoranite (Cu9Fe,Ni9S16) were also detected in the matrix of chromite as secondary minerals. Laurite [(Ru,Os)S2] was the only platinum-group minerals found as primary inclusions in chromite. They occur as euhedral to subhedral crystals trapped within chromite grains and are believed to have formed in the high temperature magmatic stage during chromite crystallization. Laurite has limited compositional variation, range between Ru0.94Os0.03Ir0.02S1.95 and Ru0.64Os0.21Ir0.10S1.85, and contain up to 1.96 at% Rh and 3.67 at% As. Close association of some laurite grains with amphibole and clinopyroxene indicates crystallization from alkali rich fluid bearing melt in the suprasubduction environment. The lack of any IPGE alloys, as well as the low Os-content of laurite, assumes that the melt from which chromite and laurite were crystallized had relatively high fS2 but never reached the fS2 to crystallize the erlichmanite. The presence of millerite, as primary inclusions in chromite, reflects the increasing fS2 during the chromite crystallization

Grammatikopoulosite, NiVP, a New Phosphide from the Chromitite of the Othrys Ophiolite, Greece

Grammatikopoulosite, NiVP, is a new phosphide discovered in the podiform chromitite and hosted in the mantle sequence of the Othrys ophiolite complex, central Greece. The studied samples were collected from the abandoned chromium mine of Agios Stefanos. Grammatikopoulosite forms small crystals (from 5 μm up to about 80 μm) and occurs as isolated grains. It is associated with nickelphosphide, awaruite, tsikourasite, and an undetermined V-sulphide. It is brittle and has a metallic luster. In plane-polarized light, it is creamy-yellow, weakly bireflectant, with measurable but not discernible pleochroism and slight anisotropy with indeterminate rotation tints. Internal reflections were not observed. Reflectance values of mineral in air (R1, R2 in %) are: 48.8–50.30 at 470 nm, 50.5–53.5 at 546 nm, 51.7–55.2 at 589 nm, and 53.2–57.1 at 650 nm. Five spot analyses of grammatikopoulosite give the average composition: P 19.90, S 0.41, Ni 21.81, V 20.85, Co 16.46, Mo 16.39, Fe 3.83, and Si 0.14, total 99.79 wt %. The empirical formula of grammatikopoulosite—based on Σ(V + Ni + Co + Mo + Fe + Si) = 2 apfu, and taking into account the structural results—is (Ni0.57Co0.32Fe0.11)Σ1.00(V0.63Mo0.26Co0.11)Σ1.00(P0.98S0.02)Σ1.00. The simplified formula is (Ni,Co)(V,Mo)P and the ideal formula is NiVP, which corresponds to Ni 41.74%, V 36.23%, P 22.03%, total 100 wt %. The density, calculated on the basis of the empirical formula and single-crystal data, is 7.085 g/cm3. The mineral is orthorhombic, space group Pnma, with a = 5.8893(8), b = 3.5723(4), c = 6.8146(9) Å, V = 143.37(3) Å3, and Z = 4. The mineral and its name have been approved by the Commission of New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA 2019-090). The mineral honors Tassos Grammatikopoulos, geoscientist at the SGS Canada Inc., for his contribution to the economic mineralogy and mineral deposits of Greece.This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited

Thalhammerite, Pd9Ag2Bi2S4, a New Mineral from the Talnakh and Oktyabrsk Deposits, Noril'sk Region, Russia

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Eliopoulosite, V7S8, A New Sulfide from the Podiform Chromitite of the Othrys Ophiolite, Greece

The new mineral species, eliopoulosite, V7S8, was discovered in the abandoned chromium mine of Agios Stefanos of the Othrys ophiolite, located in central Greece. The investigated samples consist of massive chromitite hosted in a strongly altered mantle tectonite, and are associated with nickelphosphide, awaruite, tsikourasite, and grammatikopoulosite. Eliopoulosite is brittle and has a metallic luster. In plane-reflected polarized light, it is grayish-brown and shows no internal reflections, bireflectance, and pleochroism. It is weakly anisotropic, with colors varying from light to dark greenish. Reflectance values of mineral in air (Ro, Re’ in %) are: 34.8–35.7 at 470 nm, 38–39 at 546 nm, 40–41.3 at 589 nm, and 42.5–44.2 at 650 nm. Electron-microprobe analyses yielded a mean composition (wt.%) of: S 41.78, V 54.11, Ni 1.71, Fe 1.1, Co 0.67, and Mo 0.66, totali 100.03. On the basis of Σatoms = 15 apfu and taking into account the structural data, the empirical formula of eliopoulosite is (V6.55Ni0.19Fe0.12Co0.07Mo0.04)Σ = 6.97S8.03. The simplified formula is (V, Ni, Fe)7S8 and the ideal formula is V7S8, which corresponds to V 58.16%, S 41.84%, total 100 wt.%. The density, based on the empirical formula and unit-cell volume refined form single-crystal structure XRD data, is 4.545 g·cm−3. The mineral is trigonal, space group P3221, with a = 6.689(3) Å, c = 17.403(6) Å, V = 674.4(5) Å3, Z = 3, and exhibits a twelve-fold superstructure (2a × 2a × 3c) of the NiAs-type subcell with V-atoms octahedrally coordinated by S atoms. The distribution of vacancies is discussed in relation to other pyrrhotite-like compounds. The mineral name is for Dr. Demetrios Eliopoulos (1947–2019), a geoscientist at the Institute of Geology and Mineral Exploration (IGME) of Greece and his widow, Prof. Maria Eliopoulos (nee Economou, 1947), University of Athens, Greece, for their contributions to the knowledge of ore deposits of Greece and to the mineralogical, petrographic, and geochemical studies of ophiolites, including the Othrys complex. The mineral and its name have been approved by the Commission of New Minerals, Nomenclature, and Classification of the International Mineralogical Association (No. 2019-96).© 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/)

Chromite and platinum group elements mineralization in the Santa Elena Ultramafic Nappe (Costa Rica): geodynamic implications

Chromitites associated with strongly altered peridotite from six distinct localities in the Santa Elena ultramafic nappe (Costa Rica) have been investigated for the first time. Santa Elena chromitites commonly display a compositional variation from extremely chromiferous (Cr/(Cr+Al)=0.81) to intermediate and aluminous (Cr/(Cr+Al)=0.54). This composition varies along a continuous trend, corresponding to calculated parental liquids which may have been derived from the differentiation of a single batch of boninitic magma with Cr-rich and (Al, Ti)-poor initial composition. Fractional precipitation of chromite probably occurred during differentiation of the boninitic melt and progressive metasomatic reaction with mantle peridotite. The distribution of platinum group elements (PGE) displays the high (Os+Ir+Ru)/(Rh+Pt+Pd) ratio typical of ophiolitic chromitites and, consistently, the platinum group minerals (PGM) encountered are mainly Ru-Os-Ir sulfides and arsenides. Textural relations of most of the platinum group elements suggest crystallization at magmatic temperatures, possibly under relatively high sulfur fugacity as indicated by the apparent lack of primary Os-Ir-Ru alloys. The chemical and mineralogical characteristics of chromitites from the Santa Elena ultramafic nappe have a strong affinity to podiform chromitites in the mantle section of supra-subduction-zone ophiolites. Calculated parental melts of the chromitites are consistent with the differentiation of arc-related magmas, and do not support the oceanic spreading center geodynamic setting previously proposed by some authors