ALBERT

Description: Ni-bearing magnesium phyllosilicates (garnierites) are significant Ni ores in Ni-laterites worldwide. The present paper reports a detailed TEM investigation of garnierites from the Falcondo Ni-laterite deposit (Dominican Republic). Different types of garnierites have been recognized, usually consisting of mixtures between serpentine and talc-like phases that display a wide range of textures at the nanometer scale. In particular, chrysotile tubes, polygonal serpentine, and lizardite lamellae are intergrown with less crystalline, talc-like lamellae. Samples consisting uniquely of talc-like and of sepiolite-falcondoite were also observed, occurring as distinctive thin lamellae and long ribbon-shaped fibers, respectively. HRTEM imaging indicates that serpentine is replaced by the talc-like phase, whereas TEM-AEM data show preferential concentration of Ni in the talc-like phase. We suggest, therefore, that the crystallization of Ni-bearing phyllosilicates is associated with an increase in the silica activity of the system, promoting the replacement of the Ni-poor serpentine by the Ni-enriched talc-like phase. These results have interesting implications in material science, as garnierites are natural analogs of Ni-bearing phyllosilicate-supported synthetic catalysts. Finally, SAED and HRTEM suggest that the Ni-bearing talc-like phase corresponds to a variety of talc with extra water, showing larger d 001 than talc (i.e., 9.2–9.7 Å), described as "kerolite"-"pimelite" in clay mineral literature.

Description: Chromite from Los Congos and Los Guanacos in the Eastern Pampean Ranges of Córdoba (Argentinian Central Andes) shows homogenous and exsolution textures. The composition of the exsolved phases in chromite approaches the end-members of spinel (MgAl 2 O 4 ; Spl) and magnetite ( $${\mathrm{Fe}}^{2+}{\mathrm{Fe}}_{2}^{3+}{\mathrm{O}}_{4}$$ ; Mag) that define the corners of the spinel prism at relatively constant Cr 3+ /R 3+ ratio (where R 3+ is Cr+Al+Fe 3+ ). The exsolution of these phases from the original chromite is estimated to have accounted at ≥600 °C on the basis of the major element compositions of chromite with homogenous and exsolution textures that are in equilibrium with forsterite-rich olivine (Fo 95 ). The relatively large size of the exsolved phases in chromite (up to ca. 200 μm) provided, for the first time, the ability to conduct in situ analysis with laser ablation-inductively coupled plasma-mass spectrometry for a suite of minor and trace elements to constrain their crystal-crystal partition coefficient between the spinel-rich and magnetite-rich phases $$({D}_{\mathrm{i}}^{\mathrm{Spl}/\mathrm{Mag}})$$ . Minor and trace elements listed in increasing order of compatibility with the spinel-rich phase are Ti, Sc, Ni, V, Ge, Mn, Cu, Sn, Co, Ga, and Zn. $${D}_{\mathrm{i}}^{\mathrm{Spl}/\mathrm{Mag}}$$ values span more than an order of magnitude, from $${D}_{\mathrm{Ti}}^{\mathrm{Spl}/\mathrm{Mag}}=0.30\pm 0.06$$ to $${D}_{\mathrm{Zn}}^{\mathrm{Spl}/\mathrm{Mag}}=5.48\pm 0.63$$ . Our results are in remarkable agreement with data available for exsolutions of spinel-rich and magnetite-rich phases in other chromite from nature, despite their different Cr 3+ /R 3+ ratio. The estimated crystal-crystal partitioning coefficients reflect the effect that crystal-chemistry of the exsolved phases from chromite imposes on all investigated elements, excepting Cu and Sc (and only slightly for Mn). The observed preferential partitioning of Ti and Sc into the magnetite-rich phase is consistent with high-temperature chromite/melt experiments and suggests a significant dependence on Fe 3+ substitution in the spinel structure. A compositional effect of major elements on Ga, Co, and Zn is observed in the exsolved phases from chromite but not in the experiments; this might be due to crystal-chemistry differences along the $${\mathrm{MgFe}}_{-1}{-\mathrm{Al}}_{2}{\mathrm{Fe}}_{-2}^{3+}$$ exchange vector, which is poorly covered experimentally. This inference is supported by the strong covariance of Ga, Co, and Zn observed only in chromite from layered intrusions where this exchange vector is important. A systematic increase of Zn and Co coupled with a net decrease in Ga during hydrous metamorphism of chromitite bodies cannot be explained exclusively by compositional changes of major elements in the chromite (which are enriched in the magnetite component). The most likely explanation is that the contents of minor and trace elements in chromite from metamorphosed chromitites are controlled by interactions with metamorphic fluids involved in the formation of chlorite.

Description: Garnierites represent significant Ni ore minerals in the many Ni-laterite deposits worldwide. The occurrence of a variety of garnierite minerals with variable Ni content poses questions about the conditions of their formation. From an aqueous-solution equilibrium thermodynamic point of view, the present study examines the conditions that favor the precipitation of a particular garnierite phase and the mechanism of Ni-enrichment, and gives an explanation to the temporal and spatial succession of different garnierite minerals in Ni-laterite deposits. The chemical and structural characterization of garnierite minerals from many nickel laterite deposits around the world show that this group of minerals is formed essentially by an intimate intermixing of three Mg-Ni phyllosilicate solid solutions: serpentine-népouite, kerolite-pimelite, and sepiolite-falcondoite, without or with very small amounts of Al in their composition. The present study deals with garnierites which are essentially Al-free. The published experimental dissolution constants for Mg end-members of the above solid solutions and the calculated constants for pure Ni end-members were used to calculate Lippmann diagrams for the three solid solutions, on the assumption that they are ideal. With the help of these diagrams, congruent dissolution of Ni-poor primary minerals, followed by equilibrium precipitation of Ni-rich secondary phyllosilicates, is proposed as an efficient mechanism for Ni supergene enrichment in the laterite profile. The stability fields of the solid solutions were constructed using [log aSiO2(aq), log ((aMg2+ + aNi2+)/(aH+)2)] (predominance) diagrams. These, combined with Lippmann diagrams, give an almost complete chemical characterization of the solution and the precipitating phase(s) in equilibrium. The temporal and spatial succession of hydrous Mg-Ni phyllosilicates encountered in Ni-laterite deposits is explained by the small mobility of silica and the increase in its activity.

Description: A bstract Two small grains, about 50 x 60 x 70 μm in size, occurring in the chromitite associated with the altered harzburgite of Loma Peguera (Dominican Republic) have been investigated by electron microprobe analyses, X-ray computed tomography, and X-ray diffraction. Electron microprobe data indicate the grains to be composed of Ru, Os, Ir, Fe, and O. The obtained composition is similar to those reported from podiform chromitites worldwide and often reported as evidence for the existence of PGE-bearing oxide minerals. X-ray computed tomography and X-ray diffraction data, provided for the first time in this study, reveal that the Loma Peguera grains consist of a fine intergrown of ruthenium and magnetite not detectable at the scale of the electron microprobe. We believe that the investigated grains were originally laurite, ideally (Ru,Os)S 2 , crystallized during the magmatic stage. During alteration processes at low temperature, the mineral lost its original S, which transformed the laurite to ruthenium. The newly formed ruthenium was probably porous and, during the final stage of the alteration process, oxidizing fluids enriched in Fe filled the cavities leading to the subsequent crystallization of magnetite.

Description: Two samples from the enigmatic Ni-oxide body of Bon Accord (Barberton greenstone belt, South Africa) have been investigated with the hydroseparation technique to obtain heavy mineral concentrates. The concentrates contain abundant Pt, Pd, and gold minerals never reported before from the Bon Accord Ni-oxide body. The grains occur as: (1) minute inclusions (〈3 μm) in trevorite (ideally NiFe 3+ O 4 ) and (2) larger (5–70 μm) free aggregates liberated from the host phase. The first group comprises several PGM compounds of Pd-Sb, Pd-Sb-As, Pd-Cu-Sb, Pt-Sb, Pt-As-S, Ru-As-S, Ru-S, along with free grains of Ni-Fe-As. The second consists of sperrylite (PtAs 2 ), members of the sobolevskite-kotulskite series, and electrum. These results are in good agreement with previous analyses of PGE-Au in bulk rock. Paragenetic relationships indicate that the PGM and electrum are of secondary origin, probably generated during low-temperature metamorphism of the Ni-rich mineralization. They have a terrestrial origin and are related with a low-sulfidation regime that usually accompanies hydrothermally driven serpentinization of mafic-ultramafic bodies. The ligands in the newly formed PGM (As, Sb, Bi, Te, and O) probably proceed from the same source of the hydrothermal solutions. In this model, the metals Ni-PGE-Au were original components of the primary mineral assemblage of the Bon Accord precursor, whereas As, Sb, Bi, Te, and O might have been contributed by the metasomatizing fluids, during near-surface evolution of the ore body. The data on the high-grade heavy mineral concentrates, obtained by hydroseparation, have provided new knowledge about the mineral deportment of Pd, Pt, and Au.

Description: Zaccariniite, RhNiAs, is a new platinum-group mineral discovered in the Loma Peguera ophiolitic chromitite, Dominican Republic. The mineral forms anhedral grains (1–20 μm in size) and occurs intergrown with garutiite, in association with hexaferrum, Ru-Os-Ir-Fe alloys, Ru-Os-Ir-Fe oxygenated compounds, and chromite. Zaccariniite is opaque and has a metallic luster and a grey streak. The mineral is brittle, with no cleavage. Values of VHN 5 (10 indentations on different grains of synthetic RhNiAs) fall between 166 and 286 kg/mm 2 , with a mean value of 218 kg/mm 2 , corresponding to a Mohs hardness of approximately 3.5–4. Under plane-polarized reflected light, the mineral is white with brownish to pinkish tints, has moderate to strong bireflectance, a strong white to pinkish brownish white pleochroism, and strong anisotropy, with rotation tints from orange to blue–green; it exhibits no internal reflections. Reflectance values of zaccariniite in air (R1, R2 in %) are: 49.4, 49.4 at 470 nm; 52.4, 53.2 at 546 nm; 54.2, 53.2 at 589 nm; and 56.6, 53.3 at 650 nm. Three electron microprobe analyses of natural zaccariniite gave an average composition of: Rh 41.77, Os 0.51, Ir 0.64, Ru 0.46, Pd 0.34, Ni 23.75, Fe 0.53, As 27.84, S 0.10, for a total of 96.09 wt.%, corresponding to the empirical formula (Rh 1.01 Os 0.01 Ir 0.01 Ru 0.01 Pd 0.01 ) 1.05 (Ni 1.00 Fe 0.02 ) 1.02 (As 0.92 S 0.01 ) 0.93 based on three atoms. The average result of twenty-eight analyses of synthetic zaccariniite is: Rh 44.57, Ni 24.50, and As 31.82 total 100.88 wt.%, corresponding to Rh 1.02 Ni 0.98 As 1.00 . The mineral is tetragonal, belongs to space group P 4/ nmm with lattice parameters a = 3.5498(1), c = 6.1573(2) Å, V = 77.59(1) Å 3 , Z = 2, and crystallizes with the Cu 2 Sb structure type. The strongest lines in the X-ray powder-diffraction pattern of synthetic zaccariniite [ d in Å(I)( hkl )] are: 2.5092(40)(110), 2.3252(100)(111,102), 1.9453(51)(112), 1.7758(80)(103,200), 1.2555(40)(213,220), 1.1044(22)(302,311), 1.0547(23)(312), 0.9730(42)(215). The new Rh-Ni arsenide is named after Federica Zaccarini in recognition of her important contributions to the mineralogy of platinum-group elements.

Description: The Las Cruces deposit is in the eastern end of the Iberian Pyrite Belt (SW Spain). It is currently being mined by Cobre Las Cruces S.A. The main operation is focused on the supergene Cu-enriched zone (initial reserves of 17.6 Mt @ 6.2% Cu). An Au-Ag-Pb–rich gossan resource (3.6 Mt @ 3.3% Pb, 2.5 g/t Au, and 56.3 g/t Ag) occurs in the upper part of the deposit. The Au grade ranges from 0.01 ppm to 〉100 ppm, and occurs as three different Au ore types: (1) Au mineralization in the upper part of the gossan linked to Fe-oxides lithofacies, (2) Au concentration in the lower part of the gossan associated with leached black shales, and (3) Au ore in the cementation zone related to subvertical fractures. A hydroseparation device has been used to obtain heavy mineral concentrates from selected samples of different ore types. Reflected-light microscopy, scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), and electron probe microanalysis (EPMA) were used to study the separated Au particles. Significant differences between the defined ore types include the Au-bearing lithologies, mineral associations, textural features, particle sizes, morphologies, and fineness. Au-rich minerals include native Au, Au-Ag electrum, and Au-Ag-Hg amalgams. Gold-bearing mineral associations include Pb-oxihalides, Fe-oxides, galena, pyrite, cinnabar, and Ag-sulfosalts. The Au enrichment mechanism in the supergene profile involves (1) dissolution of Au from the primary sulfides as chloride-rich ionic complexes during the weathering of the deposit under subaerial exposure; dissolved Au is transported downward through the supergene profile under acidic and oxidized conditions; (2) destabilization of the Au complexes by Fe-controlled redox reactions; as a consequence, coarse-grained, high-fineness Au particles precipitated in association with Fe-oxyhydroxides. This resulted in secondary concentration in the upper gossan; and (3) after deposition of cover sediments took place a progressive change in the system conditions resulting in a later Au remobilization as hydroxidehalide, hydroxide, thiosulfate, and bisulfide complexes in the lowermost gossan and cementation zone. The main pathways for migration of enriched fluids to the cementation zone are secondary permeability zones linked to Alpine reactivated faults. Deposition of Au seems to be related to fluid interaction with reductant lithologies, including black shales and the primary sulfides.

Description: Hosted in the Early Cretaceous bimodal tholeiite volcanic series of the Los Ranchos Formation, the Doña Amanda and Cerro Kiosko deposits in the Bayaguana district represent significant Au, Cu, and Ag resources in the Cordillera Oriental of the Dominican Republic. At Doña Amanda, a dense stockwork of quartz-sulfide veins is hosted by volcanic rocks with intense transitional phyllic-advanced argillic and silicic hydrothermal alteration assemblages, indicating a high-sulfidation environment. Wavy quartz veins with central sutures and rims of pyrite + enargite + molybdenite + fahlore (B veins) are cut by planar quartz-pyrite D veins. Primary fluid inclusions in quartz from B veins (Th: 160°–〉400°C; salinity: 7.9–16.4 wt % NaCl equiv) are interpreted as porphyry-type fluids. Inclusion fluids in quartz of quartz-pyrite veins (Th: 125°–175°C; salinity: 4.8–12.2 wt % NaCl equiv), quartz from silicic altered wall rocks (Th: 150°–175°C; salinity: 8.3–13.9 wt % NaCl equiv), and late, distal calcite veins (Th: 120°–160°C; salinity: 5.0–13.3 wt % NaCl equiv) indicate limited mixing with more dilute fluids and rule out mixing with fresh meteoric water. In Cerro Kiosko, a swarm of fault-controlled massive chalcopyrite + enargite + bornite + fahlore D veins and lodes are hosted by rocks with pervasive kaolinite alteration after sericite. 34 S values of vein sulfides from both deposits are all close to –2 and consistent with a predominance of magmatic sulfur and sulfide deposition from an oxidizing magmatic fluid. These data are consistent with a transitional environment between a deeper porphyry Cu(-Mo) and an overlying high-sulfidation epithermal deposit. An Re-Os age (112.6 ± 0.4 Ma) for molybdenite from the Doña Amanda deposit places the porphyry-epithermal mineralization as Early Cretaceous, coeval with the Los Ranchos Formation host rocks and with the Pueblo Viejo deposit. New sensitive high-resolution ion microprobe U-Pb ages on zircons from plagioclase-phyric rhyolite domes in the Bayaguana district are consistent with porphyry–high-sulfidation epithermal mineralization occurring along the Los Ranchos Formation during tonalite batholith emplacement in the basaltic island-arc basement at ca. 118 to 112 Ma and finalization of felsic volcanism at ca. 110 to 107 Ma.