ToF-SIMS-derived hydrophobicity in DTP flotation of chalcopyrite: Contact angle distributions in flotation streams

Particle hydrophobicity has been derived from Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS) measurements and its impact on the flotation behaviour of chalcopyrite investigated. Batch flotation tests were performed using a dithiophosphate-type of collector in different concentrations. Three flotation regimes were studied using particle size ranges of 20–38 μm, 75–105 μm and 150–210 μm. The individual particle contact angle, and hence, the distribution of contact angles of chalcopyrite within feed, concentrate and tail flotation samples has been determined using ToF-SIMS secondary ions. The effects of particle size and hydrophobicity on the flotation behaviour have been investigated using this new approach. The hydrodynamic effects of the particle size were highlighted by the different distributions of contact angles obtained for each concentrate size fraction, with fine and coarse sizes requiring higher average contact angles to float. This effect was overtaken by hydrophobicity when a high collector concentration was used. The broad distribution of contact angles observed in all samples, i.e. heterogeneity in hydrophobicity, has significant consequences for interpreting flotation behaviour. The methodology of analysis conducted in this study was applied to real ore and can be used as a quantitative, diagnostic tool for examining surface chemical factors affecting hydrophobicity. This new technique has promise and may advance the understanding of mechanisms, which may lead to better control strategies for improving flotation performance. Furthermore, any mineral–collector system can be targeted, provided appropriate calibration is performed.     

The role of silica in the hydrous metamorphism of chromite

Retrograde hydrous metamorphism has produced three types of microstructures in chromite grains from chromitites and enclosing rocks of the Tapo Ultramafic Massif (Central Peruvian Andes). In semi-massive chromitites (60–80 vol% chromite), (i) partly altered chromite with homogeneous cores surrounded by lower Al₂O₃ and MgO but higher Cr₂O₃ and FeO porous chromite with chlorite filling the pores. In serpentinites (ii) zoned chromite with homogeneous cores surrounded by extremely higher Fe₂O₃ non-porous chromite and magnetite rims, and (iii) non-porous chromite grains. The different patterns of zoning in chromite grains are the consequences of the infiltration of reducing and SiO₂-rich fluids and the subsequent heterogeneous interaction with more oxidizing and Fe-bearing fluids. During the first stage of alteration under reduced conditions magmatic chromite is dissolved meanwhile new metamorphogenic porous chromite crystallizes in equilibrium with chlorite. This reaction that involves dissolution and precipitation of minerals is here modeled thermodynamically for the first time. µSiO₂-µMgO pseudosection calculated for unaltered semi-massive chromitites at 2 kbar and 300 °C, the lowest P-T conditions inferred from the Tapo Ultramafic Massif and Marañón Complex, predicts that chromite + chlorite (i.e., partly altered chromite) is stable instead of chromite + chlorite + brucite at progressive higher µSiO₂ but lower µMgO. Our observation is twofold as it reveals that the important role of SiO₂ and MgO and the open-nature of this process. P-T-X diagrams computed using the different P-T pathways estimated for the enclosing Tapo Ultramafic Massif reproduce well the partial equilibrium sequence of mineral assemblages preserved in the chromitites. Nevertheless, it is restricted only to the P-T conditions of the metamorphic peak and that of the latest overprint. Our estimations reveal that a high fluid/rock ratio (1:40 ratio) is required to produce the microstructures and compositional changes observed in the chromitites from the Tapo Ultramafic Massif. The circulation of SiO₂-rich fluids and the mobilization of MgO from the chromitite bodies are linked with the formation of garnet amphibolites and carbonate-silica hydrothermalites (i.e., listwaenites and birbirites) in the ultramafic massif. The origin of these fluids is interpreted as a result of the dissolution of orthopyroxene and/or olivine from the metaharzburgites and metagabbros enclosed in the Tapo Ultramafic Massif.     

Thick chromitite of the Jacurici Complex (NE Craton São Francisco,Brazil): Cumulate chromite slurry in a conduit

The Jacurici Complex, located in the NE part of the São Francisco Craton, hosts the largest chromite deposit in Brazil. The mineralized intrusion is considered to be a single N-S elongated layered body, disrupted into many segments by subsequent deformation. The ore is hosted in a thick, massive layer. Two segments, Ipueira and Medrado, have been previously studied. We provide new geological information, and chromite composition results from the Monte Alegre Sul and Várzea do Macaco segments located farther north, and integrate these with previous results. The aim of this study is to determine and discuss the magma chamber process that could explain the formation of the thick chromitite layer. All segments exhibit similar stratigraphic successions with an ultramafic zone (250 m thick) hosting a 5–8 m thick main chromitite layer (MCL), and a mafic zone (40 m thick). The chromite composition of the MCL, Mg-numbers (0.48–0.72) and Cr-numbers (0.59–0.68), is similar to chromites from layered intrusions and other thick chromitites. Previous work concluded that the parental magma of the mineralized intrusion was very primitive based on olivine composition (up to Fo₉₃) and orthopyroxene composition (up to En₉₄) from harzburgite samples, and that it originated from an old subcontinental lithospheric mantle. We estimate that the melt from which the massive chromitite layer crystallized was similar to a boninite, or low siliceous high-Mg basalt, with a higher Fe/Mg ratio. The petrologic evidence from the mafic-ultramafic rocks suggests that a high volume of magma flowed through the sill, which acted as a dynamic conduit. Crustal contamination has previously been considered as the trigger for the chromite crystallization, based on isotope studies, as the more radiogenic signatures correlate with an increase in the volumetric percentage of amphibole (up to 20%). The abundant inclusions of hydrous silicate phases in the chromites from the massive ore suggest that the magma was hydrated during chromite crystallization. Fluids may have played an important role in the chromite formation and/or accumulation. However, the trigger for chromite crystallization remains debatable. The anomalous thickness of the chromitite is a difficult feature to explain. We suggest a combined model where chromite crystallized along the margins of the magma conduit, producing a semi-consolidated chromite slurry that slumped through the conduit forming a thick chromitite layer in the magma chamber where layered ultramafic rocks were previously formed. Subsequently, the conduit was obstructed and the resident magma fractionated to produce a more evolved composition.     

Electron probe microanalysis and microscopy: Principles and applications in characterization of mineral inclusions in chromite from diamond deposit

Electron probe microanalysis and microscopy is a widely used modern analytical technique primarily for quantifying chemical compositions of solid materials and for mapping or imaging elemental distributions or surface morphology of samples at micrometer or nanometer-scale. This technique uses an electromagnetic lens-focused electron beam, generated from an electron gun, to bombard a sample. When the electron beam interacts with the sample, signals such as secondary electron, backscattered electron and characteristic X-ray are generated from the interaction volume. These signals are then examined by detectors to acquire chemical and imaging information of the sample. A unique part of an electron probe is that it is equipped with multiple WDS spectrometers of X-ray and each spectrometer with multiple diffracting crystals in order to analyze multiple elements simultaneously. An electron probe is capable of analyzing almost all elements (from Be to U) with a spatial resolution at or below micrometer scale and a detection limit down to a few ppm.Mineral inclusions in chromite from the Wafangdian kimberlite, Liaoning Province, China were used to demonstrate the applications of electron probe microanalysis and microscopy technique in characterizing minerals associated with ore deposits, specifically, in this paper, minerals associated with diamond deposit. Chemical analysis and SE and BSE imaging show that mineral inclusions in chromite include anhydrous silicates, hydrous silicates, carbonates, and sulfides, occurring as discrete or single mineral inclusions or composite multiple mineral inclusions. The chromite–olivine pair poses a serious problem in analysis of Cr in olivine using electron probe. Secondary fluorescence of Cr in chromite by Fe in olivine drastically increases the apparent Cr₂O₃ content of an olivine inclusion in a chromite. From the chemical compositions obtained using electron probe, formation temperatures and pressures of chromite and its mineral inclusions calculated using applicable geothermobarometers are from 46 kbar and 980 °C to 53 kbar and 1130 °C, which are within the stability field of diamond, thus Cr-rich chromite is a useful indication mineral for exploration of kimberlite and diamond deposit. A composite inclusion in chromite composed of silicate and carbonate minerals has a bulk composition of 33.2 wt.% SiO₂, 2.5 wt.% Al₂O₃, 22.0 wt.% MgO, 7.5 wt.% CaO, 2.5 wt.% BaO, 0.8 wt.% K₂O, 25.5 wt.% CO₂, and 0.8 wt.% H₂O, similar to the chemical composition of the Wafangdian kimberlite, suggesting that it is trapped kimberlitic magma.     

Reworked manganese ore bodies in Bonai-Keonjhar belt,Singhbhum Craton,India: Petrology and genetic study

The genetic evolution of three types of reworked manganese ore bodies namely: Detrital, Concretionary (Mangcrete) and Wad in the Precambrian Iron Ore Group occurring in Bonai-Keonjahr belt, Singhbhum Craton, India are reported. All the reworked Mn-ore bodies are developed in a restricted area and have a limited resource. Mangcrete and wad are commonly exposed at the surface and extend to a maximum depth of 10 m while detrital ores are observed below 10–20 m from the surface.Detrital ore bodies occur as large boulders and are buried under a thick zone of laterite. Mangcrete is concretionary in nature; oolitic, spherulitic and nodular in shape. Broken fragmented of ooloids and pisoloids, often observed in mangcrete, are indications of reworking. Wad exposures are noticed above low to medium-grade bedded manganese ore bodies. Among three reworked ore types, the detrital is of low to medium-grade having Mn:Fe ratio > 5, while wad and mangcrete are of sub-grade (Mn:Fe ~ 1) and off-grade type (Mn:Fe < 1) respectively.Detrital ore bodies are of allochthonous nature and developed through several stages such as fragmentation of pre-existing ore, leaching and cementation followed by transportation and deep burial. Mangcrete represent chemogenic precipitates at several stages of contemporary Mn-Fe-Al rich fluid under supergene environment. Wad is of bio-chemogenic origin and developed in a swampy region under marine environment due to slow chemical precipitation of Mn-Fe enriched fluid, in several stages nucleating quartz/hematite/cryptomelane detritals.     

Chromitites from the Luanga Complex,Carajás,Brazil: Stratigraphic distribution and clues to processes leading to post-magmatic alteration

The Neoarchean (ca. 2.75 Ga) Luanga Complex, located in the Carajás Mineral Province in Brazil, is a medium-size layered intrusion consisting, from base to top, of ultramafic cumulates (Ultramafic Zone), interlayered ultramafic and mafic cumulates (Transition Zone) and mafic cumulates (Mafic Zone). Chromitite layers in the Luanga Complex occur in the upper portion of interlayered harzburgite and orthopyroxenite of the Transition Zone and associated with the lowermost norites of the Mafic Zone. The stratigraphic interval that hosts chromitites (∼150 meters thick) consists of several cyclic units interpreted as the result of successive influxes of primitive parental magma. The compositions of chromite in chromitites from the Transition Zone (Lower Group Chromitites) have distinctively higher Cr# (100Cr/(Cr + Al + Fe³⁺)) compared with chromite in chromitites from the Mafic Zone (Upper Group Chromitites). Chromitites hosted by noritic rocks are preceded by a thin layer of harzburgite located 15–20 cm below each chromitite layer. Lower Cr# in chromitites hosted by noritic rocks are interpreted as the result of increased Al₂O₃ activity caused by new magma influxes. Electron microprobe analyses on line transverses through 35 chromite crystals indicate that they are rimmed and/or extensively zoned. The composition of chromite in chromitites changes abruptly in the outer rim, becoming enriched in Fe³⁺ and Fe²⁺ at the expense of Mg, Cr, Al, thus moving toward the magnetite apex on the spinel prism. This outer rim, characterized by higher reflectance, is probably related to the metamorphic replacement of the primary mineralogy of the Luanga Complex. Zoned chromite crystals indicate an extensive exchange between divalent (Mg, Fe²⁺) cations and minor to none exchange between trivalent cations (Cr³⁺, Al³⁺ and Fe³⁺). This Mg-Fe zoning is interpreted as the result of subsolidus exchange of Fe²⁺ and Mg between chromite and coexisting silicates during slow cooling of the intrusion. A remarkable feature of chromitites from Luanga Complex is the occurrence of abundant silicate inclusions within chromite crystals. These inclusions show an adjacent inner rim with higher Cr# and lower Mg# (100 Mg/(Mg + Fe²⁺)) and Al# (100Al/(Cr + Al + Fe³⁺)). This compositional shift is possibly due to crystallization from a progressively more fractionated liquid trapped in the chromite crystal. Significant modification of primary cumulus composition of chromite, as indicated in our study for the Luanga Complex, is likely to be common in non-massive chromitites and the rule for disseminated chromites in mafic intrusions.     

Base metal mineral segregation and Fe-Mg exchange inducing extreme compositions of olivine and chromite from the Xiadong Alaskan-type complex in the southern part of the Central Asian Orogenic Belt

The Xiadong Alaskan-type complex shares much in common with typical Alaskan-type complexes worldwide, while showing some unique features in terms of mineral compositions. Olivine from the Xiadong dunites is characterized by extremely high Fo component of 91.7–96.7 and anomalously negative correlation of Fo with NiO, while chromite is featured by high 100 × Fe³⁺/(Fe³⁺ + Cr + Al) (>70), high 100 × Fe²⁺/(Fe²⁺ + Mg) (>70), high 100 × Cr/(Cr + Al) (>90), low MnO (<0.6 wt%) and TiO₂ contents (<0.5 wt%). To investigate these particular features, we conducted petrographic observation and mineral composition analyses for the Xiadong dunite. A number of Fe and/or Ni sulfides and alloys occurring as inclusions in olivine and chromite indicate that base metal mineral segregation took place prior to crystallization of olivine and chromite and probably induced Fe and Ni depletions in olivine. The FeO and MgO variations in profile analyses from chromite to adjacent olivine are compatible with Fe-Mg exchange. The diffusion mechanism of Fe from olivine to chromite and Mg from chromite to olivine may have elevated both Fo of olivine and 100 × Fe²⁺/(Mg + Fe²⁺) ratio of chromite and further enhanced the decoupling of Fo and NiO in olivine. We thus suggest that base metal mineral segregation and Fe-Mg exchange play important roles in the extreme compositions of the Xiadong dunite. The Ni depletion of olivine and degree of Fe-Mg exchange between olivine and chromite may be used as indicators of mineralization in mafic-ultramafic intrusions.     

Origin of the giant Allard Lake ilmenite ore deposit (Canada) by fractional crystallization,multiple magma pulses and mixing

The late-Proterozoic Allard Lake ilmenite deposit is located in the Havre-Saint-Pierre anorthosite complex, part of the allochtonous polycyclic belt of the Grenville Province. Presently the world's largest Fe–Ti oxide deposit, it had a pre-mining amount in excess of 200 Mt at grades over 60 wt.% hemo-ilmenite. The main ore body is a funnel-shaped intrusion, measuring 1.03 × 1.10 km and 100–300 m-thick. Two smaller bodies are separated by faults and anorthosite. The ore is an ilmenite-rich norite (or ilmenitite) made up of hemo-ilmenite (Hem_22.6–29.4, 66.2 wt.% on average), andesine plagioclase (An_45–50), aluminous spinel and locally orthopyroxene. Whole-rock chemical compositions are controlled by the proportions of ilmenite and plagioclase ± orthopyroxene which supports the cumulate origin of the deposit. Ore-forming processes are further constrained by normal and reverse fractionation trends of Cr concentration in cumulus ilmenite that reveal multiple magma emplacements and alternating periods of fractional crystallization and magma mixing. Mixing of magmas produced hybrids located in the stability field of ilmenite resulted in periodic crystallization of ilmenite alone. The unsystematic differentiation trends in the Allard Lake deposit, arising from a succession of magma pulses, hybridisation, and the fractionation of hemo-ilmenite alone or together with plagioclase suggest that the deposit formed within a magma conduit. This dynamic emplacement mechanism associated with continuous gravity driven accumulation of Fe–Ti oxides and possibly plagioclase buoyancy in a fractionating ferrobasalt explains the huge concentration of hemo-ilmenite. The occurrence of sapphirine associated with aluminous spinel and high-alumina orthopyroxene (7.6–9.1 wt.% Al₂O₃) lacking exsolved plagioclase supports the involvement of a metamorphic overprint during the synchronous Ottawan orogeny, which is also responsible for strong textural equilibration and external granule of exsolved aluminous spinel due to slow cooling.     

Geophysical,magmatic, and metallogenic manifestations of a mantle plume in the upper reaches of the Aldan and Amur Rivers

Gravity models of the crust and upper mantle to a depth of 100 km are analyzed to study structural relationships of tectonic and tectonophysical media of different rigidities with the distribution of shallow ore deposits above the Aldan-Zeya plume. The spatial correlation of ore clusters and districts with high crustal viscosity inhomoheneities at depths of 10, 20, and 35 km shows distinct stepwise behavior. On the other hand, media of decreased viscosity are observed in the lower crust (at depths of 25–30 km), subcrustal (40–50 km) layers, and asthenosphere (at a depth below 70 km). They are related to chambers of the complete or partial melting (heat sources) of magmatic and ore occurrences near the Earth’s surface. Lateral metallogenic zoning in the spatial distribution of the ore deposits is due to the spread and redistribution of magmas and ore-forming fluids, shielded by rigid plates in the lower crust. A naturally determined series of ore parageneses is observed from center to flanks of the plume: Au, Mo → Au, Ag, Pb, Zn → Au, Pb, Zn → Au, W → Au, Sb → W, Sn → Sn. The mutual position of the tectonomagmatic structures of different ranks within the plume head obeys hierarchical and fractal laws.     

Platinum mineralization of the Svetly Bor and Nizhny Tagil intrusions,Ural Platinum Belt

This paper presents the results of a detailed mineralogical and micro analytical study of two Ural-Alaskan type intrusions in the Ural Platinum Belt: (1) the dunite-hosted mineralization of the Svetly Bor intrusion, and (2) the chromitite mineralization of the Nizhny Tagil intrusion. Two generations of platinum minerals are typical of both intrusions: magmatic Pt–Fe(Ni) alloys, and post-magmatic Pt(Fe,Ni,Cu) alloys. A trend from ferroan platinum to isoferroplatinum (Pt,Fe → Pt₃Fe) is shown for magmatic alloys of the Svetly Bor intrusion. Magmatic alloys of the Nizhny Tagil intrusion are represented by ferroan platinum (with Ni) only, varying in Fe. The magmatic Pt–Fe alloys of both intrusions were depleted in Fe during the evolution of ore-forming systems and crystallized during the entire magmatic process, generally as fine cubic crystals and anhedral grains hosted by dunite at the magmatic stage during and after the crystallization of dunite (platinum–dunite type of the Svetly Bor intrusion). The evolution of mineral paragenesis was accompanied by a temperature drop, as well as increases in fO₂ and fS₂.Most of the platinum was concentrated in the residual melts together with chromium, and crystallized in the final stage of the magmatic process (platinum–chromite ore of the Nizhny Tagil intrusion). Post-magmatic Pt(Fe,Cu,Ni) alloys formed during the serpentinization of dunite evolved according to a general compositional trend from tetraferroplatinum and ferronickelplatinum to tulameenite and later to Pt–Cu alloy and Pt-oxide (PtFe) → Pt(Fe,Cu,Ni) → Cu₃Pt → Pt–O. Platinum-rich mineralization of both intrusions was formed in the late magmatic stage from a melt rich in volatiles, regardless of their location in dunite or chromitites. Most probably, the rock structure (fracture systems) was the determining factor in the migration of PGE-rich residual melts and ore accumulation.     

The nature of geomagnetic anomalies in metamorphosed chromite-bearing dunites: a case study of the southern Klyuchevskoy complex,Central Urals

Chromite mineralization in metamorphosed dunites from the southern Klyuchevskoy dunite-harzburgite ultramafic complex (Central Urals) has been investigated using geomagnetic surveys along with laboratory studies of ore-forming and accessory spinels of the same genetic type. Magnetization in the study area is carried mainly by accessory Fe-Cr-spinel of a variable Fe^2 +(Cr_2 -xFe_x^3 +)O₄ composition. Metamorphism caused changes in element contents and in both crystal and magnetic structure of the primary nonmagnetic accessory spinel, unlike the almost fresh ore-forming spinel. Thus, ore bodies stand against their host rocks, which is a prerequisite for the use of geomagnetic surveys for exploration of podiform chromite deposits in dunite-harzburgite complexes. Ground magnetic surveys at a test site composed of faulted rocks bearing disseminated chromite mineralization in metamorphosed dunites resolved a chromite ore zone and a fault block boundary showing up as geomagnetic anomalies. Laboratory studies using high technologies (thermomagnetic analysis at 4 to 1000 K, as well as magnetic resonance and magnetic force spectroscopy) revealed, for the first time, magnetic clusters (superparamagnetic phases) in primary nonmagnetic accessory spinel, which are responsible for the magnetic properties of the host rocks. Microscale variations in Cr-spinel correlate with the geomagnetic anomalies recorded by field surveys at the test site._{© 2015, V.S. Sobolev IGM, Siberian Branch of the RAS. Published by Elsevier B.V. All rights reserved.}     

Petrology and geochemistry of high Cr# podiform chromitites of Bulqiza,Eastern Mirdita Ophiolite (EMO), Albania

The ultramafic massif of Bulqiza, which belongs to the eastern ophiolitic belt of Albania, is a major source of metallurgical chromitite ore. The massif consists of a thick (> 4 km) sequence, composed from the base upward of tectonized harzburgite with minor dunite, a transitional zone of dunite, and a magmatic sequence of wehrlite, pyroxenite, troctolite and gabbro. Only sparse, refractory chromitites occur within the basal clinopyroxene-bearing harzburgites, whereas the upper and middle parts of the peridotite sequence contain abundant metallurgical chromitites. The transition zone dunites contain a few thin layers of metallurgical chromitite and sparse bodies are also present in the cumulate section. The Bulqiza Ophiolite shows major changes in thickness, like the 41–50 wt.% MgO composition similar with forearc peridotite as a result of its complex evolution in a suprasubduction zone (SSZ) environment. The peridotites show abundant evidence of mantle melt extraction at various scales as the orthopyroxene composition change from core to rim, and mineral compositions suggest formation in a forearc, as Fo values of olivine are in 91.1–93.0 harzburgite and 91.5–91.9 in dunite and 94.6–95.9 in massive chromitite. The composition of the melts passing through the peridotites changed gradually from tholeiite to boninite due to melt–rock reaction, leading to more High Cr# chromitites in the upper part of the body. Most of the massive and disseminated chromitites have high Cr# numbers (70–80), although there are systematic changes in olivine and magnesiochromite compositions from harzburgites, to dunite envelopes to massive chromitites, reflecting melt–rock reaction. Compositional zoning of orthopyroxene porphyroblasts in the harzburgite, incongruent melting of orthopyroxene and the presence of small, interstitial grains of spinel, olivine and pyroxene likewise attest to modification by migrating melts. All of the available evidence suggests that the Bulqiza Ophiolite formed in a suprasubduction zone mantle wedge.     

Metasomatic alteration of chromite from parts of the late Archaean Sittampundi Layered Magmatic Complex (SLC), Tamil Nadu,India

Chromite deposits associated with layered anorthosite complexes in the Archaean high-grade terranes are rare in the world. The late Archaean Sittampundi Layered Magmatic Complex, Tamil Nadu, India is one of the few such deposits in the world where layers of Fe-Al rich chromites are associated with extremely calcic (An>95) anorthosite. ‘Frozen in’ magmatic mineralogy of the chromitite and the enclosing anorthosite suggest successive crystallization of chromite + clinopyroxene and chromite + clinopyroxene + anorthite from a hydrous Al-rich basaltic melt that was emplaced in a suprasubduction zone setting. Intense deformation and upper amphibolite facies metamorphism at ∼2.45 Ga converted the magmatic assemblages to hitherto unreported hornblende + gedrite + Mg-Al rich spinel ± chlorite bearing assemblages. During metamorphic reconstitution, chromite was pseudomorphically replaced by green spinel in the domains rich in secondary amphiboles. Mass-balance calculation and algebraic analyses of the observed mineralogy suggest that a number of chemical species including chromium became mobile during the formation of spinel pseudomorph in response to infiltration driven metamorphism. Aluminium became mobile in the length scale of chromite grain but remained immobile in the length scale of a thin section.     

Chromite typology and composition characterized through multispectral specular reflectance

Determination of multispectral specular reflectance is an important tool for ore identification in reflected light microscopy, and may be used for automated characterization of ores. However, reflectance values can be affected by compositional variations in a way that is seldom understood. The aim of the present work is to investigate this problem in chromite, an ore whose composition may show typically large natural variations as member of the spinel family, and whose relatively high reflectance variations are apparently unpredictable. For this research, eighteen samples of chromian spinel covering a large range of compositions in the base of the Hagerthy prism were selected for microprobe analysis and reflectance measure on polished sections. The samples belong to a variety of deposits and types (ultramafic massif, ophiolitic, and metamorphosed types: Ojén and Ronda Massifs, Spain; Mayarí, Moa-Baracoa, Camagüey and Sagua de Tánamo, Cuba; Golyamo Kemenyane, Avren and Yakovitsa, Bulgaria). The specular reflectances are characterized as multispectral values, measured at thirteen intervals (50 nm each) in the VNIR region (Visible and Near-Infrared: 400–1000 nm), using the automated CAMEVA System.The relationship between compositional and reflectance values is studied by multivariate analysis and subsequently tested on independent samples. For this purpose, the samples have been grouped in two sets: a larger population of fifteen samples constitutes the initial data set for mathematical processing, while a selection of three samples of widely differing compositions is used to test the resulting functions, so as to gain a critical appraisal of their validity.The results obtained show that the specular reflectance of chromite depends on composition and can be used to estimate compositional parameters, as #Cr = Cr/(Cr + Al) or #Mg = Mg/(Mg + Fe²⁺), but this relationship is complex and does not allow simple direct determinations, due to the multiplicity of possible changes and coupled substitutions (e.g. Al–Cr–Fe³⁺, or Mg-Fe²⁺, Ni, Zn, Ti …) in the chromian spinel family. On the other hand, the relationship of chromite composition with deposit type is also detectable through the reflectance values, but with a higher uncertainty. Reflectance increases with increasing Cr and Fe³⁺ contents in all cases, but the relationship of reflectance with Mg seems to be specific of the deposit type: while reflectance increases with increasing #Mg in the Ojén chromites, it shows the opposite behaviour in podiform chromites. Although these results should be regarded as preliminary until further studies on larger sample populations can be achieved, they are suggestive of possible practical applications for exploration, e. g. to approach Cr-spinel compositions or chromite deposit typology, early in an exploration campaign, by inexpensive reflected light determination of specular reflectance in a few samples.     

Synchrotron XPS studies of solution exposed chalcopyrite,bornite, and heterogeneous chalcopyrite with bornite

Chalcopyrite, CuFeS₂, is an important source of copper and is recovered from ore by the flotation process. Chalcopyrite is commonly associated with other metal sulfides, e.g. bornite, Cu₅FeS₄. In this study the effect of bornite on the oxidation and leaching of chalcopyrite has been investigated by probing the surface evolution of pure chalcopyrite, bornite, and heterogeneous samples containing both chalcopyrite and bornite using Synchrotron X-ray Photoelectron Spectroscopy (SXPS). Samples were freshly fractured in a N₂ atmosphere and the resulting surfaces were oxidised in pH 9 KOH for 30 min or leached in pH 1 HCl for 2 h before being transferred into vacuum without leaving the N₂ atmosphere. Analysis of the chalcopyrite region of each sample indicates that exposure to pH 9 for 30 min when bornite is present results in a decreased concentration of hydrophobic polysulfide species (from 43% to 36% of the total S 2p spectrum). In addition to this decrease in hydrophobic species, there is an increase in the amount of hydrophilic sulfate on the surface, from trace amounts to 3%. For those samples leached at pH 1 there was a small decrease in the amount of polysulfide species (43% to 39%), but also a slight increase in disulfide species (16% to 19%) indicating an alteration to the oxidation process at low pH in the presence of bornite.     

Garnierites and garnierites: Textures,mineralogy and geochemistry of garnierites in the Falcondo Ni-laterite deposit,Dominican Republic

Garnierites (Ni–Mg-bearing phyllosilicates) are significant ore minerals in Ni-laterites of the hydrous silicate-type. In the Falcondo Ni-laterite deposit (Dominican Republic), garnierites are found within the saprolite horizon mainly as fracture-fillings and thin coatings on joints. Field observations indicate an important role of active brittle tectonics during garnierite precipitation. Different greenish colours and textures can be distinguished, which correspond to different mineral phases, defined according to X-ray diffraction (XRD) and electron microprobe (EMP) analyses: a) talc-like (10 Å-type), b) serpentine-like (7 Å-type), c) a mixture of talc- and serpentine-like, and d) sepiolite-like types. Compositional data indicate continuous Mg–Ni solid solution along the joins lizardite–népouite (serpentine-like), kerolite–pimelite (talc-like) and sepiolite–falcondoite (sepiolite-like). In general, talc-like garnierite is dominant in Falcondo Ni-laterite and displays higher Ni contents than serpentine-like garnierites. EMP analyses showing deviations from the stoichiometric Mg–Ni solid solutions of serpentine and talc are best explained by talc- and serpentine-like mixing at the nanoscale. A detailed textural study by means of quantified X-ray element imaging provides a wealth of new information about the relationships between textural position, sequence of crystallization and mineral composition of the studied garnierite samples. These results indicate several stages of growth with variable Ni content, pointing to recurrent changes in the physical–chemical conditions during garnierite precipitation. In addition, our detailed mineralogical study of the Falcondo garnierites revealed that the different types identified have characteristic H₂O content and SiO₂/MgO ratios, which play important roles during the pyrometallurgy process.     

Geochemical challenges of diverse regolith-covered terrains for mineral exploration in China

In recent years mineral exploration has concentrated on concealed deposits in regolith-covered terrains. In China, the regolith-covered landscapes mainly include desert windblown sand basins, desert peneplains, semi-arid grassland, loess plateaus, forestry land, alluvial plains and laterite terrains. These diverse regolith-covered areas represent geochemical challenges for mineral exploration in China. This paper provides an overview of recent progress on mechanisms of metal dispersion from the buried ore deposits through the transported cover to the surface and penetrating geochemical methods to detect the anomalies. Case studies show that, in arid and semi-arid desert sand-covered terrains, sampling of fine-fraction (− 120 mesh, < 0.125 mm) clay-rich horizon soil is cost-effective for regional geochemical surveys for sandstone-type uranium, gold, and base metal deposits. Fine-fraction sampling, selective-leaching and overburden drilling geochemical methods can effectively indicate the 210 gold ore body at Jinwozi goldfield. In alluvium-covered terrains, fine-grained soil sampling (− 200 mesh, < 0.074 mm) combined with selective leaching geochemistry shows clear ring-shaped anomalies of Cu and Ni over the Zhouan concealed Cu–Ni deposit. In laterite-covered terrains, the anomalies determined by the fine-fraction soils and selective leaching of absorbed metals on coatings of Fe–Mn oxides coincide well with the concealed deposit over the Yueyang ore deposits at the Zijin Au–Cu–Ag field. Nanoparticles of hexagonal crystals mainly native copper, gold and alloys of Cu–Fe, Cu–Fe–Mn, Cu–Ti, and Cu–Au were observed in gases, soils and ores using a transmission electron microscope (TEM). The findings imply that nanoparticles of gold and copper may migrate through the transported cover to the surface. Uranium is converted to uranyl ions [UO₂^2 +] under oxidizing conditions when migrating from ore bodies to the surface. The uranyl ions are absorbed on clay minerals, because clay layers have a net negative charge, which needs to be balanced by interlayer cations. Nanoparticles of Au and Cu and ion complexes of U are more readily absorbed onto fine fractions of soils containing clays, colloids, oxides and organic matters. Thus, fine-grained soils enriched with clays, oxides and colloids are useful media for regional geochemical surveys in regolith-covered terrains and in sedimentary basins. Fine-fraction soil sampling combined with selective leaching geochemistry is effective for finding concealed ore bodies in detailed surveys. Penetrating geochemistry at surface sampling provides cost-effective mineral exploration methods for delineation of regional and local targets in transported cover terrains.     

A secondary precious and base metal mineralization in chromitites linked to the development of a Paleozoic accretionary complex in Central Chile

Platinum-group element (PGE) and gold inclusions are usually present in peridotites and chromitite deposits associated with ophiolites. Here, we present the first detailed study of the mineralogy of precious metals in ultramafic rocks hosted in the Paleozoic Coastal Accretionary Complex of Central Chile. In these ultramafic rocks the mineralization of precious metals is associated with small meter-size pods and veins of massive chromitite hosted in serpentinite-filled shear zones. Crystallographic orientation maps of single chromite grains, obtained using the Electron-Backscattered Secondary Diffraction technique, allow us to identify two types of chromite in the precious-metal bearing chromitites: (1) Type A chromite, characterized by an average misorientation per grain of ≤ 2° and chemically homogeneous cores surrounded by a porous rim with abundant inclusions of chlorite, and (2) Type B chromite, which exhibits higher degrees of misorientation (2–8°) and porosity, and abundant silicate inclusions, but a relatively homogeneous chemical composition. In situ analyses using EMPA and LA-ICP-MS for major, minor and trace elements indicate that composition of the magmatic chromite is only preserved in the cores of Type A chromite grains. Core to rim chemical trends in these Type A chromites are characterized by a progressive increase of the Cr# with a decrease of the Mg#, loss of Al and addition of Fe^2 + in the porous rim. The observed changes in the microstructure and chemistry of chromite are associated with the infiltration of external fluids through shear zones filled with antigorite (± talc) developed in partly serpentinized peridotites (i.e., olivine–lizardite dunites). Thermodynamic calculations using the phase equilibria relations in the system Cr₂O₃–MgO–FeO–Al₂O₃–SiO₂–H₂O (CrMFASH) indicate that Fe^2 +-rich porous chromite + chlorite replaced the original assemblage chromite + olivine in the chromitite while prograde antigorite was formed. According to our results this transformation occurred at ~ 510–560 °C when external fluids penetrated the ultramafic/chromitite bodies through shear zones. These temperatures are slightly higher than estimated for the metamorphic peak in the host metapelitic rocks (i.e., ~ 420 °C at 9.3 kbar), suggesting that a hotter ultramafic body was captured by the metasediments of the accretionary prism during their exhumation through subduction channel. Chlorite geothermometry yielded a wide range of lower temperature from 430 to 188 °C, for chlorite present in the porous chromite rims. These results are in agreement with the retrograde overprint under greenchist-facies metamorphism conditions recorded by metapelitic host rocks and minor volcanogenic massive sulphide deposits in the area (300–400 °C, ~ 3–4 kbar). We suggest that although initially decoupled, the chromitite-bearing ultramafic rocks and their metasedimentary host undergone a common metamorphic PT pathway of exhumation during the formation and evolution of the subduction-related accretionary complex.The chromitites contain appreciable amounts of the platinum-group elements (up to 347 ppb total) and gold (up to 24 ppb), present as inclusions of platinum-group minerals (PGM) and alloys as well as native gold. The PGM identified include native osmium, laurite (RuS₂), irarsite (IrAsS), osarsite (OsAsS), omeiite (OsAs₂), Pt–Fe alloy (possibly isoferroplatinum) and a suite of inadequately identified phases such as PtSb (possibly stumpflite), PdHg (possibly potarite), RhS, Ir–Ni and Ir–Ni–Ru compounds. Only a few grains of osmium and laurite were identified in unaltered cores of chromite and therefore considered as magmatic in origin formed during the high-T event of chomite crystallisation in the upper mantle. The other PGM were located in the porous chromite associated with chlorite or base-metal minerals (BMM) that often fill the pores of this altered chromite or are intergrowth with antigorite in the host serpentinized ultramafic rock. The assemblage of BMM identified in the studied rocks include sulphides [millerite (NiS), polydymite (Ni₃S₄), violarite (FeNi₂S₄), galena (PbS), sphalerite (ZnS), chalcocite (CuS)], arsenides [(orcelite (Ni_5 − xAs₂) and maucherite (Ni₁₁As₈)], the sulpharsenide gersdorfitte (NiAsS), and native bismuth. The irregular shape of several PGM grains observed in porous chromite suggest disequilibrium, whereas others exhibit perfectly developed crystal faces with the associated secondary silicate or base-metal mineral suggesting neoformation of PGMs in situ from metamorphic fluids. We suggest that the origin of these PGM inclusions is magmatic, but some grains were reworked in situ when metalloid (i.e., As, Sb, Pb, Zn and Hg)-rich fluids released from metasediments penetrated the ultramafic rocks through active shear zones, once the ultramafic bodies became tectonically mixed with the host metasedimentary host rocks. During this event, gold sourced from the (meta)sediments was also precipitated within chromitites and serpentinites.     

Dielectric loss in ore-forming chromium spinel at temperatures from 20 to 800 °C

Physical, physicochemical, and mineralogical-petrographic methods have been applied to samples of ophiolite-hosted chromite ore from different deposits and occurrences in the Urals. Temperature dependences of dielectric loss obtained for nine chromite ore samples consisting of 95–98% Cr spinel show prominent peaks indicating a relaxation origin of the loss. The analyzed samples have the loss peaks at different temperatures depending mainly on H = (FeO/Fe₂O₃)^? : (FeO/Fe₂O₃)^??, where (FeO/Fe₂O₃)^? and (FeO/Fe₂O₃)^?? are, respectively, the ferrous/ferric oxide ratios in the samples before and after heating to 800 °C, and H is thus the heating-induced relative change in the FeO/Fe₂O₃ ratio. These peak temperatures vary from 550 °C (sample 1, high-Cr chromium spinel with more than 52% Cr₂O₃) to 750 °C (sample 2, aluminous and magnesian spinel with less than 30% Cr₂O₃), and H ranges correspondingly from 1.61 to 5.49. The temperature of the loss peaks is related with H as H = 34.30 ? 11.52N + 1.20N², with an error of σ = 0.19 (N = T · 10^?2, T is temperature in °C).     

Using platinum-group elements and Au geochemistry to constrain the genesis of podiform chromitites and associated peridotites from the Soghan mafic–ultramafic complex,Kerman, Southeastern Iran

The podiform chromite deposit of the Soghan mafic–ultramafic complex is one of the largest chromite deposits in south-east Iran (Esfandagheh area). The Soghan complex is composed mainly of dunite, harzburgite, lherzolite, pyroxenite, chromitite, wehrlite and gabbro. Olivine, orthopyroxene, and to a lesser extent clinopyroxene with highly refractory nature, are the primary silicates found in the harzburgites and dunites. The forsterite content of olivine is slightly higher in dunites (Fo₉₄) than those in harzburgites (Fo₉₂) and lherzolites (Fo₈₉). Chromian spinel mainly occurs as massive chromitite pods and as thin massive chromitite bands together with minor disseminations in dunites and harzburgites. Chromian spinels in massive chromitites show very high Cr-numbers (80–83.6), Mg-numbers (62–69) and very low TiO₂ content (averaging 0.17 wt.%) for which may reflect the crystallization of chromite from a boninitic magma. The Fe^3 +-number is very low, down to < 0.04 wt.%, in the chromian spinel of chromitites and associated peridotites of the Soghan complex.PGE contents are variable and range from 80 to 153 pbb. Chromitites have strongly fractionated chondrite-normalized PGE patterns, which are characterized by enrichments in Os, Ir and Rh relative to Pt and Pd. Moreover, the Pd/Ir value which is an indicator of PGE fractionation ranges from < 0.08 to 0.24 in chromitite of the Soghan complex. These patterns and the low PGE abundances are typical of ophiolitic chromitites and indicating a high degree of partial melting (about 20–24%) of the mantle source. Moreover, the Pd_N/Ir_N ratios in dunites are unfractionated, averaging 1.2, whereas the harzburgites and lherzolites show slightly positive slopes PGE spidergrams, together with a small positive Ru and Pd anomaly, and their Pd_N/Ir_N ratio averages 1.98 and 2.15 respectively.The mineral chemistry data and PGE geochemistry, along with the calculated parental melts in equilibrium with chromian spinel of the Soghan chromitites indicate that the Soghan complex was generated from an arc-related magma with boninitic affinity above a supra-subduction zone setting.