Ni Sulfide Research Articles

Hierarchical formation of Ni sulfide single walled carbon nanotubes heterostructure on tin-sulfide scaffolds via mediated SILAR process: Application towards long cycle-life solid-state supercapacitors

For the enhancement of cyclic life in supercapacitors (SCs), hierarchically formed metallic single-walled carbon nanotubes (m-SWNTs) mediated nickel sulfides (c–NS–TS) heterostructures are synthesized on tin-sulfides (TS) scaffolds via successive ionic layer adsorption and reaction (SILAR) process. As compared with bare SnS2, c–NS–TS formation has effects to improve electrical conductivity and to reduce volume expansion in bare SnS2 scaffolds, leading to better specific capacitance and rate performance in SCs. The film structure, morphology evolution, and capacitive kinetics of c–NS–TS thin films are systematically investigated to understand the behind mechanism on the significantly improved electrochemical performance. Thus, the incorporation of highly conductive, nano-scale m-SWNTs (c–NS–TS) yields high capacitance (1120 Fg-1) with excellent cyclic stability (95%), possibly due to inter-linkage of pure m-SWNTs in the heterostructure. For the enhanced electro-kinetic activity, this is strongly affected by the preferable formation on 3-dimensional c–NS–TS heterostructures, along with highly conductive m-SWNTs, leading to the initiation of the electroactive sites for enhanced electro-kinetic activity. For practical validation on applicability, LED lighting is successfully demonstrated, anticipating that the synthesis concept and its electrochemical properties will contribute to next-generation high-performance SC devices.

Kinetics-informed global assessment of mine tailings for CO2 removal

Chemically reactive mine tailings are a potential resource for drawing down carbon dioxide out of the atmosphere in mineral weathering schemes. Such carbon dioxide removal (CDR) systems, applied on a large scale, could help to meet internationally agreed targets for minimising climate change, but crucially we need to identify what materials could react fast enough to provide CDR at relevant climate change mitigation timescales. This study focuses on a range of silicate-dominated tailings, calculating their CDR potential from their chemical composition (specific capacity), estimated global production rates, and the speed of weathering under different reaction conditions. Tailings containing high abundances of olivine, serpentine and diopside show the highest CDR potential due to their favourable kinetics. We conclude that the most suitable tailings for CDR purposes are those associated with olivine dunites, diamond kimberlites, asbestos and talc serpentinites, Ni sulphides, and PGM layered mafic intrusions. We estimate the average annual global CDR potential of tailings weathered over the 70-year period 2030–2100 to be ~93 (unimproved conditions) to 465 (improved conditions) Mt/year.Results indicate that at least 30 countries possess tailings materials that, under improved conditions, may offer a route for CDR which is not currently utilised within the mining industry. By 2100, the total cumulative CDR could reach some 33 GtCO2, of which more than 60% is contributed by PGM tailings produced in Southern Africa, Russia, and North America. The global CDR potential could be increased by utilization of historic tailings and implementing measures to further enhance chemical reaction rates. If practical considerations can be addressed and enhanced weathering rates can be achieved, then CDR from suitable tailings could contribute significantly to national offset goals and global targets. More research is needed to establish the potential and practicality of this technology, including measurements of the mineral weathering kinetics under various conditions.

Needle-like NiSχ@MnCoOχ core–shell nanoarrays with high charge storage performance for application in hybrid supercapacitors

Herein, this work demonstrates the design and synthesis of multicomponent hybrid material NiSχ@MnCoOχ/NF core–shell nanoarrays with high charge storage performance for supercapacitors. The needle-like MnCoOχ nanoarrays as the skeleton of the core layer are grown vertically on the Ni foam via a hydrothermal method, while the NiSχ nanosheets are engineered to anchor onto the surface to form the shell via an electrodeposition method. The unique core–shell architecture provides a large number of reactive sites for MnCoOχ and NiSχ, enhances the number of ion diffusion channels and fast electron transfer pathway. As advanced electrode, NiSχ@MnCoOχ/NF delivers a high specific capacity of 1358 C g−1 (4.84 C cm−2) at 0.5 A g−1, which is 2.05 times that of MnCoOχ/NF (661 C g−1 or 1.35 C cm−2). Furthermore, the hybrid supercapacitor device (NiSχ@MnCoOχ/NF//rGO/NF) exhibits a high specific capacitance of 181.71 F g−1 (2.26 F cm−2), a long cycle life, and a maximum specific energy of 64.61 Wh kg−1, suggesting a great potential for practical application. Therefore, an ingeniously designed core–shell array structure can effectively realize the charge storage potential of the Mn–Co oxides and Ni sulfides, and this work presents an alternative method for constructing hybrid architectures for advanced electrochemical energy storage materials.

Nickel isotope fractionation during precipitation of Ni secondary minerals and synchrotron-based analysis of the precipitates

The determination of fractionation factors associated with important biogeochemical processes controlling Ni availability in the environment is necessary to confidently use Ni isotope signatures as tracers in environmental studies. In this paper we present experimental results on Ni isotope fractionation during the precipitation of Ni secondary minerals (Ni hydroxide, Ni hydroxycarbonate and Ni sulfide minerals) that can control Ni fate and mobility in settings where high dissolved Ni(II) concentrations may pose a serious threat to the environment. Results show a preferential partition of lighter isotopes into the solid phase with associated fractionation factors ε of −0.40‰ ± 0.04‰, −0.50‰ ± 0.02‰, and −0.73‰ ± 0.08‰ relative to the hydroxide, carbonate and sulfide systems, respectively. Early kinetically induced isotope fractionation, followed by possible re-equilibration with the reacting solutions was suggested for the three investigated systems. Distortions of Ni-O bonds in the octahedra constituting the structures of Ni hydroxide and hydroxycarbonate minerals could have also contributed to the isotopic fractionation measured in these systems. In contrast, for Ni sulfide system, the magnitude of Ni isotope fractionation seemed to be determined by water and sulfide ligands exchange in solution prior to mineral nucleation. Although there is insufficient evidence to determine whether complete equilibrium occurred in the three studied systems, the fractionation factors reported in this study can provide useful indicators of Ni isotope fractionation associated with fast precipitation of secondary minerals involved in the sequestration of Ni from contaminated environments. These findings also contribute to the characterization of Ni isotope systematics which is still in the early stages of development.

Chromite-PGM Mineralization in the Lherzolite Mantle Tectonite of the Kraka Ophiolite Complex (Southern Urals, Russia)

The mantle tectonite of the Kraka ophiolite contains several chromite deposits. Two of them consisting of high-Cr podiform chromitite—the Bolshoi Bashart located within harzburgite of the upper mantle transition zone and Prospect 33 located in the deep lherzolitic mantle—have been investigated. Both deposits are enveloped in dunite, and were formed by reaction between the mantle protolith and high-Mg, anhydrous magma, enriched in Al2O3, TiO2, and Na2O compared with boninite. The PGE mineralization is very poor (<100 ppb) in both deposits. Laurite (RuS2) is the most common PGM inclusion in chromite, although it is accompanied by erlichmanite (OsS2) and (Ir,Ni) sulfides in Prospect 33. Precipitation of PGM occurred at sulfur fugacity and temperatures of logƒS2 = (−3.0), 1300–1100 °C in Bolshoi Bashart, and logƒS2 = (−3.0/+1.0), 1100–800 °C in Prospect 33, respectively. The paucity of chromite-PGM mineralization compared with giant chromite deposits in the mantle tectonite in supra-subduction zones (SSZ) of the Urals (Ray-Iz, Kempirsai) is ascribed to the peculiar petrologic nature (low depleted lherzolite) and geodynamic setting (rifted continental margin?) of the Kraka ophiolite, which did not enable drainage of the upper mantle with a large volume of mafic magma.

Origin of Fe–Ni–Cu (Co) sulfide and Fe–Ti oxide minerals in the c. 1.77 Ga dolerite dyke, Singhbhum Craton (eastern India)

Abstract Dolerite dyke swarms are widespread within the Singhbhum Craton (eastern India) that emplaced from the Neoarchean to Paleoproterozoic era just after the stabilization of crust before c. 3 Ga. These dyke swarms are oriented in NE–SW to NNE–SSW, NW–SE to WNW–ESE, east–west and north–south directions. The WNW–ESE-trending c. 1.77 Ga Pipilia dyke swarm is sampled from the Satkosia area of Orissa state. The dyke shows a noticeable disparity in terms of the modal proportion and grain size of pyroxenes, plagioclase, Fe–Ti oxide minerals and texture across the trend. In places the primary silicates are altered to secondary hydrated mineral assemblages of amphibole, chlorite and sericite. The primary silicates are clinopyroxene (augite – Mg# = 65.7–82.6; En 37–48 Fs 11–17 Wo 36–41 ), orthopyroxene (clinoenstatite – Mg# = 68.5–78; En 63–70 Fs 20–29 Wo 4–5 ) and plagioclase (An 11–39 Ab 44–82 Or 1–7 ) and the Fe–Ti oxides are titanomagnetite (FeO, 34.38–39.50 wt%; Fe 2 O 3 , 48.26–56.21 wt%; TiO 2 , 5.05–9.60 wt%) and ilmenite (FeO, 40.75–43.79 wt%; Fe 2 O 3 , 3.54–10.03 wt%; TiO 2 , 47.82–50.87 wt%). Application of two-pyroxene thermometry yields an equilibration temperature range of 1065–978°C, and coexisting titanomagnetite–ilmenite pairs reveal 731.39–573.37°C under the oxygen fugacity ( f O 2 ) condition NNO + 0.3 to FMQ − 1.03. The dyke contains disseminated sulfides at the interstices of Fe–Ti oxides and silicates. Major sulfide minerals are pyrite, chalcopyrite and vaesite; pyrite–vaesite assemblages occur in association with secondary silicate minerals. Pyrite grains contain variable concentrations of Co (0.01–5.70 wt%) and Ni (0.02–1.95 wt%). Coexisting vaesite contains Co (2.42–10.44 wt%), Ni (26.40–47.88 wt%) and Fe (7.32–26.55 wt%). Texture, sulfide–silicate assemblage and the presence of low metal/S sulfides such as the pyrite–vaesite assemblage indicate that primary Fe–Ni sulfides (pyrrhotite–pentlandite) that segregated from immiscible sulfide liquid at high temperature are modified by late magmatic/hydrothermal fluid activities. Numerous sulfide-bearing deposits hosted in ultramafic–mafic intrusions of Paleoproterozoic age have been recorded globally and the occurrence of Fe–Ni sulfides in the c. 1.77 Ga Pipilia dyke swarm in the Singhbhum Craton enhances the exploration potential of this craton in eastern India.

Relative study of Ni sulfides synthesized from single and multisource precursors for photocatalytic and battery applications

Chalcogenide nanoparticles and their morphologies have contributed to the most prominent nano-chemistry field under their ease of fabrication and assorted appositeness. Herein, we demonstrate the two antithetic pathways viz., single source (S-S) and multisource (M-S) precursors to fabricate nanomaterial. The motive of the stated research work was to identify any alteration in morphologies of the resulting product by shifting the fabrication pathways. Wherefore, to deduct the results, photocatalytic activity (covered by full-spectrum versus four contrasting dyes) and battery application (electrochemical discharge/charge at voltage limits of 0.01 – 3.0 V against Li/Li+) of both materials have been executed. The nanomaterial gathered from the S-S protocol has an immense exterior area that acknowledges the photocatalytic activity rather than the product obtained from the M-S protocol.

Multi-stage sulfide evolution of the Moran Ni sulfide ore, Kambalda, Western Australia: insights into the dynamics of ore forming processes of komatiite-hosted deposits

The Moran komatiite-hosted Ni sulfide deposit at Kambalda (Australia) is one of the better preserved orebodies at Kambalda. Its geochemical signature is used to investigate the evolution of the sulfide mineralization. The orebody has several parts, including a flanking segment where massive sulfides formed relatively early and a central portion in a 40-m-deep erosional embayment representing a later generation of massive and net-textured sulfides. Basal massive sulfides within the deep embayment vary systematically in their chalcophile element contents (Ni, PGE, Au, Te, As, Bi). Elements compatible in monosulfide solid solution (MSS) exhibit the highest concentration at the edge of the orebody (up to 4.3 ppm Ir + Os + Ru + Rh), whereas incompatible elements are most concentrated in the centre (up to 11.2 ppm Pt + Pd + Au). This difference in element distributions is explained by fractional crystallization of sulfide melt from the edge towards the centre. To explain the vertical movement of the residual fractionated melt, a new model of sulfide crystallization is proposed. A low-viscosity boundary layer containing incompatible elements is formed between MSS and sulfide melt. This melt propagates with the crystallization front towards the centre of the sulfide melt pool. Trace element variations in pentlandite (e.g. Co) and composite Co- and Bi-bearing arsenide-telluride grains suggest that during the final stages of crystallization, an immiscible Co-As-Te-Bi melt is formed.

MOF-derived Zn–Co–Ni sulfides with hollow nanosword arrays for high-efficiency overall water and urea electrolysis

Water electrolysis is a promising technology to produce hydrogen but it was severely restricted by the slow oxygen evolution reaction (OER). Herein, we firstly reported an advanced electrocatalyst of MOF-derived hollow Zn–Co–Ni sulfides (ZnS@Co9S8@Ni3S2-1/2, abbreviated as ZCNS-1/2) nanosword arrays (NSAs) with remarkable hydrogen evolution reaction (HER), OER and corresponding water electrolysis performance. To reach a current density of 10 mA cm−2, the cell voltage of assembled ZCNS-1/2//ZCNS-1/2 for urea electrolysis (1.314 V) is 208 mV lower than that for water electrolysis (1.522 V) and stably catalyzed for over 15 h, substantially outperforming the most reported water and urea electrolysis electrocatalysts. Density functional theory calculations and experimental result clearly reveal that the properties of large electrochemical active surface area (ECSA) caused by hollow NSAs and fast charge transfer resulted from the Co9S8@Ni3S2 heterostructure endow the ZCNS-1/2 electrode with an enhanced electrocatalytic performance.

The Jaguar hydrothermal nickel sulfide deposit: Evidence for a nickel-rich member of IOCG-type deposits in the Carajás Mineral Province, Brazil

The Jaguar Ni sulfide deposit (mineral reserves of 58.6 Mt at 0.95 wt% Ni) occurs along a regional fault zone in the Carajás Mineral Province in the Amazonian Craton, Brazil. This study presents the first detailed description of the Jaguar deposit and provides a basic framework to constrain the origin of the Ni sulfide mineralization. Jaguar nickel sulfide orebodies are associated with ductile-brittle hydrothermal alteration zones developed over felsic subvolcanic or granitic country rocks. Prominent features of the Jaguar deposit include: i. its location along regional scale deep fault systems, ii. extensive zones of biotite-chlorite alteration overprinted by magnetite-apatite-quartz alteration zones, iii. sulfide mineralization occurring as steeply dipping orebodies closely associated with magnetite-apatite rich bodies, iv. sulfides that are disseminated or form the matrix of breccias consisting of pyrite and millerite, with minor pentlandite, chalcopyrite and pyrrhotite, v. pyrite, magnetite and apatite occur mostly as euhedral to subhedral crystals enclosed in irregular aggregates of fine-grained anhedral millerite, vi. sulfide mineralization with high Ni (Ni/S ~ 0.15–0.30) and Co (Co/S ~ 0.005–0.015) contents, high Ni/Cu ratios (~5–25) and low Zn and PGE contents, vii. metal association consisting of LREE, Fe, U, P, Pb, Bi, Te, Ni, and Co, and viii. mineralized zones with high F contents and a positive correlation of F with S, Ni and P2O5. The geological setting and characteristics of the Jaguar deposit are similar to the iron-oxide-copper-gold (IOCG) deposits in the Carajás Mineral Province, indicating that they all belong to a regional hydrothermal system. The existence of nickel-rich members of IOCG type mineralizations in the Carajás Mineral Province was previously suggested for other deposits (e.g., GT34, Castanha) and interpreted as deeper portions of the IOCG mineral system. The close association of nickel sulfide mineralization in the Jaguar deposit with magnetite-apatite-rich breccias may be interpreted as an iron-oxide-apatite (IOA) member within the regional hydrothermal system. In contrast to most hydrothermal nickel deposits in the world, the Jaguar deposit is neither hosted by mafic-ultramafic rocks nor associated with black shales. Therefore, the Jaguar deposit is interpreted as an uncommon hydrothermal Ni deposit associated with the IOCG mineral system in the Carajás Mineral Province. Our results provide new insights for worldwide exploration for Ni sulfide deposits in geological environments different from those traditionally considered prospective.

First-principles calculations of thermodynamic properties of Ni sulfides in the upper mantle

First-principles calculations of thermodynamic properties of Ni sulfides in the upper mantle

The Glafirinskoe and related skarn Cu-Au-W-Mo deposits in the Northern Altai, SW Siberia, Russia: Geology, igneous geochemistry, zircon U-Pb geochronology, mineralization, and fluid inclusion characteristics

The Glafirinskoe and related skarn Cu-Au (+Mo, W) deposits represent an Early Paleozoic (Late Cambrian to very early Ordovician) mineralization in the Altaid Belt, also known as the Central Asian Orogenic Belt. They are associated with multiphase plutons of high-K calc-alkaline to shoshonitic rocks that are related to a low-degree partial melting of metasomatically-enriched upper mantle, followed by amphibole fractionation in a deep (lower crustal ?) magma chamber and then by magma fractionation and emplacement at shallower crustal levels. Isotopic U-Pb zircon dating of the igneous rocks yields early Ordovician (ca. 480–478 Ma and 483 Ma) age. These rocks were emplaced in a continental magmatic arc after the Late Cambrian collision, in a post-collisional setting involving the stall and break-off of the subducting slab during the Late Cambrian to Early Ordovician.The deposits comprise prograde and retrograde skarns that are characterized by abundant andradite-rich garnet, which defines their oxidized type. Wider zones of potassic (quartz-K-feldspar) and calc-potassic (quartz-K-feldspar-calcite-garnet) alteration occur in the igneous rocks, with their further overprint by propylitic (with abundant scapolite) and phyllic (carbonate-phyllic) alteration. All these alteration assemblages bear abundant chalcopyrite and minor bornite. Phyllic alteration assemblages also contain various As, Sb, Pb, Zn, Co, Ni sulfides and sulfosalts, tellurides, Bi minerals, and native Au. Scheelite and/or molybdenite are locally present in some mineralized zones. The Cu-Au-Mo(-W) mineralization occurs as skarn orebodies that are spatially associated with porphyry-style alteration assemblages reflecting the high exploration potential for additional, but concealed, skarn-porphyry Cu-Au-Mo deposits in the vicinity.The retrograde skarn and potassic (calc-potassic) alteration assemblages were formed from high temperature (570–580 °C), high salinity, aqueous chloride magmatic-hydrothermal fluid, with its boiling and phase separation indicating hydrostatic conditions at a relatively deep (~6 km) skarn-porphyry environment. Propylitic alteration assemblages were formed at lower temperatures (~380–420 °C) from a Ca-Na-chloride, low salinity (~8 wt% NaCl-eq.) magmatic-hydrothermal fluid. Fluid inclusions in minerals from phyllic alteration assemblages indicate the influx of a CO2-rich fluid at about 270–290 °C and 1400 ± 50 bars and subsequent mixing with more saline (20 wt% NaCl-eq.) and cooler (~240 °C) hydrothermal fluids.

Mineralogy of fine-grained matrix, fine-grained rim, chondrule rim, and altered mesostasis of a chondrule in Asuka 12169, one of the least altered CM chondrites

Mineralogy of fine-grained matrix (FGM), fine-grained rim (FGR), chondrule rim, and altered mesostasis of a chondrule from the Asuka (A) 12169 CM3.0 chondrite was investigated by field emission scanning electron microscopy (FE-SEM), synchrotron radiation-based X-ray nano-tomography (SR-XCT), and transmission electron microscopy (TEM). SR-XCT and TEM observations revealed that both FGM and FGR contain abundant amorphous silicate embedding nano-inclusions (most are Fe–Ni sulfide). Although the amorphous silicate is more or less hydrated based on the analysis of the X-ray linear attenuation coefficients in SR-XCT, there are no areas filled by abundant phyllosilicate even in three dimensions. However, FGM and FGR contain ~2-10 μm-sized aggregates composed of tochilinite, nano-inclusions of possible magnetite, and poorly crystalline serpentine without sharp boundaries with the surroundings. It is unlikely that the heterogeneity resulted from brecciation and mixing of materials that experienced different degrees of aqueous alteration, but more likely from a very early stage of aqueous alteration that proceeded heterogeneously depending on locally different chemistry. Chondrule mesostasis near the surface of a chondrule was altered to saponite with tochilinite-rich aggregates. These observations indicate that the degree aqueous alteration of A 12169 is very low and that it is comparable with that of Acfer 094, ALH 77307, and the least altered areas of Paris.

Age, Isotopic Features, and Formation Type of Rocks and Ores of the Allarechka Cu–Ni Sulfide Deposit, Fennoscandian Shield

Age, Isotopic Features, and Formation Type of Rocks and Ores of the Allarechka Cu–Ni Sulfide Deposit, Fennoscandian Shield

Evaluation of mine waste characterization to identify opportunities for optimizing project economics using fragmentation analysis

ABSTRACT As metal mineral resources get depleted over time, there is a need to recover metals from ores of lower grades and waste. Mining wastes are largely characterized using physical and mineralogical heterogeneity properties. There is variation in the geochemical properties with different grain sizes, thus, different metal recovery potential. The research evaluated mine waste characterization and identified opportunities for optimizing project economics using fragmentation analysis. This study linked petrographic, compositional and quantitative mineralogical analyses with fragmentation data resulting from conventional mechanical communition of mined-out waste rock. The results improve the understanding of what grain sizes are optimal for metal recovery from the waste rock and established that environmental threats can be mitigated by removing fines from waste. The economic metals including Ni and Cu sulphides are predominantly held in pentlandite and chalcopyrite within the rocks. Maximum liberation and metal recovery are in the finer grains.

Geodynamic Setting and Cu-Ni Potential of Late Permian Xiwanggou Mafic-Ultramafic Rocks, East Kunlun Orogenic Belt, NW China

Several magmatic Cu–Ni sulfide deposits have recently been explored along the deep Middle Kunlun fault related to the extension of the East Kunlun orogenic belt in Qinghai Province, NW China. The Xiwanggou mafic–ultramafic rocks associated with Cu–Ni sulfide mineralization are first to be dated as late Permian compared to most of the deposits formed during late Silurian–early Devonian in this region. The Xiwanggou complexes located in the junction area between the East Kunlun and West Qinling belts, are composed of gabbros, olivine-gabbros, pyroxenites, olivine-pyroxenites, and peridotites. The Cu–Ni mineralization are mainly hosted in the olivine-pyroxenites and pyroxenites, whereas the sulfide-poor mineralization distributed in gabbros and olivine-gabbros. Zircon LA-ICP-MS U–Pb dating of the gabbro and olivine-pyroxenite revealed their crystallized ages of 250.8 ± 0.8 Ma and 257.3 ± 0.7 Ma, respectively. The trace element characteristics of the Xiwanggou fertile mafic-ultramafic rocks shows the enrichments in Sr, Rb, Th, Ba and light rare earth elements, and depletions in Nb and Ta, which are associated with the slab derived fluid input and dehydration melting of amphiboles. Meanwhile, Sr–Nd and Hf isotopic compositions of the gabbro [εNd(t) = 0.66–1.18; εHf(t) = 5.2–12] and olivine-pyroxenite [εNd(t) = −1.09 – −0.43; εHf(t) = 5.4–17.7] show that the magma was mainly derived from the metasomatized portions of subcontinental lithospheric mantle (SCLM) source in the mantle wedge. The magma primarily experienced dehydration melting processes of amphiboles and subsequently underwent hydrated melting in the overlying mantle wedge and relatively reduced background. The cool subduction process of the Anemaqen oceanic lithosphere maybe trigger large melting in the mantle wedge resulting in a relative low-Ni content in the melt. The transpressional windows formed by the right-lateral strike-slip shearing action of the Wenquan and South Kunlun faults in the South Kunlun forearc belt created a significant conduit for the magma ascending. The thermometer of Fe and Ni exchange between coexisting olivine and sulfide melt indicates the magma were yielded in a temperature range of ca. 1200–1300°C and an oxygen fugacity range of ca. –10.57 to –8.98 (log unit), which suggested that the parental magma of the Xiwanggou complex derived from a relatively reduced source favoring Ni relative to Fe in the melt. The intermediate sulfide segregation from the melt resulted in a medium tenor potential for the Xiwanggou complex.

Estimation of Formation Temperature of the Noble Metal Mineralization of the Kovdor Alkaline-Ultrabasic Massif (Kola Peninsula)

In this work, mineralogical and geochemical data are presented for sulfide-rich phoscorites and carbonatites in the Kovdor massif. The PGE and Ag-bearing mineralization of bornite–chalcopyrite and Ag‑bearing mineralization of pyrrhotite–chalcopyrite associations were investigated. In carbonatite stage formation of massif, the noble metal minerals occurred during evolution of alkaline–ultrabasic melt and after separation of primary sulfide melt enriched in PGE, Au and Ag. According to the observed relationships, the minerals of PGE, Au, and Ag in bornite–chalcopyrite association are crystallized sequentially from magmatic to hydrothermal stages. Crystallization of Os, Ir, Pt and Pd minerals (erlichmanite, rustenburgite, isoferroplatinum, mertieite–II, etc.) occurred at temperature close to 480°С, while further decrease in the temperature and an increase in the Cu and Fe activity in the melt leads to the crystallization of Sb, Pb, As, Bi and Te-bearing minerals (sperrylite, tatyanaite, moncheite, stumpflite, etc.). Formation of Au and Ag-bearing minerals (electrum, silver, stromeyerite, lenaite, etc.) occurred at temperatures below 300 °C with relatively low sulfur activity. In carbonatites and phoscorites of the middle and late magmatic stages enriched with magnetite, pyrrhotite–chalcopyrite association with silver-bearing minerals was formed at temperatures below 300°C. Ag-bearing minerals were produced during hydrothermal recrystallization of Cu–Fe–Ni sulfides at temperature close to 150°C.

Phase Relations in the Ni–S System at High Pressures from ab Initio Computations

Based on the ab initio calculations within the density functional theory and crystal structure prediction algorithms, the structure and stability of compounds in the Ni–S system at pressures of 100–400 GPa were determined. As a result, a homologous series of discrete compounds (Ni and S) consisting of Ni14S-C2/m, Ni13S-R3̅, Ni12S-R3̅, Ni5S-C2/m, Ni4S-P1̅, and Ni3S-Cmcm is revealed. We also confirmed the absence of the stable Fe-bearing compounds between Fe and Fe2S in the studied pressure range. At the Earth’s core pressures, 4 wt % of sulfur can be dissolved in solid fcc-Ni without deformation of the structure. Significant deformations in the Ni structure occur at sulfur contents from 4 to 15 wt %. In contrast, up to 0.45 wt % of sulfur could be dissolved in hcp-Fe at 350 GPa and 0 K. For Ni3S, two phases with space groups I4̅ and Cmcm were predicted. Ni3S-I4̅ is stable at least from 100 GPa, whereas above 330 GPa, it transforms into Ni3S-Cmcm. The pressure of phase transition is almost independent of temperature. The Ni2S is stable in the entire pressure range and undergoes a single-phase transition from the Pnma- to P6̅2m-phase at 266 GPa and 0 K with a Clapeyron slope of 5 MPa/K. The S-rich sulfide NiS3 is characterized by Im3̅m symmetry and is thermodynamically stable from 100 to 318 GPa. Our new data on Ni sulfides might be important to constrain detailed thermodynamic models for Fe–Ni-bearing Earth and planetary cores.

Synthesis and Performance of Presulfided NiMoP/Al2O3-SiO2 Catalyst

Presulfided NiMoP/Al2O3-SiO2 catalysts were synthesised. The BET surface area and BJH pore volume gradually decrease with P loading due to the ingress of active phases into the pores of the support. No bulk Ni sulfide phase is observed either in the XRD pattern or in the HRTEM micrographs of all catalysts. The mainly high active center is multilayered Ni-Mo-S type II phase benefited from the weak bond between Al2O3-SiO2 support and active components. The incorporation of phosphorous enhances the dispersion of MoS2 particles and formed more multilayered Ni-Mo-S type II phase. The route of hydrogenation activity increases with the content of P up to 1.2 wt.%, and the route of direct desulfurization activity in the hydrodesulfurization of dibenzothiophene decreases simultaneously. This is attributed to the higher MoS2 stacking number and shorter MoS2 slab length.

Using geochemical imaging data to map nickel sulfide deposits in Daxinganling, China

Nickel sulfide deposits occur in ultramafic rocks in the Daxinganling area, China; however, the prospectivity of these deposits has received little attention. This study transformed rasterized regional 1:200,000 geochemical data into spectral-like data and then used hyperspectral tools of the spectral angle mapper (SAM) to classify possible ultramafic lithologies and the multirange spectral feature fitting (MRSFF) method to classify prospective areas that are similar to a typical Gaxian Ni deposit. The prospective area map generated by the MRSFF implies the possible occurrence of ultramafic rocks classified by the SAM method. These results confirm the suitability of this innovative approach for prospectivity mapping of Ni sulfide deposits.