Bulk Sulfide Research Articles

A Quantitative Particle-Based Approach for the Geometallurgical Assessment of Tailings Deposits

Tailings generated during ore processing may host significant residual contents of valuable commodities, including critical metals. The particle properties of the tailings, such as mineralogy, particle size, and the surface liberation of ore minerals, strongly control processing behaviour. This study explores a novel combination of methods for incorporating particle data, derived from automated mineralogy, into geometallurgical models of tailings deposits to better understand their reprocessing potential and the economic feasibility of re-mining. This was achieved through binning of different particle types, geostatistical modelling of particle bin frequencies, and bootstrap resampling to reconstruct particle populations. The spatial distributions of processing-relevant particle properties throughout the tailings deposit were predicted with corresponding uncertainties. There are clear systematic trends in the spatial distributions of different particle types, resulting from the sedimentary-style deposition of the tailings. For instance, the tailings nearer the dam walls comprise coarser, silicate-rich particles, while fine-grained and well-liberated sulphide mineral particles are more abundant in the centre of the tailings deposit. As a result, robust models could be developed for the spatial distributions of particle size and mineralogy, which strongly control the sorting of particles during deposition, and other related properties, such as sulphide mineral grain sizes. Finally, a bulk sulphide flotation process was simulated and acid mine drainage potential estimated using the interpolated particle data. Around 58% of the sulphide minerals present could be recoverable by flotation, with the recoverable sulphide portion decreasing towards the centre of the TSF due to the fine-grained nature of the sulphide minerals. The acid mine drainage potential of the tailings is estimated to be moderate to high, indicating that the carbonate minerals present are not sufficient to neutralise the high acid-generating potential of the sulphide minerals. Overall, this study demonstrates how particle-based geometallurgical models can be developed and utilised for practical applications, with the aim of improving the accuracy of resource and reserve estimations of tailings deposits and the sustainable and responsible management of anthropogenic resources. The methodology proposed here can be easily transferred to other tailings deposits.

Development of Nb-based alloy membranes with improved resistance to corrosion by H2S

At present, the interest in non-Pd hydrogen permeation membranes mainly focuses on group 5 B metals (Nb, V, Ta) and their alloys. To solve the problem of easy oxidation and weak dissociation of hydrogen molecules, a "Pd catalytic layer" needs to be deposited on the membrane surface. Due to its limited stability towards sulfur, issues of irreversible poisoning by sulfur compounds must be addressed. To this end, Pd-, Pd65Ag35-, Pd90Cu10-, Pd80Au20-, and Pd55Ag35Au10-coated Nb30Hf35Co35 membranes were firstly synthesised by magnetron sputtering, and their hydrogen permeation behaviour in pure H2 and/or in different H2/H2S mixtures for up to 1000 ppm at 673 K were evaluated. At these conditions, the permeabilities of the Pd-coated membranes decrease rapidly with increasing the H2S concentration and cannot recover after removal of H2S from the feed mixtures. In comparison, the Pd–Ag-containing membrane greatly increases the pure H2 permeability, whereas the membrane doped with Au can effectively improve the response to H2S. Specifically, the Pd65Ag35-coated membrane shows the highest pure H2 permeability, but it loses maximum permeability value on exposure to H2/H2S feed mixtures. In contrast, Pd80Au20-containing membranes exhibit good tolerance of H2S poisoning and displayed a high fractional recovery (∼83%) of initial H2 permeability. The degradation of permeability for Pd- or Pd65Ag35-coated membranes after the H2S exposure can be ascribed to the deterioration of the structure caused by the possible formation of bulk Pd4S, which has been corroborated with EDS analysis, XRD, and XPS after testing. Finally, to improve both permeability and chemical tolerance, a Pd55Ag35Au10-coated membrane was successfully fabricated, and it possesses excellent comprehensive performance with respect to the permeability and H2S response. At 120 ppm H2S in the feed, the H2 flux equals ca. 43% of its original value at 673 K and can be stable for at least 166 h. Bulk sulfides did not form on the membrane surface after the testing. This paper not only developed a new type of group 5 B alloy membrane with improved resistance to corrosion by H2S, but also further confirmed the feasibility of improving H2S corrosion resistance by adjusting the catalytic layer type or composition of the outermost coating.

Effect of Mixing Intensity on Electrochemical Performance of Oxide/Sulfide Composite Electrolytes

Despite the variety of solid electrolytes available, no single solid electrolyte has been found that meets all the requirements of the successor technology of lithium-ion batteries in an optimum way. However, composite hybrid electrolytes that combine the desired properties such as high ionic conductivity or stability against lithium are promising. The addition of conductive oxide fillers to sulfide solid electrolytes has been reported to increase ionic conductivity and improve stability relative to the individual electrolytes, but the influence of the mixing process to create composite electrolytes has not been investigated. Here, we investigate Li3PS4 (LPS) and Li7La3Zr2O12 (LLZO) composite electrolytes using electrochemical impedance spectroscopy and distribution of relaxation times. The distinction between sulfide bulk and grain boundary polarization processes is possible with the methods used at temperatures below 10 °C. We propose lithium transport through the space-charge layer within the sulfide electrolyte, which increases the conductivity. With increasing mixing intensities in a high-energy ball mill, we show an overlay of the enhanced lithium-ion transport with the structural change of the sulfide matrix component, which increases the ionic conductivity of LPS from 4.1 × 10−5 S cm−1 to 1.7 × 10−4 S cm−1.

Partitioning of highly siderophile elements between monosulfide solid solution and sulfide melt at high pressures

Base metal sulfides (Fe–Ni–Cu–S) are ubiquitous phases in mantle and subduction-related lithologies. Sulfides in the mantle often melt incongruently, which leads to the production of a Cu–Ni-rich sulfide melt and a solid residue called monosulfide solid solution (mss). Even though peridotite-hosted sulfides, which tend to be more Ni-rich, are likely completely molten at mantle potential temperatures, the same is not true for eclogite-hosted Ni-poor, Fe-rich sulfides. Because of this, solid crystalline mss may persist at higher pressures and equilibrate with co-existing sulfide melt along colder geotherms, like those associated with subduction zones. Because highly siderophile elements (HSE—Pt, Pd, Rh, Ru, Os, Ir, and Re) are known to fractionate as a result of mss/sulfide-melt equilibrium, the persistence of an mss/sulfide-melt assemblage to higher pressures may lead to the fractionation of these elements during the subduction process. In this contribution, we carried out an experimental investigation of the partitioning behavior of the HSE, as well as Cu and Ni, between mss and sulfide melt over a pressure and temperature range relevant to equilibration between Earth’s surface and transition zone depths (0.1 MPa to 14 GPa; 930–1530 ∘\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{\\circ }$$\\end{document}C), and variable Ni contents in sulfide. Results show that at higher pressures, the HSE are considerably less fractionated as a result of mss and sulfide melt equilibrium compared to lower pressure conditions. This is exemplified by a lowering of the Dimss/melt\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$D_{i}^\\mathrm{mss/melt}$$\\end{document} for the more compatible HSE (Ru, Os, Ir, Rh and Re) from around 10 at 0.1 MPa to just above or below unity at 14 GPa. Moreover, the higher the Ni content of the bulk sulfide assemblage, the larger the degree of change in the magnitude of HSE fractionation seen over the pressure range studied. The exchange coefficient (KDRu-Pt\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$K_D^{\ extrm{Ru}-\ extrm{Pt}}$$\\end{document}) between highly compatible HSE (Ru) and less compatible Pt illustrates a notable contrast. In the Ni-poor composition (E1), KDRu-Pt\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$K_D^{\ extrm{Ru}-\ extrm{Pt}}$$\\end{document} changes from 27 at 0.1 MPa to 6 at 14 GPa. In contrast, the Ni-rich composition exhibits a broader range, with KDRu-Pt\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$K_D^{\ extrm{Ru}-\ extrm{Pt}}$$\\end{document} ranging from 150 to 17 across the same pressure interval. Our results highlight key differences between experimental data obtained at lower and higher pressure, and how composition, namely the Ni content of sulfide, affects HSE partitioning behavior.

Automated Mineralogy and Diagnostic Leaching Studies on Bulk Sulfide Flotation Concentrate of a Refractory Gold Ore

Obtaining detailed and precise information from a classified refractory gold ore has been a long-standing challenge in mineral processing and process mineralogy. Although the concept of diagnostic leaching has been extensively addressed in the literature, very little information is available linking this approach with current advanced characterization techniques such as automated mineralogy. The present research study aims to characterize the flotation concentrate of refractory gold ore by combining diagnostic leaching and automated mineralogy to examine its processability. The diagnostic leaching process was applied stepwise at five stages, and the automated mineralogy was performed on different size fractions of the flotation concentrate. The chemical (X-ray fluorescence (XRF), atomic absorption spectroscopy (AAS), and inductively coupled plasma-optical emission spectroscopy (ICP-OES)) and mineralogical (X-ray diffraction (XRD)) analyses of the feed sample confirmed that the ore is a low-grade gold ore with 0.7 g/t Au. Initially, bottle roll tests were carried out to investigate leaching behavior, and the ore’s refractory nature, and gold recoveries of bottle roll tests in different sizes were below 40 wt%; it is classified as a high refractory gold ore as a result of direct cyanide leaching. Bulk sulfide flotation was applied to increase the gold content of the material. Automated mineralogy results demonstrated that most of the gold in the concentrate is present as an invisible gold form, and 63.7 wt% of gold was distributed in pyrite. Diagnostic leaching results showed 39.7 wt% of total gold was leachable using direct cyanide leaching, and around 33 wt% of undissolved gold was located in pyrite and arsenopyrite.

Enhanced Electrochemical Performance of Metallic CoS-Based Supercapacitor by Cathodic Exfoliation.

Two-dimensional nanomaterials hold great promise as electrode materials for the construction of excellent electrochemical energy storage and transformation apparatuses. In the study, metallic layered cobalt sulfide was, firstly, applied to the area of energy storage as a supercapacitor electrode. By a facile and scalable method for cathodic electrochemical exfoliation, metallic layered cobalt sulfide bulk can be exfoliated into high-quality and few-layered nanosheets with size distributions in the micrometer scale range and thickness in the order of several nanometers. With a two-dimensional thin sheet structure of metallic cobalt sulfide nanosheets, not only was a larger active surface area created, but also, the insertion/extraction of ions in the procedure of charge and discharge were enhanced. The exfoliated cobalt sulfide was applied as a supercapacitor electrode with obvious improvement compared with the original sample, and the specific capacitance increased from 307 F∙g-1 to 450 F∙g-1 at the current density of 1 A∙g-1. The capacitance retention rate of exfoliated cobalt sulfide enlarged to 84.7% from the original 81.9% of unexfoliated samples while the current density multiplied by 5 times. Moreover, a button-type asymmetric supercapacitor assembled using exfoliated cobalt sulfide as the positive electrode exhibits a maximum specific energy of 9.4 Wh∙kg-1 at the specific power of 1520 W∙kg-1.

PGE geochemical and Os-S-Sr-Nd isotopic constraints on the genesis of the Shitoukengde magmatic sulfide deposit in the East Kunlun Orogenic Belt, NW China

Numerous early Paleozoic mafic–ultramafic intrusions that host important Ni-Cu sulfide mineralization occur in the northern part of the Qinghai-Tibet Plateau, NW China. The sulfide-bearing Shitoukengde Ni-Cu deposit, which is hosted in a ∼424 Ma mafic–ultramafic intrusion, is one of the most represent magmatic sulfide deposits in the East Kunlun Orogenic Belt. The intrusion is composed of a large gabbroic body, cut by lherzolite, olivine websterite, websterite, and minor dunite. Disseminated and net-textured sulfide mineralization occurs as lenses in the center and towards the bottom of the ultramafic bodies. The sulfide mineralization has variable sulfur contents of 0.3 to 13.6 wt% with Ni grade of 0.41 wt% on average, and low platinum-group element (PGE) concentrations (<8.2 ppb Ru and <11.9 ppb Pd). Pd and Ru tenors of bulk sulfides in the deposit are characterized by a positive correlation, indicating that PGE tenor variations are mainly controlled by varying R-factors (magma/sulfide mass ratio). The estimated PGE concentrations in the Shitoukengde magma are about three orders of magnitude lower than those in continental tholeiites. The significant PGE depletions in the Shitoukengde deposit may be due to sulfide removal in the magma conduit at depth. Our new sulfur isotope data reported range in δ34S values from −5.0 to 4.9‰ for the sulfide minerals of the Shitoukengde deposit, clearly distinct from those of mantle-derived sulfur (0 ± 2‰) and immediate country rocks (1.1 to 2.0‰). This, together with the modeling for S isotope variation as a function of R-factor, suggest that the current δ34S range is attributed to the addition of external sulfides with anomalous δ34S into the magma at depth, followed by progressive modification to crustal signature by uncontaminated pulses of magma. The ultramafic rocks exhibit low εNd(t) values (−4.71 to 2.12) and high (87Sr/86Sr)i ratios (0.7073 to 0.7130), which are more enriched relative to the isotopic compositions of depleted mantle. Mixing calculations indicate that about 15 to 20 wt% of lower crustal contamination plus variable upper crustal contamination is required to explain the variations of Sr-Nd isotopes in the Shitoukengde intrusion. Significant crustal contamination is also supported by the mineralization at Shitoukengde having high (187Os/188Os)i (0.24 to 4.51) and γOs(t) values (0.24 to 2534) that are comparable to or higher than those of the important Ni-Cu deposits worldwide. Current results provide evidence that assimilation of crustal sulfur at deep crust and siliceous material with variable crustal contamination during magma ascent and emplacement played critical roles in the attainment of sulfide saturation in the parental magma and the formation of the Shitoukengde deposit.

The Heavy-Metal Fingerprint of the Irinovskoe Hydrothermal Sulfide Field, 13°20′ N, Mid-Atlantic Ridge

A number of Cd-, Pb-, Ag- and Sb(±As)-bearing minerals are found in the Zn-rich smoker chimneys of the Irinovskoe hydrothermal sulfide field, 13°20′ N, Mid-Atlantic Ridge. Sulfide samples were studied using optical microscopy, SEM/EDS, XRD, EBDS, ICP-MS and thermodynamic approaches. The chimneys consist of major sphalerite (including Cd-bearing type with up to 41.38 wt% Cd) and wurtzite, subordinate opal, pyrite, chalcopyrite and Fe-oxyhydroxides, as well as accessory native sulfur, baryte, secondary copper sulfides, galena, CdS phase (most likely hawleyite), pyrrhotite, isocubanite, acanthite, Ag–Cu–Sb(±As)-bearing minerals, native gold, anglesite, gypsum, smectites, naumannite and lollingite. The main source of metals for the formation of Zn-rich sulfides was mafic rocks, with a subordinate role from ultramafic rocks. Crystallization of most accessory minerals at low temperatures (&lt;120 °C) under acidic/reducing conditions and low S activity could be initiated by a magmatic input, which is supported by a negative S isotopic composition of bulk sulfide samples. The finding of Cd-rich sphalerite and a CdS phase in low-temperature mineral assemblage significantly expands the temperature limits of their possible formation. The high Cd contents of easily soluble sphalerite and the presence of the CdS phase should be taken into account in possible future mining and processing of seafloor hydrothermal sulfide fields.

The Baogutu gold deposit in west Junggar, NW China: An epizonal intrusion-related gold deposit

The Baogutu gold deposit (∼4 Mt ore @ 5.5 g/t Au) in West Junggar, is hosted by Early Carboniferous volcano-sedimentary rocks and Late Carboniferous dioritic dikes. Both the dikes and gold mineralization are controlled by NE-trending faults. Two diorite dikes in direct spatial association with gold-bearing quartz veins have LA–ICP–MS zircon U–Pb ages of 316 ± 5 Ma and 314 ± 3 Ma, respectively. The emplacement ages of the dikes are a little older than reported gold mineralization ages (312–311 Ma), which is consistent with their crosscutting relationships. Gold mineralization occurs in quartz veins and stockworks in altered tuff, tuffaceous siltstone, silty mudstone, and dikes. Three gold-bearing vein stages have been identified: (I) pyrite–quartz veins in the deep part of the system; (II) stibnite–quartz veins and (III) native arsenic–quartz veins at shallower-level. Fluid inclusion study shows that the pyrite–quartz veins of stage I formed at temperatures between 345 and 265 °C from fluids with salinities of 5.1–9.1 wt% NaCl equiv, whereas the native arsenic–quartz veins of stage III formed at ∼200 °C from fluids with salinities of 1.4–3.9 wt% NaCl equiv. The ore-forming pressure is estimated to be ∼50–62 MPa, corresponding to mineralization depth of ∼3.3–4.0 km. Oxygen and hydrogen isotope compositions of the fluids (δ18OH2O = 7.9 to 11.2 ‰, δD = -88 to −96 ‰) indicate that the initial hydrothermal fluids have a magmatic source, with involvement of meteoric water in the late stage. The in-situ lead isotopic compositions of pyrite in stage I pyrite–quartz veins are similar to those of bulk sulfide minerals in the Baogutu porphyry Cu deposit, and close to the porphyry stocks, whereas the stibnite and native arsenic in stage II and III quartz veins have more radiogenic lead isotopic signatures due to water–rock exchange with the wall rocks. The Baogutu gold deposit shows affinities to epizonal gold deposits in intrusion-related gold systems (IRGS). The IRGS model suggests that, sheeted, disseminated and vein-type Au–As–Bi mineralization might be found hosted in dioritic to granitic stocks and proximal strata, and vein-type Au–As–Sb mineralization in distal faults.

Mobilization and Fractionation of Magmatic Sulfide: Emplacement and Deformation of the Munali Ni-(Cu-Platinum Group Element) Deposit, Zambia

Abstract Magmatic Ni-Cu-platinum group element (PGE) deposits are commonly located in tectonically active regions that typically undergo significant deformation and metamorphism and subsequent reworking of sulfide. The Munali Ni deposit is hosted by a dynamic intrusive mafic-ultramafic system situated within the Zambezi belt in southern Zambia. The deposit comprises Fe-Ni–dominant magmatic sulfides, present as a number of lenticular massive sulfide bodies that display a variety of magmatic and metamorphic sulfide textures. The sulfide lenses are uniformly deficient in iridium subgroup PGEs (IPGEs), Au, and Cu, with unusual but characteristically high bulk Ni/Cu ratios (~10) and a consistent precious metal mineral assemblage dominated by Pd and Pt tellurides. On a centimeter to meter scale, Cu tenors and Ni/Cu ratios are extremely variable (Ni/Cu between 0.1 and 71.5), while Ni and Pd tenors are consistent, indicative of the high mobility and variable concentrations of Cu sulfide within the deposit. Sulfur isotope signatures of the ore sulfides (δ34S ~6‰; Δ33S ~0‰) indicate a local crustal S contaminant from host marbles yet display S/Se ratios suggestive of a postmagmatic overprint. The consistent geochemical similarities of the bulk sulfide throughout the complex and the absence of primary silicate-sulfide textures suggest that the Munali ores were not sourced from a parental magma directly represented by units within the complex. Instead, it is suggested that the sulfide liquid was introduced from elsewhere in the magmatic system during the later stages of the emplacement of the complex. Fractional crystallization of the sulfide liquid during emplacement resulted in the primary segregation of a Cu-rich residual liquid that migrated away from the bulk of the Fe-Ni sulfide, accounting for the high bulk Ni/Cu ratio, with the potential for the accumulation of a separate and thus far undiscovered Cu orebody. In addition, intense deformation during the Pan-African orogeny and interaction with hydrothermal fluids have locally overprinted some of the primary magmatic textures, resulting in localized sulfide mobilization and the extreme variations of Ni/Cu ratio between sulfide samples. Munali therefore represents a complex dynamic deposit showcasing a variety of mechanisms for sulfide fractionation of an Ni-Cu-PGE orebody by both syn- and postmagmatic processes.

Using Transient XAS to Detect Minute Levels of Reversible S-O Exchange at the Active Sites of MoS2-Based Hydrotreating Catalysts: Effect of Metal Loading, Promotion, Temperature, and Oxygenate Reactant

Modulation excitation spectroscopy (MES) coupled with time-resolved X-ray absorption spectroscopy (XAS) was applied to unpromoted and Co-promoted Mo-based hydrotreating catalysts (i.e., Mo and CoMo catalysts) for investigating the minute as well as instantaneous differences in active site composition under the influence of H2S and H2O. Transient experiments during alternating sulfur- and water-rich conditions were performed at temperatures between 400 and 500 °C using catalysts with varying Co/Mo metal loadings to study the correlative effect of these factors on the stability of the active sites. For both types of catalysts, the features of the demodulated Mo K-edge spectrum matching the difference spectra of the MoS2 and MoO3 references indicate a reversible oxidation–sulfidation process during H2O/H2S cycling. In the case of CoMo catalysts with increasing metal loadings, transient XAS at the Mo K- as well as Co K-edge revealed minute levels of S-O exchange at both sulfided Mo and Co sites, although 26 to 47% of the Co was bound as stable CoAl2O4, which does not form a bulk sulfide. Thus, even in the presence of multiple Co phases (oxide and sulfide) and a low number of active sites relative to the total number of Mo atoms, transient XAS can successfully detect the changes occurring over both the active Co and Mo sites. Furthermore, the comparison of the amplitude of the demodulated spectra showed that Mo atoms are more prone to S-O exchange with increasing temperature, while Co promotion stabilized the molybdenum sulfide. MES-coupled XAS experiments with 1-propanol performed to evaluate the degree of S-O exchange in the presence of another oxygenate reactant revealed the higher affinity of water toward these sulfided Mo sites as compared to 1-propanol.

2D Palladium Sulphate for Visible‐Light‐Driven Optoelectronic Reversible Gas Sensing at Room Temperature

2D metal sulphides (MSs) have attracted enormous amounts of attention in developing high‐performance gas sensors. 2D noble metal sulphides and their derivatives, however, have been less studied due to their predominant nonlayered crystal structures for inefficient exfoliation, despite their surface and peculiar optoelectronic properties. Herein, we successfully synthesize 2D palladium sulphate (PdSO4) from palladium sulphide (PdS) bulk crystals by liquid‐phase exfoliation, in which the presence of oxygen species in the exfoliation solvent plays a key role in the sulphate transformation. Ultrathin 2D PdSO4 planar nanosheets, with thicknesses of ≈3 nm and submicrometer lateral dimensions, exhibit a broad absorption across the visible spectrum, a narrow bandgap of ≈1.35 eV, and a nanosecond scaled long exciton lifetime, which are all suitable for the visible‐light‐driven optoelectronic gas sensing applications. The 2D PdSO4‐based sensor demonstrates a reversible, selective, and sensitive response toward ppb‐leveled NO2 gas at blue light irradiation, featuring a response factor of ≈3.28% for 160 ppb NO2, a low limit of detection of 1.84 ppb, and a &gt; 3 times response factor enhancement over other gases. Herein, the possibility of realizing 2D ultrathin noble metal sulphide compounds from their nonlayered crystal structures and strong potentials in developing high‐performance chemical sensors is explored.

Effect of Temperature on Biobeneficiation of Bulk Copper-Nickel Concentrate with Thermoacidophilic Microbial Communities

Bioleaching of the bulk copper–nickel sulfide concentrate was proposed as a method to remove nickel from it and to obtain a concentrate containing copper as chalcopyrite. This approach is based on the different refractoriness of sulfide minerals in ferric sulfate solutions and oxidation by acidophilic microorganisms. The bulk concentrate contained 10.8% copper in the form of chalcopyrite (CuFeS2) and 7.2% nickel that occurred in pentlandite ((Ni,Fe)9S8) and violarite (FeNi2S4). Three microbial communities grown at 35, 40, and 50 °C were used for bioleaching. The microbial community at 40 °C was the most diverse in the genus and species composition. At all temperatures of the process, the key roles in bioleaching belonged to mixotrophic and heterotrophic acidophiles. The highest levels of nickel leaching of 97.2 and 96.3% were observed in the case of communities growing at 40 and 50 °C, respectively. At the same time, the bioleach residue, which could be characterized as a marketable high-grade copper (chalcopyrite) concentrate, was obtained only at 40 °C. This solid contained 15.6% copper and 0.54% nickel. Thus, the biobeneficiation of bulk sulfide concentrates can be a promising field of biohydrometallurgy.

In situ trace elements and sulfur isotopes of sulfides in the Dabaiyang Te-Au deposit, Hebei Province, China: Implications for Au remobilization from pyrite

Coupled dissolution–reprecipitation (CDR) reactions and low-melting point chalcophile elements (LMCE) melt scavenging are effective mechanisms for gold remobilization and are important for the formation of Te-Au deposits. The Dabaiyang deposit is a typical Te-Au deposit in the Zhangjiakou district and contains tellurides, including altaite, hessite, petzite, tetradymite and tellurobismuthite. Two generations of pyrite have been recognized in the deposit: early pyrite without fractures or alteration (Py1) and later pyrite with more porosity, inclusions and fractures (Py2), and Py2 could be separated into Py2a that containing many fractures without mineral inclusions and Py2b that containing microfractures, micropores and mineral inclusions. Pyrite containing large amounts of mineral inclusions and free of microfractures (Py-MI) has also been recognized, but timing relationships between Py-MI and Py1 (or Py2) is hard to establish. The Pyrite textures indicate that Py2a underwent brittle deformation and that Py2b underwent CDR reactions and Te-melt scavenging. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analyses show that Py2a contains trace elements similar to Py1, while Py2b contains higher Au, Ag, Te and other trace elements, indicating that brittle fracturing has no effect on element mobilization and reprecipitation, and porous pyrite has Au-Ag-Te concentrations. High Co/Ni ratios and Te contents and low Se contents show that the Dabaiyang deposit has a genetic relationship with magmatic activity. In situ δ34S values of sulfides range from −15.77‰ to −6.09‰ (mostly from −13.89 to −10.06‰), which is consistent with bulk sulfide δ34S values. The negative δ34S values more likely resulted from sulfur isotope fractionation in high fO2 hydrothermal fluids. CDR reactions liberated Au, Te, Ag and other trace elements from pyrite and formed porous textures. Then, Te-rich melts scavenged Au from fluid and wallrocks during migration. Finally, the melt precipitated as mineral inclusions in pores or fractures in pyrite. CDR reactions and LMCE melt scavenging played an important role in upgrading the ores and the occurrence of visible native gold in the Dabaiyang gold deposit, as well as other Te-Au deposits in the Zhangjiakou district.

Elucidating the underlying surface chemistry of Sn/Al2O3 catalysts during the propane dehydrogenation in the presence of H2S co-feed

Incipient wetness impregnation was used to deposit dispersed tin (Sn) atoms on γ-Al2O3. The morphology and structure of the catalysts were characterized using Raman, X-ray Photoelectron Spectroscopy (XPS), and low energy ion scattering (LEIS) combined with N2-physisorption and in situ infrared diffuse reflectance spectroscopy (DRIFTS) using NH3 and CO2 as probe molecules, H2- temperature-programmed reduction (H­2-TPR), and steady-state reaction kinetics measurements. The effects of H2S on the surface chemical composition and structure of the resulting catalysts were systematically studied. The results showed isolated and well-dispersed Sn oxide sites of the deposited catalyst with nanoparticles observed only at relatively high coverages of 10% Sn at a coverage ranging from 0.48 to 2.8 Sn atoms nm−2. DRIFT spectroscopy evidenced a decrease in the number of Lewis acid sites on H2S treated Sn/Al2O3 suggesting surface tin species re-dispersing and blocking the active sites of γ-Al2O3. Overall, the surface analysis results presented here suggest that the active catalytic sites in the presence of H2S involve Al2O3 rather than bulk sulfide and Sn atoms dispersed over alumina towards propane dehydrogenation.

A flotation-based approach to the quantification of pyrrhotite in concrete aggregates

Pyrrhotite-bearing aggregates are a major cause of internal sulphate attack (ISA) in concrete. The concentration of pyrrhotite is usually too low to permit direct accurate quantification. Hence, safety restrictions put on aggregates are expressed in terms of the total sulphur content. This paper outlines an analytical approach in which froth flotation is employed to produce a bulk sulphide concentrate amenable to direct quantification of pyrrhotite. The concentration of pyrrhotite in the concentrate is expected to be more than an order of magnitude higher than that of the original sample. Aided by mass balancing based on conventional sulphur analysis, a safe and more accurate estimate of the maximal concentration of pyrrhotite in the original feed can be obtained. This could facilitate better resource utilization. Extensive work is required to develop and optimize the specific flotation procedure in order to obtain a robust analytical protocol.

Collector for Copper-Arsenic Ore Flotation

Copper and scheelite concentrates are produced from scheelite-sulfide ores of the Vostok-2 deposit at the Primorsky processing plant. Chalcopyrite, gold, silver, and harmful impurities (arsenopyrite, pyrrhotite) are extracted into the copper concentrate. As a collector, dialkyldithiophosphate-type IMA-I413p reagent is used. Bulk sulfide concentrate is produced using activated carbon and trisodium phosphate; copper cleaner flotation is carried out in the medium of ferrous sulfate. The commercial copper concentrate contains 16 % copper, 33 g/t gold, and 280 g/t silver. The recovery of the metals is 67.6, 44.7, and 50.1 %, respectively. The weight fraction of arsenic in the ore fluctuates in the range of 0.04–0.25%, and that in the concentrate, 0.7–2.3 %. The enterprise looks for ways to increase recovery of the valuable metals and decrease content of arsenic in the copper concentrate to below 1% at the expense of increasing contrast in the separation of chalcopyrite from iron sulfides/arsenopyrite/pyrrhotite. For solving this problem, we performed a study of flotation properties of sulfide collectors based on dialkyldithiophosphates: BTF-15221, BTF -271, non-ionic collector Reaflot-277, and combinations of Reaflot-277 and IMA-I413p. Applying BTF-15221 collector allowed, as compared to the standard IMA-I413p reagent, to increase recovery of copper, gold, and silver and reduce arsenic content in the copper concentrate. The higher selectivity of BTF-15221 as compared to IMA-I413p was confirmed by the fact that the bulk of the increase in copper recovery and decrease in the weight fraction of arsenic in the copper concentrate was achieved in the selective cycle. Besides, during the study, surface activity and hydrophobizing ability of the water-soluble collectors were assessed. Using the example of BTF-15221, it was shown that improvement of the reagent collecting properties can be achieved not only due to increasing the surface activity of the reagent, but also at its decrease – in case of sufficient hydrophobizing ability of the reagent, close to that of the standard reagent. By adjusting these parameters through the use of low-molecular weight homologues of the main components, it is feasible to increase or decrease the selectivity and collecting ability of the reagent. Collector BTF-15221 is of practical interest for further testing in flotation of copper-arsenic and other ore types.

Decomposition of hydrogen sulfide into elements in the cyclic chemisorption-catalytic regime

The research was devoted to experimental study of low-temperature cyclic chemisorption-catalytic process for H2S decomposition, including the identification of optimal chemisorbent-catalysts and quantitative investigation of process characteristics. The study involved sulfides of transient metals (Fe, Co and Ni) both in bulk and supported forms. The highest efficiency was achieved with bulk sulfides NiS, CoS and especially FeS. Sorption capacity of up to 10 % by weight is observed for these systems, while all the hydrogen sulfide is absorbed irreversibly. It was shown that at elevated temperatures (250−600 °C) the reaction can proceed in a quasi-stationary mode, in which the conversion of hydrogen sulfide and the yield of hydrogen are observed almost unchanged during rather long period of time. In this case, the conversion of H2S and the yield of H2 significantly exceed the equilibrium values for direct H2S decomposition reaction, thus indicating a noticeable contribution of chemisorption processes. In the optimal temperature range (350−400 °C), the hydrogen yield on these systems varies from 11 to 95 % with an average value of 26–34 % per cycle.

Arsenian Pyrite and Cinnabar from Active Submarine Nearshore Vents, Paleochori Bay, Milos Island, Greece

Active, shallow-water (2–10 m below sea level) and low temperature (up to 115 °C) hydrothermal venting at Paleochori Bay, nearshore Milos Island, Greece, discharges CO2 and H2S rich vapors (e.g., low-Cl fluid) and high-salinity liquids, which leads to a diverse assemblage of sulfide and alteration phases in an area of approximately 1 km2. Volcaniclastic detritus recovered from the seafloor is cemented by hydrothermal pyrite and marcasite, while semi-massive to massive pyrite-marcasite constitute mounds and chimney-like edifices. Paragenetic relationships indicate deposition of two distinct mineralogical assemblages related to the venting of high-Cl and low-Cl fluids, respectively: (1) colloform As- and Hg-bearing pyrite (Py I), associated with marcasite, calcite, and apatite, as well as (2) porous and/or massive As-rich pyrite (Py II), associated with barite, alunite/jarosite, and late-stage hydrous ferric oxides. Mercury, in the form of cinnabar, occurs within the As-rich pyrite (Py I) layers, usually forming distinct cinnabar-enriched micro-layers. Arsenic in colloform pyrite I shows a negative correlation with S indicating that As1− dominates in the pyrite structure suggesting formation from a relatively reducing As-rich fluid at conditions similar to low-sulfidation epithermal systems. On the contrary, As3+ dominates in the structure of porous to massive pyrite II suggesting deposition from a sulfate-dominated fluid with lower pH and higher fO2. Bulk sulfide data of pyrite-bearing hydrothermal precipitates also show elevated As (up to 2587 ppm) together with various epithermal-type elements, such as Sb (up to 274 ppm), Tl (up to 513 ppm), and Hg (up to 34 ppm) suggesting an epithermal nature for the hydrothermal activity at Paleochori Bay. Textural relationships indicate a contemporaneous deposition of As and Hg, which is suggested to be the result of venting from both high-salinity, liquid-dominated, as well as CO2- and H2S-rich vapor-dominated fluids that formed during fluid boiling. The CO2- and H2S-rich vapor that physically separated during fluid boiling from the high-salinity liquid led to calcite formation upon condensation in seawater together with the precipitation of As- and Hg-bearing pyrite I. This also led to the formation of sulfuric acid, thereby causing leaching and dissolution of primary iron-rich minerals in the volcaniclastic sediments, finally resulting in pyrite II precipitation in association with alunite/jarosite. The Paleochori vents contain the first documented occurrence of cinnabar on the seafloor in the Mediterranean area and provide an important link between offshore hydrothermal activity and the onshore mercury and arsenic mineralizing system on Milos Island. The results of this study therefore demonstrate that metal and metalloid precipitation in shallow-water continental arc environments is controlled by epithermal processes known from their subaerial analogues.

A novel hydrometallurgical treatment for the recovery of copper, zinc, lead and silver from bulk concentrates

Nowadays sulphide ores exploitation is undergoing some troubles, which are hindering the treatment through traditional routes. Bulk flotation followed by a novel hydrometallurgical process can dodge these difficulties. In this work, an integral hydrometallurgical process consists of two ferric leaching steps, followed by a hot brine leaching stage, is proposed to recover target metals from a bulk sulphide concentrate (2.9% Cu, 7.4% Zn, 2.5% Pb, 67 ppm Ag and 37.2% Fe). In the first ferric leaching step, sphalerite, galena and copper secondary sulphides are dissolved and, in the second leaching step, a silver salt is added in order to catalyse chalcopyrite oxidation. If silver salt is added at the beginning of the process, sphalerite passivation is observed, and therefore zinc recovery is not possible. However, when catalytic leaching is performed after a previous ferric leaching, copper and zinc recoveries higher than 95% are achieved. The leached concentrate (0.3% Cu, 0.8% Zn, 3.3% Pb, 1438 ppm Ag, 38.0% Fe and 6.6% S0), is treated by a hot brine leaching. When hot brine leaching is performed at high pulp density, elemental sulphur removal is necessary to recover all silver added as a catalyst. Extractions higher than 95% for Zn, Cu and Pb are achieved as well as the total recovery of catalyst. The proposed process is silver surplus; therefore, this agent can be recirculated.