Metal Sulfide Minerals Research Articles

Recovering Cobalt and Sulfur in Low Grade Cobalt-Bearing V–Ti Magnetite Tailings Using Flotation Process

There is 0.032% cobalt and 0.56% sulfur in the cobalt-bearing V–Ti tailings in the Panxi Region, with the metal sulfide minerals mainly including FeS2, Fe1−xS, Co3S4, and (Fe,Co)S2, and the gangue minerals mainly including aluminosilicate minerals. The flotation process was used to recover cobalt and sulfur in the cobalt-bearing V–Ti tailings. The results showed that an optimized cobalt–sulfur concentrate with a cobalt grade of 2.08%, sulfur content of 36.12%, sulfur recovery of 85.79%, and cobalt recovery and 84.77% were obtained by flotation process of one roughing, three sweeping, and three cleaning under roughing conditions, which employed pulp pH of 8, grinding fineness of <0.074 mm occupying 80%, flotation concentration of 30%, and dosages of butyl xanthate, copper sulfate, and pine oil of 100 g/t, 30 g/t, and 20 g/t, respectively. Optimized one sweeping, two sweeping, and three sweeping conditions used a pulp pH of 9, and dosages of butyl xanthate, copper sulfate, and pine oil of 50 g/t, 15 g/t, 10 g/t; 25 g/t, 7.5 g/t, 5 g/t; 20 g/t, 5 g/t, 5 g/t, respectively. Optimized one cleaning, two cleaning, and three cleaning condition dosages of sodium silicate of 200 g/t, 100 g/t, 50 g/t, respectively. Study of analysis and characterization of cobalt–sulfur concentrate by X-ray diffraction (XRD), automatic mineral analyzer (MLA), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) showed that the main minerals in cobalt–sulfur concentrate are FeS2, Co3S4 and (Fe,Co)S2, of which FeS2 and (Fe,Co)S2 accounted for 65.64% and Co3S4 for 22.64%. Gangue minerals accounted for 11.72%. The element Co in (Fe,Co)S2 is closely related to pyrite in the form of isomorphism, and the flotability difference between cobalt and pyrite is very small, which makes it difficult to separate cobalt and sulfur. Cobalt–sulfur concentrate can be used as raw material for further separation of cobalt and sulfur in smelting by pyrometallurgical or hydrometallurgical methods.

Significance of the metasomatized lithospheric mantle in the formation of early basalts and Cu – platinum group element sulfide mineralization in the Coldwell Complex, Midcontinent Rift, Canada

A diverse suite of tholeiitic to alkaline basalt and gabbroic intrusions located in the Coldwell Complex on the northern margin of the Midcontinent Rift exhibit unusual trace element signatures that show enriched large ion lithophile elements and light rare earth elements with negative Nb and Zr anomalies. These features are not typical of magmas derived by partial melting within or above a rising mantle plume, as might be expected in an early Midcontinent Rift magmatic event. In this paper, we provide a detailed geochemical study of a 500 m thick sequence of metabasalt that represents the earliest stage of magmatism in the Coldwell Complex. We show that contamination or crystallization processes or subsequent metasomatism cannot explain the trace element variations. Instead, we propose partial melting in a metasomatized Subcontinental Lithospheric Mantle source to explain the decoupled behavior of large ion lithophile elements from light rare earth elements and heavy rare earth elements and rare earth elements from high field strength elements and the enriched Nd isotope signature of metabasalt. Similar features occur in unit 5b of the Mamainse Point Volcanic Group located at the northern margin of the Rift. An objective of this paper is to relate Two Duck Lake gabbro, host rock for low-sulfur, high precious metal sulfide mineralization at the Marathon deposit, to the metabasalt sequence. The excellent match of trace element abundances in Two Duck Lake gabbro to metabasalt unit 3 confirms an early Coldwell Complex age for metabasalt and a Subcontinental Lithospheric Mantle source for Cu – platinum group element mineralized gabbros.

The synergistic interaction between dithiophosphate collectors and frothers at the air-water and sulphide mineral interface

Dialkyl dithiophosphates (DTP) are commonly used as primary or secondary collectors in base metal sulfide and platinum group mineral flotation. However, evidence in the literature suggests that, under basic conditions, DTP does not adsorb onto certain minerals. The purpose of this study was to investigate the interactions between DTP or xanthate collectors and frothers at the solid-liquid and air-liquid interfaces. Microflotation and contact time tests showed that DTP synergistically improved recoveries and attachment probabilities of galena and pyrite in the presence of frother. These improvements were not seen for any of the single reagents or, most importantly, for mixtures of a xanthate collector and frother. By measuring the residual collector concentration in solution, it was shown that no DTP adsorbed onto the galena surface and only minimal amounts onto the pyrite surface, either in the presence or absence of frother. In contrast, all of the xanthate collector adsorbed onto both pyrite and galena. Investigations at the air-water interface included surface tension and bubble size measurements. These showed that DTP, unlike xanthate, was weakly active at the air-water interface, but did not show evidence of synergistic interaction with frother. It was concluded that DTP can have an alternative mechanism of flotation enhancement to conventional collectors by adsorbing at the air-liquid interface and not the solid-liquid interface. Various theories of the detailed mechanism are discussed in the paper.

Micromorphology and environmental behavior of oxide deposit layers in sulfide-rich tailings in Tongling, Anhui Province, China

Sulfide-rich tailings produced by mineral processing are prone to oxidation and cause many pollution problems in the surrounding environment; therefore, this issue has become a focus of attention. The Tongling Shuimuchong tailings reservoir contains a large amount of sulfide minerals, especially pyrrhotite and pyrite. This reservoir features obvious oxidation in the surface layer, and the slab is very hard. Mineralogical and environmental geochemical analyses were performed on tailings with different degrees of oxidation in the Shuimuchong tailings reservoir to investigate the influence of the formation of the hard oxidized layer on environmental pollution in the tailings pond. The samples were first subjected to particle-size analysis. The shallow tailings were mainly composed of medium particle; the proportions of coarse particle and fine tailings particles were equal; and the proportions of clay and silt were less than those of the other size fractions. Mineralogical analysis showed that pyrrhotite and pyrite were replaced by residual structures in the oxide layer. The secondary minerals goethite, hematite and jarosite were attached to the edges and fractures of sulfide minerals. The samples were geochemically analyzed to determine the total concentrations of 5 elements, the pH and the major anions. The maximum SO42− concentrations of 33,970 and 32,749 mg/kg were observed at a depth of 40 cm in profiles 1 and 2, respectively. Metal sulfide mineral oxidation in the tailings lowered the pH of the materials to values less than 4. The concentration of HCO3− (122–635 mg/kg) in the tailings samples was very low, and the concentration of CO32− was zero. As (53.2–133.7 mg/kg), Pb (24.2–307.5 mg/kg) and Hg (0.03–0.06 mg/kg) were concentrated in the highly oxidized layer at the surface; the Cd content (0.23–10.5 mg/kg) increased with decreasing oxidation degree of the tailings; and the Cr content (38.0–54.9 mg/kg) fluctuated around a certain value.

He-Ar Isotopes and Trace Gas Compositions of Fluid Inclusions in Massive Sulphides from the Yushui Copper-Polymetallic Deposit, South China: Metallogenic Implications

The Yushui ore deposit, located in the middle section of the Yong’an-Meixian Hercynian depression, is a medium-sized Cu-polymetallic massive sulphide deposit in Eastern Guangdong Province, South China. This deposit is characterized by unusually high copper grade (up to 50–60 wt. % Cu). Other metallic elements, such as lead, zinc and silver, are also economically important in the Yushui ore bodies. The aim of this study was to apply N2–Ar–He systematics, together with organic gases (light-hydrocarbon tracers), to constrain the origin and evolution of ore-forming fluids. The helium-argon isotopes and trace gas compositions of fluid inclusions trapped within metal sulphide minerals were measured for a number of bonanza ores from the Yushui deposit. The noble gas concentrations in the studied samples vary over one to two orders of magnitude (4He: 2.27–160.00 × 10−5 cm3 STP g−1; 3He: 0.53–34.88 × 10−12 cm3 STP g−1; 40Ar: 6.28–37.82 × 10−7 cm3 STP g−1; 36Ar: 1.25–10.40 × 10−9 cm3 STP g−1). Our data show a narrow range of 3He/4He ratios from 0.006 to 0.056 Ra (~0.026 Ra on average, n = 8), which are considerably lower than the modern atmospheric end-member value; whereas the 40Ar/36Ar ratios (ranging from 333.76 to 501.68, with an average of 397.53) are significantly greater than that of air-saturated water. Most of the bornite samples have somewhat higher 3He/4He ratios of trapped fluids when compared to chalcopyrite. Overall, these He-Ar results are well within the range of crustal reservoir, thus implying a predominantly crustal source (originated from Caledonian basement) for ore-forming solutions, with little contribution from mantle-derived fluids. Analysis of the N2–Ar–He composition in Cu-rich sulphides indicates that the Yushui ore-forming fluids were probably derived from formation water (or basinal hot brines). Moreover, organic gas species identified in sulphide-hosted fluid inclusions are mainly composed of C1–C4 alkanes, while the concentrations of unsaturated olefins and aromatic hydrocarbons are very low. In particular, most chalcopyrite samples with relatively low 3He/4He ratios (0.006–0.016 Ra) and 40Ar*/4He values (0.0002–0.0012) are generally characterized by very high CO2/CH4 ratios (~60–102). All these suggest that main-stage Cu-Ag metallogenic processes might have not been affected by high-temperature magmatic activities or superimposed by strong metamorphic overprinting, although some chalcopyrite-rich ores appear to be influenced by later stage hydrothermal processes. In summary, neither magmatic input nor convecting seawater has played an important role in the formation of Yushui copper-polymetallic deposit. The massive sulphide ore bodies were products of water–rock interaction between metal-bearing basinal brines and the host sedimentary strata.

The mineralogy and mineral associations of platinum-group elements and precious metals in the Aurora Cu-Ni-Au-PGE deposit, Northern Limb, Bushveld Complex

Aurora is a platinum-group element (PGE) prospect hosted in the Northern Limb of the Bushveld Complex, South Africa. It is one of only three deposits discovered in the Northern Limb so far to be hosted in the melanocratic-leucocratic gabbroic cumulates of the Main Zone of the Rustenberg Layered Suite (Aurora, Moorddrift and Waterberg T Zone deposits), rather than in predominantly ultramafic rocks (e.g. Platreef). The host cumulates at Aurora have been divided into three principal units and they intrude the dolomites of the lower Transvaal Supergroup. Base metal sulphide (BMS) mineralisation with PGE is present in the leucogabbronorites and gabbronorites of Unit 2, and in coarse grained gabbronorite veins which intrude the peridotites of Unit 1. These veins contain up to 50% interstitial pyrrhotite-pentlandite-chalcopyrite ± pyrite. Unit 2 contains 1–3% pentlandite-pyrrhotite-chalcopyrite assemblages, and 1–5% chalcopyrite ± pyrite/pyrrhotite associated with hydrothermal alteration. The PGE content of Aurora however is predominantly controlled by the presence of platinum-group minerals (PGM), not BMS. LA-ICP-MS analysis of sulphides shows the BMS in Aurora have lower PGE concentrations than other Bushveld magmatic sulphides, with pentlandite carrying much lower concentrations of Pd (average 23 ppm) than the Platreef or the Merensky Reef. SEM-EDS analysis of 26 sections characterised 995 platinum-group minerals (PGM) and precious metal-bearing minerals (PMM), with a total area of 27850 μm2 and an average size of 28.2 μm2. Of the PGM and PMM identified in Aurora 85% (by area) are Pd-Te-Bi minerals, with 6% Pd-Te minerals, 4% electrum and 3% Ag-Te minerals, along with minor Pd-Bi, Pd-As, Pt-Te-Bi, Pt-As and Pt-S minerals that collectively comprise 2% of total area. Only 25% of the PGM and PMM in Aurora are BMS hosted, with the rest hosted in silicates. Of the total PGM and PMM area 22% are hosted in alteration-silicates (quartz, chlorite or actinolite) in an alteration halo around sulphides. Unusually, 52% of the PGM and PMM are spatially removed from BMS, instead hosted in alteration silicates and within cracks in primary silicates away from any BMS. This indicates a multi-stage ore genesis model, with hydrothermal remobilisation of PGE important for ore formation. The style and host rocks for mineralisation in the Aurora deposit are fundamentally different from other deposits in the Northern Limb of the Bushveld hosted in ultramafic rocks, such as the Platreef, GNPA member deposits and the F zone of the Waterberg deposit, all of which contain a greater diversity of PGM and BMS with higher precious metal contents. The mineralisation most similar to Aurora is the T Zone of the Waterberg deposit, located to the north of Aurora, which been suggested to be an along-strike equivalent of the Aurora Main Zone mineralisation. However, despite strong similarities in PGM mineralogy and S isotope signatures there are significant differences in BMS mineralisation and host lithology meaning it is unlikely they are directly linked stratigraphically. At present it seems more likely that Aurora and the Waterberg T Zone reflect similar fluid-influenced processes operating in different parts of the Main Zone, perhaps at different times and in different structural basins, rather than a continuous mineralised zone along strike.

Mineralization of the Zechstein Lower Anhydrite in the Fore-Sudetic Monocline

The paper presents the characteristics of ore mineralization of the Lower Anhydrite in the Fore-Sudetic Monocline. Both reduced and oxidized (Rote Fäule) rocks have been investigated. Reduced anhydrites are characterized by significant variability of metal concentrations and sulphide minerals. The most intensely mineralized anhydrites occur above the oxidized bottom part of the Lower Anhydrite. Mineralization in this part is dominated by copper sulphides (chalcocite, digenite, covellite, bornite and chalcopyrite) which are accompanied by galena and sphalerite. Further away from the oxidized zone, zinc and lead sulphides predominate over copper sulphides, and pyrite mineralization is also observed. Complex intergrowths and replacement textures of sulphides, as well as intergrowths of the ore minerals with sulphates and carbonates are considered to have formed after lithification of the enclosing sediments, and indicate that the original associations of sulphides were overprinted by superimposed later mineralization. Oxidized anhydrites generally have no significant concentrations of metals like Cu, Pb and Zn. The relict mineralization there is represented by remnants of tiny grains of copper sulphides (mainly covellite, digenite and chalcocite) and pyrite, profoundly altered as a result of their partial replacement by hematite. This mineralization present in the oxidized anhydrites indicates that hematite emplacement overlapped deposition of the original sulphides and extended oxidation up into the Lower Anhydrite. Position of the reduced and oxidized areas of anhydrites enriched in metals indicates centres of the most intense activity of the ascending mineralizing fluids.

He–Ar–S Isotopic Compositions of Polymetallic Sulphides from Hydrothermal Vent Fields along the Ultraslow-Spreading Southwest Indian Ridge and Their Geological Implications

Noble gases have become a powerful tool to constrain the origin and evolution of ore-forming fluids in seafloor hydrothermal systems. The aim of this study was to apply these tracers to understand the genesis of newly discovered polymetallic sulphide deposits along the ultraslow-spreading Southwest Indian Ridge (SWIR). The helium, argon, and sulphur isotope compositions of metal sulphide minerals were measured for a number of active/inactive vent fields in the Indian Ocean. The helium concentrations and isotopic ratios in these ore samples are variable (4He: 0.09–2.42 × 10−8 cm3STP∙g−1; 3He: 0.06–3.28 × 10−13 cm3STP∙g−1; 3He/4He: 1.12–9.67 Ra) and generally greater than the modern atmosphere, but significantly lower than those in massive sulphides from the fast-spreading East Pacific Rise (EPR), especially for three Cu–Fe-rich samples from the ultramafic-hosted Tianzuo and Kairei vent fields. On the contrary, most of the SWIR sulphide deposits have somewhat higher 40Ar/36Ar ratios of trapped fluids (ranging from 290.6 to 303.4) when compared to the EPR ore samples. Moreover, the majority of sulphide minerals from the Indian Ocean have much higher δ34S values (3.0‰–9.8‰, ~5.9 on average, n = 49) than other basaltic-hosted active hydrothermal systems on the EPR. Overall, these He–Ar–S results are well within the range of seafloor massive sulphide deposits at global sediment-starved mid-ocean ridges (MORs), lying between those of air-saturated water (ASW) and mid-ocean ridge basalt (MORB) end members. Therefore, our study suggests that the helium was derived mainly from the MORB mantle by degassing during the high-temperature stage of hydrothermal activity, as well as from a mixture of vent fluids with variable amounts of ambient seawater during either earlier or late-stage low-temperature hydrothermal episodes, whereas the argon in ore-forming fluids trapped within sulphide minerals was predominantly derived from deep-sea water. Additionally, relatively high δ34S values exhibit a great estimated proportion (up to nearly 40%) of seawater-derived components. In summary, sub-seafloor extensive fluid circulation, pervasive low-temperature alteration, shallow seawater entrainment, and mixing processes, may make a larger contribution to the SWIR hydrothermal ore-forming systems, compared to fast-spreading centres.

Chemical Diversity of Metal Sulfide Minerals and Its Implications for the Origin of Life.

Prebiotic organic synthesis catalyzed by Earth-abundant metal sulfides is a key process for understanding the evolution of biochemistry from inorganic molecules, yet the catalytic functions of sulfides have remained poorly explored in the context of the origin of life. Past studies on prebiotic chemistry have mostly focused on a few types of metal sulfide catalysts, such as FeS or NiS, which form limited types of products with inferior activity and selectivity. To explore the potential of metal sulfides on catalyzing prebiotic chemical reactions, here, the chemical diversity (variations in chemical composition and phase structure) of 304 natural metal sulfide minerals in a mineralogy database was surveyed. Approaches to rationally predict the catalytic functions of metal sulfides are discussed based on advanced theories and analytical tools of electrocatalysis such as proton-coupled electron transfer, structural comparisons between enzymes and minerals, and in situ spectroscopy. To this end, we introduce a model of geoelectrochemistry driven prebiotic synthesis for chemical evolution, as it helps us to predict kinetics and selectivity of targeted prebiotic chemistry under “chemically messy conditions”. We expect that combining the data-mining of mineral databases with experimental methods, theories, and machine-learning approaches developed in the field of electrocatalysis will facilitate the prediction and verification of catalytic performance under a wide range of pH and Eh conditions, and will aid in the rational screening of mineral catalysts involved in the origin of life.

Syn-tectonic sulphide remobilization and trace element redistribution at the Falun pyritic Zn-Pb-Cu-(Au-Ag) sulphide deposit, Bergslagen, Sweden

Mineralization types at the Palaeoproterozoic Falun base metal sulphide deposit are predominantly pyritic Zn-Pb-Cu-rich massive sulphide mineralization, disseminated to semi-massive Cu-Au mineralization, auriferous quartz veins, and mineralized shear zones of talc-chlorite-dominated schist. The massive and disseminated to semi-massive sulphide mineralization types were subject to polyphase ductile deformation (D1 and D2) and metamorphism under low-P, lower-amphibolite facies conditions, which led to the development of ore textures and paragenetic relationships indicating both mechanical and chemical remobilization of sulphides. In the massive sulphide mineralization, rare inclusion-rich pyrite occurs as relic cores inside inclusion-poor metamorphosed pyrite. Imaging and spot analysis using multielement laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) reveal that inclusion-poor pyrite was depleted in trace elements, which were originally present as non-stoichiometric lattice substitutions or in mineral inclusions. The inclusion-rich pyrite was shielded from depletion and, at least partly, retained its initially higher trace element concentrations, including Au.Gold is also associated with chalcopyrite in the disseminated to semi-massive Cu-Au mineralization and in the system of auriferous quartz veins hosted therein, the latter being also affected by the D2 ductile strain. It is inferred that emplacement of the vein system took place after the peak of metamorphism, which occurred between D1 and D2, but prior to and possibly even shortly after completion of the D2 deformational event. Similarities in trace element signatures in chalcopyrite are compatible with the interpretation that the quartz veins formed by local chemical remobilization of components from the Cu-Au mineralization. Transport of liberated Au from pyrite during grain growth in the massive sulphide mineralization may have upgraded the Au endowment in the quartz veins, leading to the additional formation of native gold in the veins. A strong correspondence between elements liberated from pyrite (e.g. Pb, Bi, Se and Au) and those forming discrete and characteristic mineral phases in the quartz veins (Pb-Bi sulphosalts, native gold) supports this hypothesis.Trace element signatures for the main sulphide minerals pyrite, chalcopyrite, sphalerite and galena are similar to previously published data from other metamorphosed massive sulphide deposits. The association of the Falun mineralization with elevated Bi is reflected by its occurrence in sulphide minerals (e.g. galena) and in abundant mineral inclusions of Pb-Bi sulphosalts (e.g. weibullite), especially in the disseminated to semi-massive Cu-Au mineralization. Elevated Sn concentrations in the lattice and/or as cassiterite inclusions in chalcopyrite, sphalerite and galena are compatible with a hot, acidic and reducing fluid during formation of the syn-volcanic, base metal sulphide mineralization and associated host-rock alteration.

The galvanic interaction between chalcopyrite and pyrite in the presence of lignosulfonate-based biopolymers and its effects on flotation performance

Pyrite, a gangue mineral, is commonly associated with valuable base metal sulfide minerals and the separation of pyrite from these valuable sulfide minerals by flotation is difficult. In this study, a type of biopolymers, modified from lignosulfonates, was used to reject pyrite in chalcopyrite flotation based on the previous investigations. It was found that these biopolymers selectively depressed pyrite flotation with little effect on chalcopyrite flotation. The presence of pyrite decreased the depression effect of biopolymers on chalcopyrite flotation due to the preferential adsorption of biopolymers on copper-activated pyrite as revealed by the adsorption isotherms and ToF-SIMS (Time-of-Flight Secondary Ion Mass Spectrometry) analyses. The presence of chalcopyrite increased the depression effect of biopolymers on the flotation of copper-activated pyrite due to enhanced oxidation of the copper activation product, Cu(I)S, on pyrite as a result of the galvanic interaction among Cu(I)S, pyrite and chalcopyrite.

Geochemical vectors for stratiform Zn-Pb-Ag sulfide and associated dolomite-hosted Cu mineralization at Zinkgruvan, Bergslagen, Sweden

The Zinkgruvan deposit is the largest stratiform Zn-Pb-Ag mineralization in Sweden. The most recent genetic model attributes ore formation to the discharge of oxidized, near-neutral pH, metalliferous brines into a reduced basin, forming laterally extensive, stratiform sulfide mineralization on the seafloor. It has a known strike extent of 5 km and is underlain by a regionally extensive zone of K-altered metavolcanic rock and dolomitic marble, the latter hosting Cu-(Co-Ni) replacement mineralization near the inferred hydrothermal vent to the stratiform sulfides. The deposit is stratigraphically overlain by migmatized, pyrrhotite- and graphite-rich pelite that is in turn overlain by a banded almandine-biotite-quartz-ferrosilite-bearing unit at the base of a regionally extensive metasedimentary succession. These laterally continuous units are interpreted as metamorphosed organic-rich sulfidic mudstone and silicate-dominated Fe formation, respectively.The favorable stratigraphic interval contains anomalously high Zn, Pb, Ag, Cu, K2O/(K2O + Na2O), Mn, Co, Tl, Ba and B relative to adjacent metatuffite. However, only Zn, Pb, Ag, K2O/(K2O + Na2O) and Mn are significantly enriched relative to adjacent strata beyond the known lateral extent of the ore. Elevated copper, Co and Tl only occur in the vent-proximal part of the deposit, whereas anomalous enrichments of Ba and B are sporadic and occur mainly in the stratigraphic footwall. Many elements such as Si, Fe, Mg, Ca and Cs are of limited use in vectoring due to low enrichment factors relative to inferred background compositions and/or strong lithological controls on their distribution.Although ore metal (Zn, Pb and Ag) enrichments are the best quantitative and qualitative guides to ore, K, Mn and Co enrichments also provide corroborative support. The most useful elements for vectoring have been synthesized into exploration indices. The Modified Sedex Metal Index (MSMI; Zn + 3Pb + 100Ag) is a vector towards stratiform Zn-Pb-Ag mineralization, whereas MSMI2 [Zn + 3Pb + 10(Cu + Co)] also allows targeting of proximal Cu mineralization.The banded iron formation and the pyrrhotite- and graphite-rich pelite of the stratigraphic hanging wall are consistently enriched in base metals (e.g. 500–1000 ppm Zn), total S and Mn throughout the entire Zinkgruvan area. However, these units are not known to grade laterally along strata into economic base metal sulfide mineralization, and they are not obviously products of the same hydrothermal system which formed the stratiform Zn-Pb-Ag deposit.In a vent-distal setting, the somewhat spurious metal anomalies of the hanging wall units can be difficult to distinguish from those of the favorable interval. The favorable stratigraphic interval can, however, be recognized by also taking into account that positive Zn anomalies are mainly coincident with positive anomalies in both K and Mn only in the favorable interval. Furthermore, samples from the favorable interval generally have Co/Ni > 1 and display a positive Co/Ni vs. Zn trend, whereas samples of the pyrrhotite- and graphite-rich pelite have Co/Ni < 1 and define a negative Co/Ni vs. Zn trend. Thus, the index (Co/Ni)*Zn allows easy detection of weak Zn anomalies associated with the stratiform Zn-Pb-Ag mineralization.

Investigating the interaction of thiol collectors and collector mixtures with sulphide minerals using thermochemistry and microflotation

In order to recover minerals by flotation, the sub-processes of collector adsorption onto the valuable minerals followed by bubble-particle attachment should occur efficiently. This paper investigates both of these sub-processes for various thiol collectors and their mixtures onto base metal sulfide minerals. The aim of the work was to investigate whether there is a correlation between the strength of the collector interaction with the mineral and the subsequent bubble-particle attachment. The collector-mineral interaction was measured experimentally using an isothermal titration calorimeter in order to determine the molar enthalpy of adsorption for each collector-mineral system. The bubble-particle attachment was measured using a microflotation device which essentially determines the hydrophobicity of the mineral. Sodium ethyl xanthate (SEX) and sodium diethyl dithiocarbamate (diethyl-DTC) and mixtures thereof were used as collectors with either single minerals or binary mixtures of pyrite and chalcopyrite, respectively. The adsorption enthalpies of the collectors were interpreted with reference to the chemical structure of the collector molecule and showed that the greater the positive inductive effect of the collector, which may be qualitatively related to their pKa values, the greater their affinity for the mineral surface. When mixtures of collectors were used there was clear evidence of synergistic effects in enhanced enthalpies of interaction between collectors and the mineral surface and in increased microflotation recoveries. When mixtures of pyrite and chalcopyrite were used the flotation recovery and enthalpy of adsorption of SEX onto the individual pyrite particles in the mixture also increased substantially compared to the case of pyrite alone. Mechanisms are proposed to interpret these observations.

Interactions of Oxygen and Water Molecules with Pyrite Surface: A New Insight.

Pyrite is the most common sulfide in nature, and it is well-known for its roles in acid mine drainage, flotation separation of useful metal (Cu, Pb, Zn, and Mo) sulfide minerals, optoelectronic and photovoltaic application, pneumoconiosis, and even in the origin of life. However, the detailed oxidation behaviors of pyrite are still unclear and not well-understood. New oxidation pathways by O2 on the pyrite (100) surface have been found in this work for the first time using density functional theory simulation; that is, besides Fe sites, S sites are also possible oxidation sites in the initial oxidation state of pyrite, where easier and stronger oxidation may occur. This is the first time to confirm the other researchers' conjecture on the direct oxidation of S sites, which explains the isotopic composition experiments that a minor amount of O2 is permanently incorporated into SO42- during pyrite oxidation (O in SO42- is mainly derived from water). We constructed various H2O-O2 coadsorption models on the pyrite surface by considering the adsorption sequence of H2O and O2. It is found that the H2O molecule undergoes step-wise dissociation in the presence of the O2 molecule. Hydroxyl radical •OH is the reactive oxygen species during H2O dissociation. Cyclic voltammetric measurements confirm the presence of •OH. In addition, H2O2 may also be formed on the surface in terms of H2O-then-O2 sequence adsorption.

Potential Processing Routes for Recovery of Platinum Group Metals from Southern African Oxidized PGM Ores: A Review

The beneficiation of platinum group metals (PGMs) from pristine (unweathered) sulfide ores has conventionally been conducted through froth flotation, which typically achieves platinum recoveries of over 85%. The achieved successes of PGM concentration by flotation from the pristine sulfide ores are largely due to the occurrence of PGMs in close association with base metal sulfide minerals like chalcopyrite, pentlantite, and pyrrhotite which are easily floatable. However, the fast depletion of sulfide PGM-bearing minerals has triggered interest in exploring the recovery of the PGMs from near-surface oxidized PGM ores which have proven to be more difficult to process by conventional means as an alternative source to sustain production of PGMs. Earlier attempts to process the oxidized PGM ores by conventional flotation methods achieved poor recoveries (typically less than 50%). The resource estimates of oxidized PGM ores which are either unmined, mined, and stockpiled or discarded as overburden waste in South Africa and Zimbabwe are over 500 million tonnes. The economic benefits that could be realized in the event of an alternative and effective processing technique being developed would be immense. This paper reviews and discusses different research efforts that have been made to improve PGM recoveries from oxidized ores, and their merits and demerits.

Fluid origin and evolution of Cu-Pb-Zn mineralization in rhyolite breccias in the Lón area, southeastern Iceland

Iceland, the landward extension of the Mid-Atlantic Ridge, hosts dilute, predominantly meteoric hydrothermal systems that rarely form base metal (Cu-Pb-Zn) mineralization. One occurrence of Cu-Pb-Zn mineralization in intrusive rhyolitic breccias is in the Lón area of southeastern Iceland. Petrographic, electron-probe, fluid inclusion, stable isotope, and U-Pb zircon dating analyses on samples from Lón constrain the conditions and timing of sulfide mineral formation.Observations of outcrops and hand samples suggest that hydrothermal fluids precipitated chalcopyrite, sphalerite, galena, quartz, epidote, chlorite and calcite in rhyolitic breccia pipes and adjacent basalt flows. The mean salinity of liquid-dominated, multi-phase fluid inclusions in quartz coeval with chalcopyrite inclusions in quartz is 4.2wt% NaCl, and the mean trapping temperature is 332°C, which is consistent with the results of δ34S geothermometry of coexisting galena and chalcopyrite. Calculated δ18O and δD values of fluids in equilibrium with epidote coeval with chalcopyrite range from −5.2 to −2.7±0.1‰ and from −35.9 to −27.7±0.1‰, respectively. The δ18O values of fluids in equilibrium with quartz coeval with chalcopyrite are up to 5‰ larger than those of fluids in equilibrium with late stage quartz precipitated after chalcopyrite. The U-Pb crystallization age of magmatic zircons in the rhyolite breccia is 2.6±0.1Ma, significantly younger than the proximal 3.7 to 7.3Ma silicic intrusions of southeastern Iceland.Our results indicate that early-stage, mineralizing fluids derived from a mixture of meteoric water, seawater, and a minor magmatic water component exsolved from an evolved anatexis-produced melt. Late-stage fluids were derived exclusively from meteoric waters. Although anatectic dehydration melting of altered basalt produced millions of years of felsic magmatism in southeastern Iceland, only hydrothermal fluids that derived from a mixture of meteoric water, seawater, and brine exsolved from a highly evolved melt concentrated base metals in significant quantity to produce base metal sulfide mineralization.

EPITHERMAL MANGANESE MINERALIZATION, KIMOLOS ISLAND, SOUTH AEGEAN VOLCANIC ARC, GREECE

Manganese mineralization is hosted by a marine monomictic, lithic volcaniclastic breccia, possibly an andesitic in situ hyaloclastite, and shallow-marine or subaerial epiclastic conglomerates, in the Korakies area, NE Kimolos, active south Aegean volcanic arc. Old mine workings (in the form of rubble, adit and shaft), and abandoned rail and ship loading facilities, exist in the area. Mineralization occurs as a quartz/chalcedony vein system filling extensional NNE-SSW–trending faults and fractures, of Pliocene age. Maximum vein width reaches 5 m; length may extend to 250 m. The ore shares strong textural analogies with volcanic-hosted epithermal-style deposits, i.e. crustiform banding, vugs, hydrothermal breccias, cockade and comb textures. Vein wall rocks are hydrothermally altered to quartz-adularia±illite, chlorite and barite. Pyrolusite, hollandite, cryptomelane, and coronadite are the main ore minerals, with quartz, chalcedony, jasper and barite gangue. Ore samples contain up to 25.8 % MnO2, 14.7 % FeOTOT, 2860 ppm Zn, 1132 ppm Pb and 136 ppm Cu; Mn and Zn show mutual positive correlation (r2=0.61). Trace element enrichment (i.e. Zn, Pb, and Cu) may suggest a proximal base metal sulfide mineralization. Concentrations of 4.3 % Na, 0.09 % Mg and barite presence may suggest genetic involvement of sea water. The mineralization studied is similar to volcanic-hosted low-sulfidation epithermal ore deposits deposited from neutral pH fluids. This is a rare example of a vein-type epithermal-style hydrothermal manganese deposit formed in a marine environment.

NEW METALLOGENETIC CONCEPTS AND SUBSTAINABILITY PERSPECTIVES FO NON-ENERGY METALLIC MINERALS IN CENTRAL MACEDONIA, GREECE

Greece’s geology favours a potent and dynamic use of mineral resources, which became a major incentive of the country’s mining business, and economic and social growth. Among the Non-Energy Metallic Minerals (NEMM) commodities, base and precious metals, in particular copper and gold, is becoming an increasingly important and rapidly growing target of the mining industry. In the region of central Macedonia, where most of their deposits are hosted, the NEMM occur in a wide range of genetic types related to Alpine orogenic and subduction related ore forming processes extending from Mesozoic to Cenozoic times, and culminating during the Tertiary (Arvanitidis and Amov, 2006). From the global metallogenetic point of view the post-Alpine Tertiary geodynamic systems in SE Europe are potential in producing high-grade ore deposits of base and precious metal sulphide minerals. The classification of NEMM mineralizations to specific genetic types, along with the geological knowledge available, is contributing (a) to more efficient exploration and prospect evaluation (b) to safer assessment of ore potential and economic perspectives (c) to rational management of resource production, and (d) in applying sustainable development practices.

A laser ablation inductively coupled plasma mass spectrometry study of the distribution of chalcophile elements among sulfide phases in sedimentary and magmatic rocks of the Duluth Complex, Minnesota, USA

Nickel-copper sulfide deposits occur in the basal unit of the Partridge River Intrusion, Duluth Complex (Minnesota, USA). Many lines of evidence suggest that these sulfides are formed after assimilation of the proterozoic S-rich black shales, known as the Bedded Pyrrhotite Unit. In addition to S, black shales are enriched in Te, As, Bi, Sb and Sn (TABS) and the basaltic magma of the intrusion is contaminated by the partial melt of the black shales. The TABS are chalcophile and together with the platinum-group elements, Ni and Cu partitioned into the magmatic sulfide liquid that segregated from the Duluth magma. The TABS are important for the formation of platinum-group minerals (PGM) thus their role during crystallization of the base metal sulfide minerals could affect the distribution of the PGE. However, the concentrations of TABS in magmatic Ni-Cu-PGE deposits and their distribution among base metal sulfide minerals are poorly documented. In order to investigate whether the base metal sulfide minerals host TABS in magmatic Ni-Cu-PGE deposits, a petrographic and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) study has been carried out on base metal sulfide and silicate phases of the Partridge River Intrusion, Duluth Complex.Petrographic observations showed that the proportions of the base metal sulfide minerals vary with rock type. The sulfide assemblage of the least metamorphosed Bedded Pyrrhotite Unit from outside the contact metamorphic aureole consists of pyrite with minor pyrrhotite plus chalcopyrite (<5%), whereas within the contact aureole the sulfide assemblage of the Bedded Pyrrhotite Unit rocks consists dominantly of pyrrhotite (>95%) with small amount of chalcopyrite (<2%). The sulfide mineral assemblage in the xenoliths of the Bedded Pyrrhotite Unit and in the mafic rocks of the basal unit contains two additional sulfides, pentlandite and cubanite.Our LA-ICP-MS study shows that sulfides of the Bedded Pyrrhotite Unit are rich in TABS; consistent with these S-rich black shales being the source of TABS that contaminated the mafic magma. Most of the TABS are associated with sulfides and platinum-group minerals in the rocks of the Bedded Pyrrhotite Unit from the contact aureole, the Bedded Pyrrhotite Unit xenoliths and the mafic rocks of the Duluth Complex. In addition to these phases the laser maps show that silicate phases, i.e., orthopyroxene and plagioclase contain Sn and Pb respectively. In contrast, in the least metamorphosed samples of the Bedded Pyrrhotite Unit from outside the contact aureole although the pyrite contains some TABS mass balance calculations indicates that most the TABS are contained in other phases. In these rocks, galena hosts significant amounts of Te, Bi, Sb, Sn and Ag and few very small grains of Sb-rich phases were also observed. The host phases for As were not established but possibly organic compounds may have contributed.

Scale-fragment formation impairing geothermal energy production: interacting H2S corrosion and CaCO3 crystal growth

BackgroundMineral precipitates (scaling) from deep saline thermal waters often constitute a major problem during geothermal energy production. The occurrence of scale-fragments accumulating and clogging pipes, filters, and heat exchangers is of particular concern regarding an efficient energy extraction.MethodsCarbonate scale-fragments from different sections of two geothermal power plants were collected and studied in a high-resolution scaling forensic approach comprising of microstructural characterization, elemental mapping, and stable carbon and oxygen isotope transects. The solid-phase analyses were evaluated in the context of natural environmental and technical (man-made) production conditions.Results and discussionOur results indicate an interaction of metal sulfide mineral layers mainly from H2S corrosion of the steel pipes and CaCO3 nucleation and crystal growth. A conceptual model of scale-fragment development addresses the relevance of two key interfaces: 1) the corrosion layer between the steel substrate and calcite scale and 2) the scale surface versus thermal fluid flow. The corrosion products constitute an attractive crystallization substrate of brittle and mechanically weak consistency. A rough carbonate scale surface tends to induce (micro) turbulences and increased flow resistance (frictional forces). These factors promote partial exfoliation, scale-fragment mobilization, and rapid clogging. This investigation highlights the potential of detailed petrographic and geochemical analyses of mineral precipitates for evaluating favorable versus unfavorable processes in geotechnical environmental settings.