Sulfide Minerals Research Articles

Influence of Mineralogy and Mineralogy Approach to Optimize Processing: A Case Study of Tin–Copper Polymetallic Ore

Tin-Copper polymetallic ore is a type of typical ore that cassiterite is closely associated with sulfide minerals. In mineral processing of tin–copper polymetallic ore, flotation is generally used to recover valuable sulfide minerals, while gravity separation is used to recover cassiterite. A mine in Yunnan, China, uses the traditional “flotation–gravity separation” process to recover copper and tin but faces several problems during processing, such as an insufficient copper grade in Cu concentrate, a much higher grade of As in S concentrate, and a grade of S in Sn concentrate that exceeds the standard. A process mineralogy study was conducted, with a focus on Cu–S mixed concentrate, S concentrate, and Sn rough concentrate. It was determined that the main cause of these problems is not the liberation or size distribution of valuable minerals but the superstructure of pyrrhotite, which represents one of the most abundant minerals in the products. Based on EMPA, SEM-EDS, and XRD data, both monoclinic pyrrhotite and hexagonal pyrrhotite occurred in all samples. The abundance of different superstructures of pyrrhotite in one sample was determined by means of particle extraction and area calculation from microscopic images, and the distribution characteristics of monoclinic pyrrhotite and hexagonal pyrrhotite in the whole process were clarified. This process mineralogy study indicates that the strong magnetic hexagonal pyrrhotite mainly affects the copper recovery during flotation, and the hexagonal pyrrhotite mainly affects the recovery of cassiterite during gravity separation. Strong magnetic monoclinic pyrrhotite and weak magnetic hexagonal pyrrhotite should be fully considered in the optimization of mineral processing, and the magnetic separation of pyrrhotite should be adopted to optimize the overall environment of copper flotation and tin gravity separation.

Copper sulfide mineral performs non-enzymatic anaerobic ammonium oxidation through a hydrazine intermediate.

Anaerobic ammonium oxidation (anammox)-the biological process that activates ammonium with nitrite-is responsible for a significant fraction of N2 production in marine environments. Despite decades of biochemical research, however, no synthetic models capable of anammox have been identified. Here we report that a copper sulfide mineral replicates the entire biological anammox pathway catalysed by three metalloenzymes. We identified a copper-nitrosonium {CuNO}10 complex, formed by nitrite reduction, as the oxidant for ammonium oxidation that leads to heterolytic N-N bond formation from nitrite and ammonium. Similar to the biological process, N2 production was mediated by the highly reactive intermediate hydrazine, one of the most potent reductants in nature. We also found another pathway involving N-N bond heterocoupling for the formation of hybrid N2O, a potent greenhouse gas with a unique isotope composition. Our study represents a rare example of non-enzymatic anammox reaction that interconnects six redox states in the abiotic nitrogen cycle.

Hollow drop bubbles: A preliminary study of simplified prototype for improving copper(II) extraction with ACORGA® M5640 using coated bubble swarm

There are two well-defined processes for the types of copper ores. One for the processing of copper sulfides and another for the processing of the copper oxides. There are similarities between the two, particularly in the preparation stage of the run of mine (ROM) such as the crushing. However, significant differences exist in how to concentrate the elements of interest. Flotation is the most used concentration process to separate copper sulfide minerals from other minerals using air bubbles. For oxides, after the dissolution of copper, the solvent extraction (SX) process is the preferred path using two immiscible liquids to separate the copper.A line of investigation for solvent extraction is the use of a bubble coated with solvent to extract the metal of interest from the aqueous solution, some devices have been built and tested for this purpose using different principles to generate a coated bubble swarm. However, those equipments have been tested on laboratory and have not been scaled up to an industry level.The Hollow Drop (HD) concept was born from the idea of building a device to generate coated bubbles in a continuous swarm that could be scalable to an industry level. In this paper two columns were built and operated: a proof-of-concept column and a scale-up attempt for the extraction of Cu(II) fom an aqueous solution of 2.5 g L−1 using ACORGA® M5640 (25% v/v) in the Kerosene.The results show that we could generate a bubble swarm and conduct the solvent extraction process at a 97% recovery using our proposed coated bubble generator. However, in our scaled prototype test only a 70% recovery was achieved, which shows that our column is working but the scaling-up needs more investigation regarding the dimensions and flows of the process.

Osmotic response in Leptospirillum ferriphilum isolated from an industrial copper bioleaching environment to sulfate

Iron and sulfur-oxidizing microorganisms play important roles in several natural and industrial processes. Leptospirillum (L.) ferriphilum, is an iron-oxidizing microorganism with a remarkable adaptability to thrive in extreme acidic environments, including heap bioleaching processes, acid mine drainage (AMD) and natural acidic water. A strain of L. ferriphilum (IESL25) was isolated from an industrial bioleaching process in northern Chile. This strain was challenged to grow at increasing concentrations of sulfate in order to assess changes in protein expression profiles, cells shape and to determine potential compatible solute molecules. The results unveiled changes in three proteins: succinyl CoA (SCoA) synthetase, isocitrate dehydrogenase (IDH) and aspartate semialdehyde dehydrogenase (ASD); which were notably overexpressed when the strain grew at elevated concentrations of sulfate. ASD plays a pivotal role in the synthesis of the compatible solute ectoine, which was identified along with hydroxyectoine by using matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF). The relationship between IDH, SCoA, and ectoine production could be due to the TCA cycle, in which both enzymes produce metabolites that can be utilized as precursors or intermediates in the biosynthesis of ectoine. In addition, distinct filamentous cellular morphology in L. ferriphilum IESL25 was observed when growing under sulfate stress conditions. This study highlights a new insight into the possible cellular responses of L. ferriphilum under the presence of high sulfate levels, commonly found in bioleaching of sulfide minerals or AMD environments.

Timing and Evolution of Gold Mineralization in the Maljavr Occurrence (NW Russia), NE Part of the Fennoscandian Shield

Gold occurrence Maljavr is the first Archean conglomerate-hosted gold mineralization found in the Fennoscandian Shield. Gold-mineralized metasomatic rocks form a set of lenses within a 10 m thick linear zone, conformable to the bedding of host conglomerates. The lenses are up to 10 m long and up to 1 m thick and they clearly exhibit three alteration envelopes: the rock in the central part consists of garnet and quartz or garnet-only; biotite, garnet, and quartz make the intermediate biotite–garnet envelope; hornblende, hedenbergite, and quartz are the principal rock-forming minerals in the outer zone of the lenses. All metasomatic rocks contain sulfide mineralization up to 15–20 vol.% and up to 0.6 g/t Au. The main ore mineral is pyrrhotite, and the minor minerals are arsenopyrite, chalcopyrite, pentlandite, löllingite, and troilite. The age of zircon from biotite gneiss in the zone of alteration is 2664 ± 18 Ma, this is considered as the time of formation of lenses of metasomatic rocks. Biotite gneiss-conglomerate and metasomatic rocks were later intruded by tourmaline granite pegmatite 2508 ± 7 Ma. The injection of pegmatite caused re-crystallization of sulfides (mainly arsenopyrite and löllingite) and redistribution of gold. Visible gold in association with Bi minerals native bismuth, ehrigite, maldonite, bismuthinite, joseite-B, and hedleyite was found in inclusions in recrystallized arsenopyrite and löllingite. Au content in the rocks with recrystallized arsenopyrite and löllingite is >1 g/t, up to 30 g/t in hand samples. The 2508 Ma pegmatite is interpreted as synchronous with formation of gold mineralization in its present form. The linkage of gold mineralization with pegmatite and geochemical association Au-As-Se-Te-Bi in the mineralized rocks agree with characteristics of intrusion-related gold deposits worldwide. Biotite gneiss–metaconglomerate, hosting the mineralized altered rocks, was the probable primary source of arsenic and gold for mineralization.

High-Grade REE accumulation in regolith: Insights from supergene alteration of an apatite-rich vein at the Kapunda Cu mine, South Australia

AbstractThe stratiform and vein-hosted Kapunda Cu deposit in South Australia contains a saprolitized hydrothermal vein with 12.37 wt.% total rare earth oxide (TREO). The vein was analyzed by X-ray diffraction, scanning electron microscopy, synchrotron-based X-ray fluorescence microscopy and electron backscatter diffraction to understand the controls that govern high-grade REE accumulation during periods of intense weathering. Petrological assessments indicate the transformation of an apatite-calcite-aluminosilicate-bearing protolith to a supergene assemblage of Fe-oxides, kaolinite and REE-phosphate minerals that include rhabdophane-(Ce), monazite-(Ce) and florencite-(Ce). This transformation was facilitated by progressive acidification of the weathering fluid, which is indicated by: 1) the increasing crystallinity of authigenic Fe-oxides and kaolinite, which led to REE desorption; 2) the textural evolution and increase in grain size of authigenic REE-phosphates from nanoscopic crystallites, to acicular needles, to micro-scale hexagonal prisms; 3) the late dissolution of REE-phosphates; and 4) the replacement of goethite by jarosite, whose sulfate component originated from the oxidation and weathering of proximal sulfide minerals. Alongside the depletion of pH-buffering carbonate minerals that are indicated by the preservation of calcite menisci, this sulfide dissolution also facilitated acid generation. Results illustrate how highly acidic weathering fluids might facilitate either REE mobilization or REE accumulation in regolith. High-grade REE accumulation under acidic supergene conditions is prioritized when the host-rock contains a significant source of depositional ligands (i.e., phosphate in the form of apatite) that can be readily leached during intense weathering. Exploration companies should therefore assay routinely for REEs in any heavily weathered phosphatic rock, due to the observed efficiency of phosphate minerals as geochemical traps for REE accumulation.

Metal mobilization from thawing permafrost to aquatic ecosystems is driving rusting of Arctic streams

Climate change in the Arctic is altering watershed hydrologic processes and biogeochemistry. Here, we present an emergent threat to Arctic watersheds based on observations from 75 streams in Alaska’s Brooks Range that recently turned orange, reflecting increased loading of iron and toxic metals. Using remote sensing, we constrain the timing of stream discoloration to the last 10 years, a period of rapid warming and snowfall, suggesting impairment is likely due to permafrost thaw. Thawing permafrost can foster chemical weathering of minerals, microbial reduction of soil iron, and groundwater transport of metals to streams. Compared to clear reference streams, orange streams have lower pH, higher turbidity, and higher sulfate, iron, and trace metal concentrations, supporting sulfide mineral weathering as a primary mobilization process. Stream discoloration was associated with dramatic declines in macroinvertebrate diversity and fish abundance. These findings have considerable implications for drinking water supplies and subsistence fisheries in rural Alaska.

Selective depression of biodegradable talc depressant sodium carboxymethyl starch on molybdenite flotation with sodium diethyldithiocarbamate

The selective separation of molybdenite and talc is still a challenging problem owing to its excellent inherent hydrophobicity. In this study, sodium carboxymethyl starch was evaluated for the first time as a cost-effective talc depressant to achieve the molybdenite-talc separation with sodium diethyldithiocarbamate, a collector widely used to float sulfide minerals. The single-mineral and multi-mineral flotation tests witness carboxymethyl starch has shown a selective depression on talc and has little effect on molybdenite recovery with sodium diethyldithiocarbamate as a collector, terpineol as a frother and pH = 8 ± 0.5 (at an industrially relevant pH). Furthermore, experimental comparison of FTIR, equilibrium adsorption and XPS analysis demonstrate that the adsorption of sodium carboxymethyl starch on the talc surface can be considered to be irreversible under these conditions, and the higher adsorption density of sodium diethyldithiocarbamate on molybdenite over talc has highlighted the importance of differential adsorption density in the predictions of the efficient separation of molybdenite and talc. The innovative method may be applied efficiently in industrial applications to improve the comprehensive utilization of resources.

In-situ groundwater remediation of contaminant mixture of As(III), Cr(VI), and sulfanilamide via electrochemical degradation/transformation using pyrite

Electrochemical advanced oxidation processes (EAOPs) are effective in removing persistent contaminants from groundwater. However, their practical applicability depends significantly on various site-specific characteristics. Therefore, the primary objective of this investigation was to study the feasibility of EAOPs and pyrite, which is a sulfide mineral, to effectively remove the mixture of arsenic (As (III)), chromium (Cr (VI)), and sulfanilamide in groundwater. We conducted a comparison of three systems: (1) EAOP alone, (2) pyrite alone, and (3) a combined EAOP and pyrite system. In EAOP alone, sulfanilamide was effectively oxidized (80%), while the electrochemical transformation of As(III)/Cr(VI) into As(V)/Cr(III) was limited. In just the pyrite system, As(III), Cr(VI), and sulfanilamide were adsorbed onto the surface of pyrite (60%, 20%, and 18%). Neither the EAOP nor the pyrite system alone could effectively treat the contaminants mixture. Nonetheless, the combined system completely removed As(III), Cr(VI), and sulfanilamide by the synergistic reaction. This could be attributed to the formation of green rust, a natural adsorbent mineral produced as a reaction of dissolved iron, generated via electrochemical pyrite oxidation, with the groundwater electrolyte (e.g., CO3 or SO4). This system harmonized the combined approach of EAOP and pyrite to effectively eliminate both organic and inorganic contaminants. Environmental implicationA paper proposed electrochemical oxidation (EO) with pyrite to remove both organic and inorganic contaminants from groundwater. The removal performance of the combined system was evaluated, and the synergistic mechanism was revealed. The combination of EO and pyrite with synergistic removal effectively removed the mixture of both contaminants. This could be attributed by the formation of green-rust by electrochemical activation for pyrite. Compared to the single system of EO and pyrite alone, the combined system with EO and pyrite improved removal performance. Results suggested that the combined system could be used for green groundwater remediation.

Selective depression and adsorption of a novel eco-friendly depressant on the flotation separation of chalcopyrite from carrollite

Carrollite is often associated with chalcopyrite, and their natural floatability is similar, which makes it difficult to separate the two minerals by flotation in industrial production. In this study, the depression behavior and mechanism of flaxseed gum (FG) introduced as carrollite depressant on carrollite and chalcopyrite in PBX flotation system was investigated through micro-flotation, zeta potential, total organic carbon (TOC), fourier transform infrared (FT-IR), and X-ray photoelectron spectroscopy (XPS). The flotation results indicated that FG was a highly effective depressant to separate 92.39 % chalcopyrite from the mixture with carrollite at pH 9.0 with a reagent scheme of 50 mg/L of FG and 8.0 × 10−5 mol/L of PBX. The zeta potential and TOC analysis results demonstrated that both carrollite and chalcopyrite exhibited a favorable affinity to FG, and pre-treated FG significantly hindered the adsorption of PBX on carrollite, while only slightly decreased that on chalcopyrite, resulting in the considerable difference in floatability between carrollite and chalcopyrite. In addition, FT-IR spectra and XPS detection results further confirmed that the affinity of FG towards carrollite superior to PBX might be due to the bidentate coordination of the carboxyl groups in FG with Co sites on carrollite surface, whereas the interaction between its carboxyl groups and Cu sites on both minerals was very weak or did not happen. Therefore, FG was promising in flotation separation of copper-cobalt sulfide minerals as a new friendly efficient depressant.

The behavior of pyrite during in-situ leaching of uranium by CO2 + O2: A case study of the Qianjiadian uranium deposit in the Songliao Basin, northeastern China

Oxidative weathering of pyrite, a widespread iron sulfide mineral, is crucial for the uranium mineralization in sandstone-hosted uranium deposits and the ore utilization leaching under manual intervention. To understand the behavior of pyrite under CO2 + O2 leaching conditions in sandstone-hosted uranium deposits, samples of uranium ore from the mineralized zone of the Qianjiadian IV uranium deposit located in the lower section of the Yaojia Formation were collected for this study. The stirring leaching experiment was carried out through the processes of the pyrite-bearing uranium ore samples thinned before and after the reaction, followed by an optical microscopic study and the TESCAN Integrated Mineral Analyzer analysis, and finally, the thermodynamic simulation by making use of PHREEQC3.0.The results revealed the following: (1) The dissolution particles of pyrite become smaller, which may increase the porosity of the ore layer and the exposure ratio of uranium minerals. And more soluble pyrite with a high free surface will be more competitive with uranium minerals for the consumption of O2. (2) The ion (Fe2+) produced by the dissolution of pyrite will be oxidized to Fe3+ by excess O2 (4 mol), which provides an oxidant for the oxidation of uranium minerals, and the generated SO42- will combine with the Ca2+ released from calcite to form a permanent precipitate of gypsum, which may block pores and cover the uranium ore. (3) Pyrite and calcite will consume O2 and CO2 in the injection system, thus jointly inhibiting the leaching of uranium minerals. After the injection of excessive CO2 and O2, the concentration of Ca2+, SO42-, Fe3+, UO22+, and HCO3– in the system will continue to accumulate, resulting in the secondary precipitation of calcite, co-precipitation of gypsum, iron minerals, colloids, and hexavalent uranium minerals, resulting in plugging pores and seriously affecting the effective leaching of uranium.This study contributes to the understanding of the behavior of pyrite during uranium recovery through CO2 + O2 leaching. It also contributes to the understanding of quantitative uranium mineralization in sandstone-hosted uranium deposits and process parameters in in-situ leaching (ISL) of uranium.

In Situ Characterization of the Locked Particle Behavior of Sulfide Minerals Using Non-Destructive Electrochemical Measurements

In Situ Characterization of the Locked Particle Behavior of Sulfide Minerals Using Non-Destructive Electrochemical Measurements

Impact of Pyrite Textures Prevalence on Flotation Performance in Mount Isa Copper Orebodies

ABSTRACT Pyrite, the most abundant sulfide mineral in base-metal deposits, presents significant challenges in mineral processing due to its deleterious effects when not properly managed. Its undesirable association with valuable minerals leads to low-quality concentrates, hindering smelting processes. Pyrite’s distinct textures and variable elemental compositions affect its floatability, with complex textures challenging to depress. Moreover, since multiple textures can be present within an orebody, their relative proportion in the ore could affect the overall flotation performance. Therefore, understanding the types of pyrite present, their abundance, and how they affect the flotation behavior of the ore is critical for an efficient depression and possible reclamation of pyrite. At the Mount Isa copper deposit, framboidal or ‘carbonaceous’ pyrite has been an ongoing challenge to the copper concentration operation, reducing the flotation circuit’s efficiency. Previous work by Yenial-Arslan et al. showed that high pyrite recoveries could be strongly linked to the prevalence of fine-grained pyrite. However, samples belonging to the coarse pyrite domain exhibited low natural floatability. This study further investigates the effect of the prevalence of pyrite textures on the flotation performance of copper orebodies at the Mount Isa deposit. The prevalence of pyrite textures was quantified and statistically linked to the natural floatability of pyrite, proving that fine-grained and framboidal pyrite greatly influence pyrite’s overall recovery. Furthermore, various mineral characterization techniques, such as synchrotron X-ray fluorescence microscopy (XFM) analysis, were used to explore how the natural floatability of pyrite was affected.

Extreme shifts in pyrite sulfur isotope compositions reveal the path to bonanza gold

Pyrite is the most common sulfide mineral in hydrothermal ore-forming systems. The ubiquity and abundance of pyrite, combined with its ability to record and preserve a history of fluid evolution in crustal environments, make it an ideal mineral for studying the genesis of hydrothermal ore deposits, including those that host critical metals. However, with the exception of boiling, few studies have been able to directly link changes in pyrite chemistry to the processes responsible for bonanza-style gold mineralization. Here, we report the results of high-resolution secondary-ion mass spectrometry and electron microprobe analyses conducted on pyrite from the Brucejack epithermal gold deposit, British Columbia. Our δ34S and trace element results reveal that the Brucejack hydrothermal system experienced abrupt fluctuations in fluid chemistry, which preceded and ultimately coincided with the onset of ultra-high-grade mineralization. We argue that these fluctuations, which include the occurrence of extraordinarily negative δ34S values (e.g., -36.1‰) in zones of auriferous, arsenian pyrite, followed by sharp increases of δ34S values in syn-electrum zones of nonarsenian pyrite, were caused by vigorous, fault valve-induced episodic boiling (flashing) and subsequent inundation of the hydrothermal system by seawater. We conclude that the influx of seawater was the essential step to forming bonanza-grade electrum mineralization by triggering, through the addition of cationic flocculants and cooling, the aggregation of colloidal gold suspensions. Moreover, our study demonstrates the efficacy of employing high-resolution, in situ analytical techniques to map out individual ore-forming events in a hydrothermal system.

Effects of water-table changes following rainfall events on arsenic fate and transport in groundwater–surface water mixing zones

This study investigated the effects of groundwater–surface water (GW–SW) interactions on the fate and transport of arsenic (As) following rainfall events and subsequent water-table changes in GW–SW mixing zones, comprising the riparian and hyporheic zones, near an abandoned gold mine. During the dry and wet periods, stream conditions changed from flow-through to gaining, respectively. Water-table changes caused by rainfall events controlled flow paths between riparian zones and the stream, affecting spatiotemporal variation in the redox and pH conditions of the aquatic environment. Subsequently, the fate and transport of As in GW–SW mixing zones was responsive to variations in redox and pH conditions. Through the oxidative dissolution of As-bearing sulfide minerals and the reductive dissolution of iron (Fe) oxides with adsorbed As, As was released into the groundwater in the riparian zones and transported to the stream and streambed along the baseflow discharge. However, As was also immobilized in the sediment through adsorption onto Fe-oxides and coprecipitation with calcium (Ca) and zinc (Zn), suggesting that the sediment acts as a sink-and-source of As in aquatic environments. Therefore, water-table changes and GW–SW interactions could play an important role in the fate and transport of As in aquatic environments, specifically groundwater–riparian–streambed–stream systems. The findings of this study will provide scientific insights into the mechanisms of As in aquatic environments, aiding in improved decision–making to ensure safe and sustainable water management in response to future climate change.

Microwave Treatment of Copper–Nickel Sulfide Ore for Promotion of Grinding and Flotation

The effect of microwave treatment on the grinding and flotation performance of a typical copper–nickel sulfide ore was evaluated, based on the determination of its microwave absorption capability, grinding and flotation indexes such as crack percentage, mineral liberation degree, particle size distribution, relative work index (RWI), metal enrichment ratio and recovery. There were obvious differences between the microwave absorption capabilities of the main minerals in the ore, as demonstrated by their different microwave penetration depths. They also induced temperature differences between sulfide minerals and gangue minerals which could reach 418 °C after microwave treatment for 20 s. It was shown that microwave treatment could effectively improve the grindability of the ore, as proven by the increase in fine particles smaller than 0.074 mm and the decrease in RWI after grinding due to the higher crack percentage and mineral liberation degree. Moreover, microwave treatment affected the ore floatability because of the generation of cuprite, retgersite, and rozenite with poor floatability when the treatment time was extended. By microwave treatment for a proper time, 20 s, an optimal balance between the grindability and flotation performance could be achieved. Compared with the untreated ore, the RWI of the ore decreased by 11.5%. After flotation, the Cu and Ni enrichment ratios of the flotation concentrate increased by 0.3 and 0.2, respectively. Meanwhile, their corresponding recoveries increased by 4.2% and 3.1%. This study provides new insights for the treatment of copper–nickel sulfide ore to enhance the grinding and flotation process.

Solid phase speciation controls copper mobilisation from marine sediments by methanobactin

Although marine environments represent huge reservoirs of the potent greenhouse gas methane, they currently contribute little to global net methane emissions. Most of the methane is oxidized by methanotrophs, minimizing escape to the atmosphere. Aerobic methanotrophs oxidize methane mostly via the copper (Cu)-bearing enzyme particulate methane monooxygenase (pMMO). Therefore, aerobic methane oxidation depends on sufficient Cu acquisition by methanotrophs. Because they require both oxygen and methane, aerobic methanotrophs reside at oxic-anoxic interfaces, often close to sulphidic zones where Cu bioavailability can be limited by poorly soluble Cu sulphide mineral phases. Under Cu-limiting conditions, certain aerobic methanotrophs exude Cu-binding ligands termed chalkophores, such as methanobactin (mb) exuded by Methylosinus trichosporium OB3b. Our main objective was to establish whether chalkophores can mobilise Cu from Cu sulphide-bearing marine sediments to enhance Cu bioavailability.Through a series of kinetic batch experiments, we investigated Cu mobilisation by mb from a set of well-characterized sulphidic marine sediments differing in sediment properties, including Cu content and phase distribution. Characterization of solid-phase Cu speciation included X-ray absorption spectroscopy and a targeted sequential extraction. Furthermore, in batch experiments, we investigated to what extent adsorption of metal-free mb and Cu-mb complexes to marine sediments constrains Cu mobilisation.Our results are the first to show that both solid phase Cu speciation and chalkophore adsorption can constrain methanotrophic Cu acquisition from marine sediments. Only for certain sediments did mb addition enhance dissolved Cu concentrations. Cu mobilisation by mb was not correlated to the total Cu content of the sediment, but was controlled by solid-phase Cu speciation. Cu was only mobilised from sediments containing a mono-Cu-sulphide (CuSx) phase. We also show that mb adsorption to sediments limits Cu acquisition by mb to less compact (surface) sediments. Therefore, in sulphidic sediments, mb-mediated Cu acquisition is presumably constrained to surface-sediment interfaces containing mono-Cu-sulphide phases.

New insights into the origin and depositional setting of the Haerdaban Pb[sbnd]Zn deposit, Chinese western Tianshan: Evidence from geology, chert geochemistry, and detrital zircon U[sbnd]Pb geochronology

The Haerdaban PbZn deposit (with an ore reserve of 10.93 Mt. at 1.0–25.65 % Zn and 0.7–12.29 % Pb) is hosted in weakly metamorphosed clastic‑carbonate rocks from the Proterozoic Haerdaban Group. It represents a significant addition of the sediment-hosted PbZn deposits in the Yili block, Chinese western Tianshan. Currently, there are ongoing debates regarding its genesis, with a particular focus on the crucial metallogenic mechanism (syngenetic sedimentary exhalation or epigenetic reworking) responsible for the primary sulfide mineralization. Mineralization at Haerdaban primarily occurs as banded to stratiform ore layers or lenses conformably sandwiched in their host rocks. Vein and stockwork ores occur locally below the stratiform ore layers. A syn-sedimentary fault trending SN was identified based on abrupt lateral changes in lithofacies and thickness of the stratigraphic units. The ore mineralogy is dominated by sphalerite, galena, quartz, and dolomite, with a small amount of pyrite, barite, and organic matter. Detrital zircon LA-ICP-MS UPb dating of the Haerdaban siltstones obtained a maximum depositional age of about 604 Ma. Their geochemical composition similar to the passive continental margin signatures, with rare earth element (REE) patterns enriched in LREE and negative Eu anomalies (Eu/Eu* = 0.50–1.14). Stratiform beds of chert that host disseminated ores have relatively high contents of hydrothermal components (e.g., Ba, Zn), with apparent positive Eu anomalies (Eu/Eu* = 7.38–49.34) and negligible negative Ce anomalies (Ce/Ce* = 0.85–0.98). They are thus interpreted to be hydrothermal sedimentary rocks (exhalites) deposited in a suboxic-anoxic environment proximal to the hydrothermal vents. Integrated geological and geochemical evidence indicates that the Haerdaban PbZn deposit is a typical vent-proximal sedimentary exhalative (SEDEX) deposit formed in a Neoproterozoic Sinian (Ediacaran) passive continental margin rift basin. Post-depositional metamorphism and deformation in the Paleozoic may have caused partial remobilization of primary ores but did not significantly alter the morphology of the orebodies. Furthermore, establishing a genetic model for the Haerdaban deposit has important implications for the exploration of similar deposits preserved in the equivalent stratigraphy within the Chinese western Tianshan region.

Synthesis of sulfide mineral crystals by incongruent methods using the example of Cu-Fe-S and Cu-Fe-Se systems

Research subject. Understanding the structure and thermodynamic properties of sulfide minerals is important for studying the paragenesis of sulfide formation on Earth and in space, as well as for analyzing technological issues in the processing of ores and polysulfide product concentrates. There is a lack of experimental and theoretical information on many representatives of the Cu-Fe-S and Cu-Fe-Se systems. Aim. To synthesize crystals in the Cu-Fe-S and Cu-Fe-Se systems at the lowest possible temperatures for the subsequent study of their physical properties, while solving the main problem of materials science related to interrelations between composition, structure, and properties. Materials and methods. Crystal synthesis was carried out by the solution-melt method in a stationary temperature gradient, in evacuated sealed quartz glass ampoules. Two types of ampoules were used in the experiment, standard and long. The ampoules were filled with a charge and a salt mixture of RbCl-LiCl of eutectic composition, evacuated and sealed, then placed in several quartz or ceramic glasses. The glasses were placed in tubular furnaces such that the ends of the ampoules with the charge were located closer to the center of the furnace, and the opposite ends were closer to the edge to create a temperature gradient. For standard ampoules, the hot end temperature was 520–469℃, and the cold end was 456–415℃. For long ones: 470℃ – hot end and 340℃ – cold. The synthesis duration ranged from three to four months. Results. Depending on the composition of the charge, crystals of chalcocine Cu2S, bornite Cu5FeS4, chalcopyrite CuFeS2, isocubanite CuFe2S3, and iron-containing dicopper sulfide with an iron content of up to 8 at % and various equilibrium associations with their participation and with the participation of pyrite FeS2 and pyrrhotites Fe1–xS were obtained. Copper dendrites were also found in some samples. In addition, crystals of a phase with the approximate composition of CuFeSe2 were obtained. It is shown that due to different combinations of oxidation states of all three elements dissolved in a salt electrolyte, it is possible to obtain phases with almost any stoichiometric ratio. Chalcopyrite and isocubanite are reliably detected using Raman spectroscopy. In this case, some samples are locally characterized by the “absence” of a spectrum, which probably indicates the metallic (semi-metallic) properties of the samples. Conclusion. Using the Cu-Fe-S and Cu-Fe-Se systems as an example, the possibility of obtaining sulfide crystals in a RbCl-LiCl salt melt up to a eutectic temperature of 313℃ is shown. Due to the low synthesis temperature, the synthesis should be carried out over several months, resulting in crystals a fraction of a millimeter in size.

Copper and zinc isotopic variations in Ni-Cu-PGE ores of the Noril’sk Province (Russia)

Research subject. Mineral assemblages of sulfides from massive and disseminated sulfide nickel-copper-platinum-group element (Ni-Cu-PGE) and low-sulfide PGE ores of the Noril’sk Province, which hosts the richest complex deposits of platinum-group metals, nickel, and copper. Aim. In order to identify sources of ore material and explore new forecasting approaches for Ni-Cu-PGE deposits, we study the Cu- and Zn isotopic compositions of sulfides from economic Kharaelakh and Noril’sk-1 intrusions containing unique and large sulphide Ni-Cu-PGE deposits (Oktyabr’sk and Noril’sk-1, respectively), subeconmic Zub-Marksheider and Vologochan intrusions containing small- to medium-size Ni-Cu-PGE deposits, and non-economic Nizhny Talnakh and Nizhny Noril’sk intrusions containing low grade disseminated Ni-Cu mineralization. Results. The analyzed samples are characterized by sulfide mineral assemblages, which contain mainly chalcopyrite, pyrrhotite, pentlandite, troilite, cubanite, and galena. Sulfide Ni-Cu-PGE ores of the Oktyabr’sk and Noril’sk-1 deposits, associated with economic intrusions (i.e., Kharaelakh and Noril’sk-1), demonstrate distinct δ65Cu values from –2.42 to –1.40‰ and from –0.33 to 0.60‰, respectively, which differ from the δ65Cu values for sulfides from other Ni-Cu-PGE deposits and ore occurrences of the Noril’sk Province (data comprise 36 analyses). We note that the Cu-isotopic composition for sulfide minerals of massive and disseminated ores from the Kharaelakh intrusion has similar “isotope-light” characteristics. The most pronounced shift towards “isotope-heavy” copper was found in the horizon of low-sulfide PGE ores of the Noril’sk-1 intrusion (δ65Cu = 0.51–0.60‰). The isotopic composition of Zn (δ66Zn) for the studied sulfide samples from economic, subeconomic, and non-economic intrusions, with the exception of one sample (0.73 ± 0.14‰), is characterized by similar “isotope-light” values (from –0.65 to –0.03‰). Conclusions. The revealed variations in the Cu- and Zn-isotopic composition in the studied sulfide assemblages from all types of ores reflect their primary characteristics; however, for the unique Oktyabr’sk Ni-Cu-PGE deposit, characterized by the most “isotopically light” composition of copper (δ65Cu = –1.9 ± 0.34‰), the possibility of assimilation of an external source of Cu during the formation of sulfide Ni-Cu-PGE ores cannot be excluded. The combined use of Cu and Zn isotopic parameters proved to be a weakly informative predictive indicator for the detection of high-grade sulfide ores, primarily due to the similarity of the Zn isotopic composition of the ore material in all investigated intrusions of the Noril’sk Province.