Base Metal Sulfide Mineralization Research Articles

Variation of chalcophile elements in base metal sulfide minerals from the Jinchuan magmatic Ni–Cu sulfide deposit, NW China: Implications for mineral exploration

Magmatic sulfide ores from the western and eastern intrusions of the world's third-largest Jinchuan Ni–Cu deposit are separated into disseminated, net-textured, and massive sulfides, or Fe-rich, transitional, Cu-rich ores. However, the composition of base metal sulfide (BMS) minerals from each intrusion and ore type still lacks investigation. By comparing the variations of chalcophile element composition of BMS minerals from different intrusions, sulfide textures, and ore types, new discriminant diagrams are constructed for subsequent exploration. BMS minerals from the eastern intrusion host more slightly chalcophile elements (Zn As, Sn Cd) because of the higher degree of crustal contamination, and less strongly chalcophile elements (Co, Bi, Se, Re, Ag, Te) due to the lower amount of prior sulfide segregation. R-factor modeling indicates that disseminated sulfides are formed at the highest R-factors, while massive sulfides are formed at the lowest. Correspondingly, R-factor upgrading results in higher concentrations of Se and Ag in BMS minerals from disseminated sulfides compared to net-textured sulfides. Most chalcophile elements in BMS minerals show positive or negative correlations with whole-rock Cu/Nic ratios (Nic represents corrected whole-rock Ni content after deducting Ni in olivine), suggesting extensive chalcophile element fractionation occurred during progressive sulfide fractionation. Furthermore, the elements that are slightly to moderately incompatible with monosulfide solid solution (MSS) while predominately hosted by BMS minerals (e.g., Cd, Se, Ag, and Te in chalcopyrite) show better correlations, making them preferable for tracing the sulfide fractionation. Utilizing the partial least squares-discriminant analysis models, we propose plots of Cd/(Co + As) vs. Bi/(Co + As), Ag vs. Bi/(Ag + Cd), and Co/(Ag + Cd) vs. Bi/(Ag + Cd) to discriminate chalcopyrite from different intrusions, sulfide textures, and ore types, respectively. Additionally, the occurrence of chalcopyrite with increased Bi/(Ag + Cd) and Co/(Ag + Cd) ratios and decreased Ag content presents promising clues for exploring Fe-rich massive sulfide ores.

Applied geochemistry for the discrimination between mafic and ultramafic rocks in Cu-Ni-PGE-bearing layered complexes: A case study at the la Jovita-Las Águilas belt, Sierra Grande de San Luis, Argentina

The Virorco intrusive body is comprised in La Jovita-Las Águilas mafic-ultramafic belt, Sierra Grande de San Luis, Argentina. The ultramafic rocks of this belt carry a base metal sulphide mineralization and platinum group minerals. Macroscopic description of mafic and ultramafic rocks, done by the mining exploration companies, can not differentiate the mineral percentages. Therefore, considering the geochemical composition of the already classified mafic-ultramafic rocks of surface samples from the mentioned belt, we established compositional ranges of geochemical parameters (MgO, Al2O3, Na2O, Sr and Cr) for both mafic and ultramafic rocks. Linking the geochemical data of drill cores made by Castillian Resources Corp. company over the Virorco body, with the mentioned ranges, it was possible to discriminate between mafic and ultramafic rocks present in such drill cores. This provides a useful prospecting tool to identify the mafic and ultramafic units that carry the mineralization and to correlate mineralized units from the different drill cores. This method can be applied, not only on the bodies of the mentioned belt, but in other similar deposits elsewhere. The methodology proposed in the present contribution was validated by the Machine Learning algorithm Random Forrest with a 91% success rate.

Tectonic evolution of the Aggeneys-Gamsberg Ore District, South Africa, and implications for the geodynamic setting of the Namaqua Sector

Understanding the deformation history of the structurally complex Aggeneys-Gamsberg Ore District (A-GOD), in the Namaqua Sector of the Mesoproterozoic Namaqua-Natal Metamorphic Province of South Africa, is key to discovering additional metasediment-hosted base metal sulphide mineralization. Although several studies have examined the structure of the main ore deposits and outcrops in the district, and others have investigated the timing of sedimentation, magmatism, and metamorphism, no previous studies have focused on integrating these two datasets. We therefore combine structural observations and the resulting relative timeline of events with new and existing zircon U-Pb geochronology, to yield a temporally constrained tectonic history for the district.The regionally recognized Paleoproterozoic D1 deformation is not recorded in the A-GOD, which preserves only Mesoproterozoic rocks. The largely stratiform base metal deposits occur near the top of a sequence of metamorphosed siliciclastic sediments (Wortel and Hotson Formations), deposited after 1261 ± 5 Ma (youngest reliable detrital zircons). These metasediments are tectonically interleaved with the intrusive ∼ 1190 Ma Little Namaqualand Suite (Aroams Gneiss) and younger ∼ 1175–1145 Ma metagranitoids (Achab Gneiss, Hoogoor Gneiss, aplite sills). Magmatism occurred early during D2a deformation, which created kilometre-scale isoclinal folds and thrusts during S/SW-directed contraction, as recorded at the Swartberg and Broken Hill-Deeps deposits. Associated M2a metamorphism is dated at ∼ 1200 Ma (metamorphic zircon rims), but this was not the peak metamorphic episode as previously thought. The sequence was then exhumed, and the unconformably overlying clastics and bimodal volcanics of the Koeris Formation were deposited in local transtensional pull-apart basins at ∼ 1130 Ma. Thrust stacking in the Aggeneys Mountains may have occurred during subsequent D2c contraction, associated with ∼ 1075 Ma M2c metamorphism, but evidence remains cryptic. The entire sequence is affected by kilometre-scale sheath folds that close downwards to the ∼ ENE (as at Gamsberg and the Quarry Fold Nappe), associated with ∼ ENE-trending open, upright folds. These developed during D3a ∼ ENE-directed extensional to constrictional shearing at peak M3 amphibolite-facies conditions, which re-used the gently dipping D2 regional fabric and overprinted it with new ∼ E-W trending D3 linear features. Abundant metamorphic zircon dates suggest an age of ∼ 1025 Ma for D3a and M3. Ongoing extension at retrograde conditions reactivated earlier structures, such as the Swartberg Thrust, as D3b low-angle, ductile–brittle detachment faults. Finally, dextral transform motion created local D4 monoclines and dextral strike-slip faults, possibly associated with ∼ 1000 Ma M4 metamorphic zircon growth and emplacement of a regional pegmatite swarm.The A-GOD has traditionally been fitted into a regional tectonic model involving accretion of distinct terranes onto the Kaapvaal Craton, during the polyphase ∼ 1.2–1.0 Ga Namaquan Orogeny. In contrast, recent studies propose that the entire Namaqua Sector instead occupied a back-arc setting between ∼ 1.35 and < 1.1 Ga. Our results support a hybrid model, involving accretion and translation of previously extended crustal fragments against the craton, with initially the entire Namaqua Sector - but later only the western portion - located in a hot back-arc setting influenced by subducting slab dynamics.

Hydrothermal Pentlandite (Ni,Fe)9S8 from Kambalda, Western Australia: Occurrences, Formation Conditions, and Association with Orogenic Gold

Abstract Pentlandite, (Ni,Fe)9S8, most commonly occurs in mafic or ultramafic rocks in association with other sulfide minerals, including pyrrhotite and chalcopyrite. However, at a few localities pentlandite has been found in hydrothermal settings. At Kambalda in Western Australia, hydrothermal pentlandite occurs in three different vein types: (1) sulfide veins, (2) quartz-calcite veins associated with biotite-epidote alteration, and (3) calcite veins containing arsenides and base metal sulfide minerals. In all three vein types, pentlandite (1) is restricted to veins crosscutting magmatic Ni sulfide lenses, (2) only occurs within &amp;lt;10 m of sulfide bodies, and (3) is associated only with pyrrhotite. In some cases, the pentlandite in the hydrothermal veins has higher Fe and lower Co contents compared to that in the magmatic Ni sulfide ores. The sulfarsenide minerals also show a bimodal distribution in terms of their chemistry: those associated with hydrothermal veins are dominated by Ni, whereas those associated with a primary magmatic origin are rich in Co. Intermediate compositions are observed, notably where hydrothermal sulfarsenide minerals directly overgrow earlier magmatic sulfide minerals. Thermodynamic calculations show that the hydrothermal pentlandite-pyrrhotite assemblages can form from highly reduced, hydrothermal fluids at near neutral pH. Pentlandite deposition can be triggered by an increase in pH and/or a decrease in temperature. Associated gangue minerals, such as biotite, feldspar, and quartz, are likely deposited as a result of concomitant fluid–rock interaction. High fluid temperatures (i.e., 400–500 °C) favor pentlandite formation due to an increase in Ni solubility. The pentlandite-pyrrhotite-biotite assemblage has a narrow stability field coinciding with a field of elevated Au solubility, which prevents coprecipitation of native gold with this mineral assemblage. In contrast, the pentlandite-arsenide mineral assemblage shows a larger stability field which overlaps with conditions allowing Au precipitation. The modeling results suggest that identification of the mineral assemblages in which pentlandite occurs is important in mineral exploration, one implication being that pentlandite-rich, hydrothermal veins will be expected to be Au-free. Conversely, pentlandite-poor or -absent veins, possibly containing Ni-arsenide minerals, may contain gold and could thus be indicative of enhanced prospectivity for gold.

Enhanced separation of base metal sulfides in flotation systems using Chitosan-grafted-Polyacrylamides

• Chitosan-grafted-Polyacrylamide (Chi-g-PAM) was prepared and characterized. • Adsorption studies of Chi-g-PAM on metal sulfide surfaces were conducted. • Chi-g-PAM was tested as pyrite’s depressant in metal sulfide flotation. • Chi-g-PAM outperformed other depressants at producing less pyrite-diluted products. In this study, chitosan-grafted-polyacrylamide (Chi-g-PAM), a synthetic biocompatible polymer was investigated as a selective depressant of iron sulfide minerals [i.e., pyrite (FeS 2 )] in the flotation process of base metal sulfide minerals [i.e., galena (PbS), chalcopyrite (CuFeS 2 ), and sphalerite (ZnS)]. Chi-g-PAM was successfully synthesized by grafting polyacrylamide chains onto chitosan backbone. The synthesized polymer was characterized using Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR), Nuclear Magnetic Resonance (NMR), Scanning Electron Microscopy (SEM), and X-ray Powder Diffraction (XRD) analysis. Adsorption studies of Chi-g-PAM on mineral surfaces were conducted using zeta potential, contact angle, and total organic carbon (TOC) measurements in addition to X-ray Photoelectron Spectroscopy (XPS). Adsorption tests showed that Chi-g-PAM was most selective to pyrite as compared to the base metal sulfides indicating that this polymer may have the potential to be used as pyrite’s depressant in the flotation of base metal sulfides under specific conditions. XPS studies suggested that the depression of pyrite by Chi-g-PAM was due to chemisorption of the amine, amide, and hydroxyl groups of Chi-g-PAM at pyrite-water interface. The impact of Chi-g-PAM on the flotation response of sulfide minerals was investigated in both microflotation and batch flotation systems using model minerals and real sulfide ore, respectively. In microflotation tests of model minerals, the best separation efficiencies between valuable base metal sulfides and pyrite were achieved at pH 7. In batch flotation tests of complex sulfide ore of Mississippi Valley type (MVT) at natural pH (7.8), a separation efficiency of 61% was achieved between galena and pyrite when Chi-g-PAM was used compared to 35% with sodium cyanide (NaCN), the depressant that is commonly applied for this type of ore. However, the separation efficiency between chalcopyrite and pyrite was 15% and 21% with Chi-g-PAM and NaCN, respectively. Comparative studies indicated that Chi-g-PAM outperformed other depressants at producing less pyrite-diluted flotation concentrates.

Towards the Biobeneficiation of PGMs: Reviewing the Opportunities

Conventional beneficiation of the Platinum Group of Metals (PGMs) relies on the use of inorganic chemicals. With the depreciation of high grade deposits, these conventional processes are becoming less economically viable. Furthermore, the use of chemicals has serious negative impacts on the environment. To address the challenges of conventional PGM beneficiation, biobeneficiation has been proposed. In conventional flotation, the flotation behavior of the associated sulphides determines overall PGM recovery. The same principle may also be applied for the bio-beneficiation of PGMs. Therefore, this paper discusses the biobeneficiation behavior of sulphides closely associated with PGMs with the aim of postulating the bio-beneficiation behavior of PGMs associated with the same base metal sulphides. Conventional PGM processes are briefly discussed, as bio-beneficiation of PGMs is governed by similar underlying principles. Potential microorganisms for the biobeneficiation of PGMs are highlighted, as well as the corresponding conditions for their effectiveness. The use of both single cultures and mixed cultures is discussed. Depending on conditions, PGMs associated with pyrite and/or chalcopyrite were projected to be biofloatable with B. polymyxa, P. polymyxa, A. ferrooxidans, L. ferrooxidans, B. pumilus, B. subtilis, halophilic bacteria, Alicyclobacillus ferrooxidans, sulphate reducing bacteria, and mixed cultures of A. ferrooxidans, A. thiooxidans and L. ferrooxidans. Pyrite-associated PGMsare expected to be generally prone to biodepression, whereas chalcopyrite-associated PGMs are expected to be generally recovered as the floatable phase. Sulphate-reducing bacteria were reported to have a dual role on the bioflotation of sulphide ores (flotation and depression), depending on the conditions. Therefore, this type of microorganism may serve as both a depressant or a collector in the recovery of PGMs. Based on the bioflotation response of pyrrhotite to L. ferrooxidans, it is anticipated that pyrrhotite-associated PGMS can be biodepressed using L. ferrooxidans. In terms of bioflocculation, PGMs associated with chalcopyrite may be recovered using L. ferrooxidans, whereas A. ferrooxidans, A. thiooxidans, B. polyxyma and B. subtilis can be used in the bioflocculation of pyrite-associated PGMs. M. phlei can be employed in the reverse bioflocculation of pyrite-associated PGMs. Although no information was found on the biobeneficiation of pentlandite, postulations were made based on other sulphide minerals. It was postulated that biobeneficiation (biodepression and bioflotation) with pentlandite-associated PGMs should be possible using A. ferrooxidans. It is also projected that sulphate-reducing bacteria will be suitable for the bioflotation of PGMs associated with pentlandite. The removal of gangue species such as silicates and chromites associated with PGM concentrates was also discussed. A. ferrooxidans, P. polymyxa and B. mucilaginous are candidates for the removal of gangue species. Furthermore, the need to control process conditions was highlighted. The most suitable conditions for biobeneficiation of the various base metal sulphide minerals associated with PGMs are presented in the paper. Most of the challenges associated with biobeneficiation of PGMs are already common to conventional methods, and the means of circumventing them are already well established. Developments in genetic engineering and the advent of new data science techniques are tools that could make the biobeneficiation of PGMs a possibility.

A revised age, structural model and origin for the North Pennine Orefield in the Alston Block, northern England: intrusion (Whin Sill)-related base metal (Cu–Pb–Zn–F) mineralization

Mineralization and associated fluid migration events in the c. 1500 km2 North Pennine Orefield (NPO) are known to be associated with tectonic activity, but the age of these tectonic events and origins of the base metal sulfide mineralization remain unresolved. New fieldwork in the Alston Block shows that mineralization post-dates a weakly developed phase of north–south shortening consistent with far-field Variscan basin inversion during the late Carboniferous. New observations of field relationships, coupled with microstructural observations and stress inversion analyses, together with Re–Os sulfide geochronology show that the vein-hosted mineralization (apart from barium minerals) was synchronous with a phase of north–south extension and east–west shortening coeval with emplacement of the Whin Sill (c. 297–294 Ma). Thus the development of the NPO was related to an early Permian regional phase of transtensional deformation, mantle-sourced hydrothermal mineralization and magmatism in northern Britain. Previously proposed Mississippi Valley Type models, or alternatives relating mineralization to the influx of Mesozoic brines, can no longer be applied to the development of the NPO in the Alston Block. Our findings also mean that existing models for equivalent base metal sulfide fields worldwide (e.g. Zn–Pb districts of Silesia, Poland and Tennessee, USA) may need to be reassessed.

Host rock peculiarities and influence of major structures on gold and base metal sulfide mineralization in northern Pakistan

For decades, the streams and rivers in northern areas of Pakistan are being explored for gold but the source rock for primary gold is yet to be located. Recent geological surveys have identified several areas for follow-up study for Cu-Au mineralization in Chitral and Gilgit-Baltistan regions. The rocks exposed at various localities are variably altered and/ or mineralized and intensely deformed, which mostly include diorite, granodiorite, greenschists, limestones and undeformed volcanic rocks and granitoids of the Kohistan island arc. The results of petrographic and X-ray diffraction (XRD) analyses of a variety of representative rock samples from a number sites have revealed that mineralization in the Chitral and Gilgit-Baltistan regions is dominantly in the form of pyrite, tetrahedrite, chalcopyrite and galena with subordinate amounts of magnetite, malachite and azurite. The associated/ gangue minerals include albite, quartz, actinolite, biotite, chlorite, epidote, calcite, garnet, illite and titanite (sphene). Diffraction patterns of glycolated samples did not show the existence of swelling clay (e.g., smectite). Sericitic, chloritic and carbonatic alterations have been observed in the studied altered rocks. Mass balance calculations indicate that most of the sulfide-bearing samples are enriched in Cu, Au, Sb, As and Pb and depleted in the rest of the metals reflecting differences in elements mobility during the ore-forming processes. Some of the mineralized rocks especially limestone have experienced a significant volume change due to mobilization of some of the major element oxides e.g. CaO, Fe2O3, SiO2 and ore-forming components e.g. Cu and Pb. The mineralization is of epithermal type in most of the investigated sites, however a few areas show ore formation though orogenic processes and very rarely the ore deposit displays features of the volcanogenic massive sulfide type. Some of the areas are quite promising with respect to their ore element contents and the highly mineralized zones lie in close proximity to major structures in the region. Besides, results from the current study indicate that the mineralization shows close spatial association and hence a strong genetic link with strike slip faults especially where they bend and merge together.

Base metal sulphide geochemistry of southern African mantle eclogites (Roberts Victor): Implications for cratonic mafic magmatism and metallogenesis

Platinum-group elements (PGE) display a chalcophile behaviour and are largely hosted by base metal sulphide (BMS) minerals in the mantle. During partial melting of the mantle, BMS release their metal budget into the magma generated. The fertility of magma sources is a key component of the mineralisation potential of large igneous provinces (LIP) and the origin of orthomagmatic sulphide deposits hosted in cratonic mafic magmatic systems. Fertility of mantle-derived magma is therefore predicated on our understanding of the abundance of metals, such as the PGE, in the asthenospheric and lithospheric mantle. Estimations of the abundance of chalcophile elements in the upper mantle are based on observations from mantle xenoliths and BMS inclusions in diamonds. Whilst previous assessments exist for the BMS composition and chalcophile element budget of peridotitic mantle, relatively few analyses have been published for eclogitic mantle. Here, we present sulphide petrography and an extensive in situ dataset of BMS trace element compositions from Roberts Victor eclogite xenoliths (Kaapvaal Craton, South Africa). The BMS are dominated by pyrite-chalcopyrite-pentlandite (± pyrrhotite) assemblages with S/Se ratios ranging 1200 to 36,840 (with 87% of analyses having S/Se <10,000. Total PGE abundance in BMS range from 0.17 to 223 ppm. We recognise four end-member compositions (types i to iv), distinguished by total PGE abundance and Pt/Pd and Au/Pd ratios. The majority of BMS have low PGE abundances (< 10 ppm) but Type iv BMS have the highest concentration of PGE recorded in eclogites so far (> 100 ppm) and are characteristically enriched in Os, Ir, Ru and Rh. Nano- and micron-scale Pd-Pt antimonide, telluride and arsenide platinum-group minerals (PGM) are observed spatially associated with BMS. We suggest that the predominance of pyrite in the xenoliths reflects the process of eclogitisation and that the trace element composition of the eclogite BMS was inherited from oceanic crustal protoliths of the eclogites, introduced into the SCLM via ancient subduction during formation of the Colesberg Magnetic Lineament c. 2.9 Ga and the cratonisation of the Kaapvaal Craton. Crucially, we demonstrate that the PGE budget of eclogitic SCLM may be substantially higher than previously reported, akin to peridotitic compositions, with significant implications for the PGE fertility of cratonic mafic magmatism and metallogenesis. We quantitatively assess these implications by modelling the chalcophile geochemistry of an eclogitic melt component in parental magmas of the mafic Rustenburg Layered Suite of the Bushveld Complex.

A New Approach to Selectively Reject Naturally Hydrophobic Gangue in the Flotation of Base Metal Sulphide Minerals

Efficient separation of naturally hydrophobic gangue, such as talc and carbonaceous materials, from sulphide minerals in flotation is becoming a significant challenge in many processing plants due to the need to process lower grade and more complex ores. Considering the hydrophobic nature of these gangue minerals, prefloating them at the beginning of the flotation circuit in the absence of collectors and rejecting the concentrate is a common practice to remove these gangue minerals. However, sulphide minerals, such as chalcopyrite, can become naturally floatable due to surface oxidation and therefore may float together with naturally hydrophobic gangue. In this study, a new approach was developed to maximize the prefloat of hydrophobic gangue while minimizing the loss of sulphide minerals. The new approach introduced a prefloat cleaner stage where sulphide minerals recovered to the prefloat concentrate was depressed and separated from other hydrophobic gangue minerals at a low pulp potential with the prefloat cleaner tailing fed back to the main sulphide flotation circuit. Flotation tests were conducted using chalcopyrite and organic carbon. The results show that the proposed approach can significantly reduce the loss of valuable minerals in the prefloat flotation without affecting the reject of naturally hydrophobic gangue. Applying pulp potential control at the prefloat cleaner flotation stage also reduces the consumption of reducing agents while minimizing the effect of reducing agents on downstream rougher flotation.

A combined multivariate approach analyzing geochemical data for knowledge discovery: The Vazante – Paracatu Zinc District, Minas Gerais, Brazil

The Vazante Group comprises a Proterozoic sequence of carbonate and siliciclastic rocks located in Minas Gerais, Brazil. It is the host of the Vazante-Paracatu Zinc District, including world-class hypogene zinc silicate deposits, in the southern part, and several Pb – Zn sulfide deposits in the northern part, all hosted in dolomitic rocks. A recent study revealed the occurrence of base metal sulfide mineralization that formed prior to the Brasiliano orogenic event in the siliciclastic rocks (Serra do Garrote Formation) that underlie these dolomite-hosted silicates and sulfide deposits. These siliciclastic rocks were considered as potential sources of elements for the hydrothermal fluids that formed the dolomite-hosted deposits, however there was little evidence of depletion of the source rocks during the orogenic event. In this paper, Random Forest is used in unsupervised mode along with t-distributed Stochastic Neighbor Embedding (t-SNE) and principal component analysis (PCA) over a lithogeochemical dataset of samples of the Serra do Garrote siliciclastic rocks collected throughout the basin to provide insights about processes related to the mineralizing system at the Vazante-Paracatu District.Multivariate analysis reveals that the Serra do Garrote Formation geochemical signature typical of pre-orogenic mineralization. This is characterized by PC1+ with association of Zn, Cd, Cu, Hg, In, V ± Sb, Se, Mo, Re, which corresponds to nearly 60% of the variance in the data. This suggest that these elements are related to a widespread and/or, long-living hydrothermal activity without an efficient mechanism to focus the metal-bearing fluids, causing basin-scale sub-economical Zn and related metal enrichment. Furthermore, PC2 and PC6 distinguish the zones with signatures interpreted to be related to depletion. PC2+ separates Cd-poor sphalerite, which is typical of the generation of sphalerite that occur in zones with textural evidence of remobilization. PC6+ with association of As, organic carbon and S, identified the zones where sphalerite was leached from the pyrite-rich layers. Areas with multivariate signatures of both pre-orogenic enrichment and syn-orogenic depletion in the source siliciclastic rocks include the Vazante-North Extension and Varginha zinc silicate deposits/occurrence, Ambrósia silicate zinc deposit and the Engenho Velho prospect. Preliminary exploration in this prospect revealed hydrothermal alteration typical of the zinc silicate deposits. This study is pioneering in applying these numerical models in possible source rocks to assist in identifying targets for exploration in basins.

Zircon U-Pb Dating of Magmatism and Mineralizing Hydrothermal Activity in the Variscan Karkonosze Massif and Its Eastern Metamorphic Cover (SW Poland)

SHRIMP (Sensitive high resolution ion microprobe) zircon U-Pb dating of the two main igneous rocks types in the Karkonosze Pluton, porphyritic and equigranular monzogranite, yield 206Pb/238U ages between 312.0 ± 2.9 and 306.9 ± 3.0 Ma. These coincide, within uncertainty, with the majority of previous dates from the pluton, which indicate development of the main magmatic processes between ca. 315 and 303 Ma. They also coincide with molybdenite and sulfide Re-Os ages from ore deposits developed during magmatic and pneumatolitic-hydrothermal (e.g., Szklarska Poręba Huta and Michałowice) or/and metasomatic and hydrothermal (e.g., Kowary, Czarnów and Miedzianka) processes forming Mo-W-Sn-Fe-Cu-As-REE-Y-Nb-Th-U mineralization. The 206Pb/238U zircon age of 300.7 ± 2.4 Ma from a rhyolite porphyry dyke (with disseminated base metal sulfide mineralization) in the Miedzianka Cu-(U) deposit coincides with the development of regional tectonic processes along the Intra-Sudetic Fault. Moreover, at the end-Carboniferous, transition from a collisional to within-plate tectonic setting in the central part of the European Variscides introduced volcanism in the Intra-Sudetic Basin. Together, these processes produced brecciation of older ore mineralization, as well as metal remobilization and deposition of younger medium- and low-temperature hydrothermal mineralization (mainly Cu-Fe-Zn-Pb-Ag-Au-Bi-Se, and Th-U), which became superimposed on earlier high-temperature Mo-W-Sn- Fe-As-Cu-REE mineralization. A few 206Pb/238U ages &gt; 320 Ma remain to be reconciled, but might be due to the high U and Th contents of the zircon and the strong influence of overprinting pneumatolitic-hydrothermal processes.

Chapter 7 Småland lithotectonic unit dominated by Paleoproterozoic (1.8 Ga) syn-orogenic magmatism, Svecokarelian orogen

AbstractThe Småland lithotectonic unit in the 2.0−1.8 Ga Svecokarelian orogen, southeastern Sweden, is dominated by a c. 1.81−1.77 Ga alkali–calcic magmatic suite (the Transscandinavian Igneous Belt or TIB-1). At least in its central part, the TIB-1 suite was deposited on, or emplaced into, c. 1.83–1.82 Ga calc-alkaline magmatic rocks with base metal sulphide mineralization and siliciclastic sedimentary rocks (the Oskarshamn–Jönköping Belt). Ductile deformation and metamorphism under low- to medium-grade conditions affected the Oskarshamn–Jönköping Belt prior to c. 1.81 Ga. Both suites were subsequently affected by low-grade ductile deformation, mainly along steeply dipping, east–west to NW–SE shear zones with dip-slip and dextral strike-slip displacement. Sinistral strike-slip NE–SW zones are also present. In the northern part of the lithotectonic unit, 1.9 Ga magmatic rocks, c. 1.87–1.81 Ga siliciclastic sedimentary rocks and basalt, and c. 1.86–1.85 Ga granite show fabric development, folding along steep NW–SE axial surfaces and medium- or high-grade metamorphism prior to c. 1.81 Ga and, at least partly, at c. 1.86–1.85 Ga; base metal sulphide, Fe oxide and U or U–REE mineralizations also occur. Magmatism and siliciclastic sedimentation along an active continental margin associated with subduction-related, accretionary tectonic processes is inferred over about 100 million years.

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.

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.

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.