Massive Sulfide Deposits Research Articles

Relative timing and controls on advanced argillic and conventional alteration of the Neoarchean Onaman volcanogenic massive sulfide deposit, Ontario, Canada

Relative timing and controls on advanced argillic and conventional alteration of the Neoarchean Onaman volcanogenic massive sulfide deposit, Ontario, Canada

Sulfur and metal mobilization during the life cycle of an oceanic core complex: Implications for seafloor massive sulfide deposits formation at slow and ultra-slow spreading ridges

Seafloor massive sulfide (SMS) deposits at slow and ultra-slow spreading ridges are often spatially related to, or hosted in oceanic core complexes (OCCs). The specific oceanic crust architecture, magmatism, hydrothermal fluid circulation and lithologies at OCCs, however, imply different S and metal (e.g. Cu, Zn, Co, Ni) fluxes relative to well-structured oceanic crust at-fast spreading ridges and which are not yet fully constrained. The study of S and metal distribution in the ODP Hole 735B deep drill core from the Atlantis bank allows to understand these fluxes along detachment faults and to better constrain the source zone of S and metals for OCC-related SMS deposits. Significant depletion of S, Cu, Zn and Ni are observed within the upper 250 m of the drill core where intense deformation and hydrothermal fluid circulation occurred. During the complex tectono-magmatic-hydrothermal evolution of the Atlantis Bank, four important stages are recognized for S and metal mobilization: 1) magmatic stratification leading to a higher proportion of sulfide-rich and S, Cu, Zn and Co fertile oxide gabbros in the root zone of the Atlantis Bank detachment, 2) high temperature ductile deformation leading to magmatic sulfide reworking and onset of sulfide leaching with limited metal mobilization, 3) extensive sulfide leaching and metal mobilization during amphibolite to greenschist facies metasomatism and, 4) late stage secondary sulfide precipitation and S enrichment during low temperature fluid circulation. Mass balance calculations from the source zones of the Atlantis Bank detachment highlights that metal mobilization during hydrothermal alteration of gabbroic rocks along detachment faults can fully account for the formation of OCC-related SMS deposits at slow and ultraslow spreading ridges. The Atlantis Bank detachment system, however, is gabbroic-dominated and represent the magmatic end-member of OCCs and further work is necessary for understanding metal fluxes in ultramafic-dominated detachment systems.

Bio-mediated enhancement of supergene copper mineralization: Evidence from Cu isotope geochemistry

The relationship between microbial activity and the supergene modification of ore systems has been a major subject of debate. Here, we present isotopic evidence of microbial-driven secondary copper mineralization in the active cementation zone of the Las Cruces deposit, a volcanogenic massive sulfide deposit located in Iberian Pyrite Belt, Spain. Copper isotopic data show that the lower isotopic ratios (δ65Cu ≈ −9.2 ± 0.11 ‰, the lowest value measured worldwide in a supergene environment) are found in the upper part of the cementation zone, the same zone where the maximum copper grades are found and where there is direct evidence of extremophilic microbial activity. There is a tendency towards higher values downwards through the cementation zone (−9.2 ± 0.11 ‰ to + 1.67 ± 0.11 ‰ δ65Cu) and upwards into the former Cu-depleted gossan that originally capped the cementation zone (−7.79 ± 0.11 ‰ to −1.32 ± 0.11 ‰ δ65Cu). As microbes preferentially sequester the lighter isotope when incorporating intracellular Cu, this distribution indicates that microbes played a major role in the formation of the high-grade zones. Water arrives to the deposit enriched in isotopically heavy copper, likely because it has leached other ore bodies upstream. δ65Cu values of water currently flowing into the system are remarkably more positive than those in the ore, indicating that microbial activity is a major cause of copper isotope fractionation. At least half of the copper transported by the incoming waters remains within the ore body. Our best interpretation is that the large and high-grade cementation zone at Las Cruces is of biogenic origin, and that the primary mineralization acted as a trap for copper transported by groundwater, leading to the formation of an exotic mineralization distal to sub-eroded massive sulfides located upstream.

The occurrence of cobaltite nanoparticles in pyrite from the De’erni deposit, NW China

Cobalt (Co) is a critical metal that occurs in many types of deposits, Co minerals and sulfide hosts are the main forms of Co occurrence. Pyrite is the most important cobalt-bearing mineral in the De’erni Cu-Zn-Co ultramafic-hosted volcanogenic massive sulfide deposits. However, the occurrence and enrichment of Co in pyrite remain unclear. In this study, a combination of LA-ICP-MS and STEM techniques was employed to conduct a detailed mineralogical investigation of pyrite in the De’erni deposit. The results revealed significant variations in cobalt content among pyrite samples from different mineral assemblages. Pyrite associated with magnetite (Mag), pyrrhotite (Po), chalcopyrite (Ccp), arsenopyrite (Apy), and bornite (Bn) (Py-Mag-Po-Ccp-Apy-Bn suite of mineral assemblages) exhibited the highest cobalt content, which ranged from 672.6 ppm to 2007 ppm. Cobalt occurs in two forms in the pyrite from the De’erni deposit: as cobaltite nanoparticles (NPs) and as a substitute for iron (Fe) in the pyrite lattice. The enrichment mechanism of cobalt in pyrite was explored at the deposit and mineral scales. The results indicate that a decrease in ore-forming fluid temperature and an increase in cobalt content may be significant factors contributing to cobalt enrichment at the deposit scale. Lattice defects may play a crucial role in cobalt enrichment within the pyrite lattice. Furthermore, the discovery of cobaltite NPs in pyrite could provide new insights for explaining the complex zonation of the cobalt element in pyrite.

Classification of volcanogenic massive sulfide deposits in North Qilian, China: Evidenced from lithostratigraphy and geodynamic setting

Volcanogenic massive sulfide (VMS) deposits are widely distributed both geographically and temporally, occurring from ancient Archean cratons to modern submarine volcanic environments, with a notable surge during the Paleozoic era. The North Qilian orogenic belt in China is a prominent Paleozoic VMS metallogenic province, shaped by complex geological processes such as the opening of the Qilian Ocean, oceanic subduction, and arc-continent collision. Previous research has constrained the timing of VMS mineralization in the North Qilian to between 440 and 470 Ma, identifying two primary deposit types: Kuroko-type and Cyprus-type. However, ongoing debates persist regarding the classification and geodynamic framework of these VMS deposits. The recent surge in international research on VMS deposit classification and tectonic settings has prompted a reassessment of VMS mineralization within the North Qilian belt. This study revisits the geological and geochemical characteristics of VMS deposits in the region, identifying two distinct types: Mafic VMS deposits and Bimodal-Felsic VMS deposits. Furthermore, the metallogenic dynamics of the Shijuli, Jiugequan, and Baiyinchang deposits have been re-evaluated in the context of the structural evolution and contemporary interpretations in this area.

The Fate of “Immobile” Ti in Hyaloclastites: An Evidence from Silica–Iron-Rich Sedimentary Rocks of the Urals Paleozoic Massive Sulfide Deposits

The formation of Paleozoic silica–iron-rich sedimentary rocks in the Urals volcanic-hosted massive sulfide (VHMS) deposits is considered a result of seafloor alteration of hyaloclastites mixed with calcareous/organic or sulfide material. These rocks host various Ti mineral phases pointing to the transformation of precursor metacolloidal TiO2 phases to disordered anatase during seafloor alteration of hyaloclastites, which was later converted to globules and clusters and further to diagenetic rutile. The LA-ICP-MS analysis showed that the Ti content of hyaloclasts partly replaced by finely dispersed Si–Fe aggregates increases to 540–2950 ppm and decreases (<5 ppm) in full Si–Fe pseudomorphs after hyaloclasts. LA-ICP-MS element mapping reveals the enrichment in V, U, Cr, W, Nb, Pb, and Th of the anatase globules and the local accumulation of Zr, Y, and REE on their periphery. Corrosive biogenic textures in the outer zones of some hyaloclasts and biomorphic aggregates in rocks contain anatase particles in assemblage with apatite indicating the biophilic properties of Ti. This work fills the knowledge gaps about Ti mobilization during low-temperature seafloor alteration of hyaloclastites in VHMS deposits.

Synchronous felsic volcanism and carbonate sedimentation as a setting for VMS deposits localization at the Salair terrane, NE Central Asian Orogenic Belt

The Salair terrane located in the northern part of the Central Asian Orogenic Belt (CAOB) contains many epithermal deposits including volcanogenic massive sulphide (VMS) deposits. The host rocks mainly consist of felsic volcanic rocks such as lavas, volcanic breccias and tuffs that associated with thick strata of carbonates. In this study, we present zircon U–Pb ages, whole rock geochemistry, and Nd isotope data from the volcanic rocks, and results of geochemical and isotope (Sr, C, O) studies of carbonates to constrain their age and petrogenesis, and to characterize the tectonic setting. Zircon U–Pb dating reveals that the ore-bearing felsic lavas have age of 519.3 ± 1.9 Ma, while the felsic tuffs have age of 516.0 ± 0.9 Ma. These volcanic rocks are characterized by high SiO2 and Na2O contents, enrichment in light rare-earth elements, remarkable negative Eu anomalies, and pronounced depletion in Nb, Ta, P, and Ti. They have depleted ɛNd(t) values ranging from +4.9 to +6.3, and young two-stage Nd model ages (from 0.82 to 0.64 Ga). The felsic volcanic rocks from the Salair terrane are interpreted as highly evolved I-type magmatic rocks that might be produced by high degree partial melting of juvenile lower crust without a significant contribution of ancient crust and without crustal reworking.Felsic volcanism was accompanied by the formation of thick strata of carbonates. These carbonates are marine limestones with Mg/Ca ratios less than 0.007, δ18O(SMOW) values from 17.1 to 23.8 ‰ and δ13C(PDB) values between –0.9 and +0.9. Their Sr isotope composition varies in a narrow range within 0.70844–0.70859 that interpreted as representing proxy for coeval seawater. These values are consistent with depositional ages of 520–510 Ma and confirms the synchronicity of the formation of carbonates and felsic volcanism. Based on the regional geology and geochemistry, the ore-host rocks of the Salair terrane were formed in the back-arc setting where the marine transgression occurred as a result of graben subsidence. It is important for better understanding epithermal deposits in the northern CAOB and might provide new insights about prospecting the VMS deposits in similar tectonic settings.

The flotation of magmatic sulfides transfers Cu-Au from magmas to seafloor massive sulfide deposits

Copper and gold-rich seafloor massive sulfide deposits formed in intra-oceanic subduction settings are typically associated with hydrous and oxidized magmas, but processes leading to their formation remain controversial. Sulfide-bubble interaction has been suggested to play an important role in metal transfer from magmas to seawater-derived hydrothermal fluids. Here we use textural observations of magmatic sulfides, geochemical numerical models of chalcophile element concentrations, and numerical models of magmatic sulfide growth within a mafic to felsic submarine magmatic suite (Fatu Kapa, SW Pacific) associated with copper-gold-rich seafloor massive sulfide deposits. We demonstrate that concomitant sulfide and aqueous fluid formation at the andesitic stage results in floating sulfide-bubble compound drops in magmas, which play a crucial role in the transfer of copper and gold toward the surface. We emphasize that late sulfide saturation in copper-gold-rich intra-oceanic subduction-derived felsic magmas favors upward sulfide transfer via flotation.

Whole rock lithogeochemical analysis of the Mount Read Volcanics: a new tool for geochemical exploration

The Mount Read Volcanics (MRV) of western Tasmania is a belt of Middle to Late Cambrian submarine volcanics and volcaniclastics and one of the major base and precious metal provinces within Australia. Exploration success in the MRV has been in decline in recent years due to a variety of challenges including intensely altered rocks with complex stratigraphy and lithofacies variation, and a lack of accessible outcrop. As a result, local and regional mapping of the MRV is often restricted to Group-level stratigraphy, rendering geological mapping ineffective for identifying decametre-scale mine stratigraphy. Surface rock chip and drill hole samples were collected and analysed using commercially available geochemical assays to create a regional geochemical dataset of the MRV, covering the entire province and all major stratigraphic units. From these data, a lithogeochemical methodology was developed, utilizing Ti/Nb and V/Sc systematics that effectively characterizes the samples according to composition and magmatic processes. This method is shown to be robust to biases due to alteration and lithofacies, eliminating the need for highly selective sampling or extensive data filtering. To demonstrate the utility of this method in an exploration context, data from the K-lens of the Rosebery polymetallic volcanic-hosted massive sulfide (VHMS) deposit was used as a case study. Using Ti/Nb–V/Sc systematics, a rock composition classification was developed that allowed for discrimination of the footwall, hanging wall and host stratigraphy of the Rosebery mine sequence. A geochemical fingerprint for the footwall stratigraphy to mineralization was developed, and by correlating this signature to the regional unclassified samples, geochemical analogues for the Rosebery footwall were readily identified. This approach rapidly reduces the exploration search space and provides valuable information for future mineral exploration. The methodology is applicable in other terrains; however, appropriate orientation studies are required to investigate potential biases due to lithofacies, alteration and mineralogical variability.

Updating Geological Information about the Metallogenesis of the Iberian Pyrite Belt

The Iberian Pyrite Belt (IPB) represents one of the largest districts of volcanogenic massive sulfide (VMS) deposits in the world, and is a critical source of base metals (Cu, Pb, and Zn) for Europe. Confirmed resources exceed 1700 Mt of massive sulfides with grades of around 1.2% Cu, 1% Pb, and 3% Zn as well as more than 300 Mt of stockwork-type copper mineralization. Significant resources of Sn, precious metals (Au and Ag), and critical metals (Co, Bi, Sb, In, and Se) have also been evaluated. The genesis of these deposits is related to a complex geological evolution during the late Devonian and Mississippian periods. The geological record of such evolution is represented by three main lithological units: Phyllite–Quartzite Group, the volcano–sedimentary Complex (VSC), and the so-called Culm Group. The sulfide deposits are located in the VSC, associated with felsic volcanic rocks or sedimentary rocks such as black shales. The massive sulfide deposits occur as tabular bodies and replacement masses associated with both volcanic and sedimentary rocks. Their mineralogical composition is relatively simple, dominated by pyrite, chalcopyrite, sphalerite, and galena. Their origin is related to three evolutionary stages at increasing temperatures, and a subsequent stage associated with the Variscan deformation. The present paper summarizes the latest developments in the IPB and revises research areas requiring further investigation.

Assessment of atmospheric pollution by potentially toxic elements in the urban areas of the Riotinto mining district

Ore mineralizations in bedrock and their exploitation may have a negative impact on air quality of surrounding urban areas and, subsequently, on human health. This study uses lichens as bioindicators of atmospheric pollution to evaluate the spatial distribution of potentially toxic elements (PTEs) in the towns close to the massive sulfide deposits of the Iberian Pyrite Belt (IPB) in SW Spain. Altogether 89 native lichen samples of Xanthoria parietina were collected from the mining towns, control towns out of the reach of the mining activity, as well as from distal sampling sites. The samples were analyzed for 29 elements after acid digestion. The concentrations for Co, Ni, Cu, Zn, As, Rb, Mo, Cd, Sn, Sb, Cs, Ba, W, Tl, Pb, S, and Fe are significantly higher in the mining towns in comparison to the control towns. The ore mineral-associated PTEs, including Cu, Zn, As, Ba, and Pb, exhibit extreme concentrations in the urban areas close to the mining activity, and particularly in the small settlement of La Dehesa next to the mineral processing plant and the tailings pond. The distal samples confirm the decrease in the concentrations of all PTEs, and these samples present similar values as in the control areas. The results, point at increased bioaccumulation of PTEs in the lichen thalli of the adjacent urban areas, suggesting that the air quality of the adjacent urban areas is locally impacted by the massive polymetallic sulfide deposits which is enhanced by the mining activity. Therefore, monitoring the urban air quality is recommended.

Insights into the indium enrichment of the Ashele VMS Cu-Zn deposit, Altay, NW China

Indium (In) is a critical metal used in the photovoltaic and semiconductor industries, which have exhibited extraordinary growth in demand. Indium is produced as a by-product of mining from different ore deposits (e.g., epithermal, sediment-hosted, and skarn). Volcanogenic massive sulfide (VMS) deposits are an important source of In; however, the mechanism of In enrichment is not fully understood. Here, we combine mineralogy with in situ trace element and S-Pb isotope geochemistry to reveal the enrichment of indium in the Ashele VMS Cu-Zn deposit (1.08 Mt. Cu, 0.43 Mt. Zn) located in Altay, NW China. The Ashele deposit is hosted in the metamorphosed Devonian felsic-bimodal volcanic rocks. This deposit consists of seafloor hydrothermal, metamorphic hydrothermal, and supergene stages. The seafloor hydrothermal stage comprises macro-scale Cu-rich bands (chalcopyrite, pyrite, and minor sphalerite) and Zn-rich bands (sphalerite, pyrite, and minor chalcopyrite). Indium is mainly hosted by chalcopyrite (mean 178 ppm) and sphalerite (mean 214 ppm) and occurs in the lattice. Mineral assemblages and trace element geochemistry suggest that the Cu-rich bands were deposited under high temperatures (> 300–350 °C) and sulfur fugacity (−7.2 to −4.9), whereas the Zn-rich bands were formed under lower temperatures (180–220 °C) and sulfur fugacity (−15.7 to −11.5). The interlayered Cu-rich and Zn-rich bands may reflect the oscillating temperature and sulfur fugacity variations. In situ S isotopic compositions of sulfides cluster within two ranges: 1–3 ‰ and 3–6 ‰, suggesting two endmembers: volcanic origin and reduced seawater sulfate. Pb isotopic ratios are similar to those of the host volcanic rocks, indicating that the metals may be derived from the felsic volcanic system. During metamorphism, the indium may be retained, but Cu contents of sphalerite become more homogeneous. Most In-rich VMS deposits worldwide are hosted by the felsic-dominant system in island arc and back-arc settings. These tectonic settings are conducive to the production of felsic volcanic systems, which are more likely to contain In mineralization. This study highlights the enrichment mechanism of indium in VMS deposits and suggests that the South Altay could become an important source of In.

Compositional balance analysis for Cu–Zn(±Co) geochemical anomaly mapping in Trøndelag county, Norway

Trøndelag county has been recently the focus of a new mineral exploration wave given its well-known base metal mineralization potential associated with the occurrence of volcanogenic Cu–Zn (±Co ± Ag ± Au) massive sulfide deposits (VMS). This study evaluates a regional low-density soil sampling survey by implementing principal component analysis (PCA), and compositional balance analysis (CoBA) to target prospective areas for base metal mineralization. Principal component analysis indicates a dominant base metal mineralization signature characterized by a correlation between As and Cu–Cr–Co–Ni, which is consistent with the occurrences of mafic metavolcanic and associated low K–Ca metasedimentary rocks. However, several other Cu–Zn occurrences hosted in K- and/or Ca-rich (meta-)sedimentary (e.g., Røros districts) and felsic (meta-)igneous lithologies have been overlooked by this approach. Data- and knowledge-driven balances (i.e., isometric log-ratios) were then constructed to enhance these “weaker” Cu–Zn (±Co) mineralization fingerprints. Most of the data-driven balances (dcobals) are shown to be very noisy, and less useful for base metal geochemical anomaly mapping compared to their more coherent knowledge-driven counterparts (kcobals). However, the kcobals (e.g., for Cu, Zn and Co) highlight relatively large anomalous areas, which makes them less practical if used as individual exploration vectors. To further define zones of economic interest, common anomalous areas (defined as kcobal >75th percentile) have been filtered out from selected kcobal pairs. This has resulted in the identification of several prospective areas that correspond with 15%–20% of the Trøndelag county.This study not only explores the combined use of CoBA and PCA for detecting base metal anomalies, but also elaborates on some factors that can affect the interpretation and performance of multivariate approaches (e.g., mineralization/alteration extension versus survey resolution, geological framework, and deposit type). The visualization and implementation of CoBA presented in this paper aim to improve geoscientists’ understanding of the reach and limitations of using isometric log-ratios for mineral exploration studies.

Geochemical characteristics of Neoproterozoic metavolcanic rocks of Ariab Auriferous Volcanogenic Massive Sulfide deposit, Red Sea hills, North-East Sudan

The Ariab volcanogenic massive sulfide (VMS, ∼118.3 Mt with >2 Moz Au recovered) district is part of the Ariab-Arbaat belt located in the Haya terrane, Red Sea Hills, Northeast Sudan. The gold-bearing gossan and VMS deposits are mainly hosted by Neoproterozoic bimodal volcanic succession. The petrogenesis, age dating, metallogenic evolution, and tectonic environment as well as the relationship between the metals occurrences and hosting materials remain poorly constrained and controversial. The study aims to investigate the geochemical characteristics of metavolcanic rocks of Ariab Auriferous Volcanogenic Massive Sulfide. XRF and ICP-MS techniques were employed to analyze major, trace, and rare earth elements content. The metavolcanics composition of Ariab VMS hosting rocks ranging from basalt to rhyolitic lava with variable pyroclastics. The chemical affinity varies from sub-alkaline tholeiitic to calc-alkaline nature, raising an argument against the possibility of fractional crystallization. The Ariab VMS metavolcanics were likely formed in the intra-oceanic arc tectonic environment. Ariab mafic lava is characterized notably by high Cr and Ni concentrations. The negative and positive anomalies in trace element profiles are typically ocean island basalt patterns, implying minimal crustal contamination. The geochemical results of dacitic and rhyolitic rocks reveal an assimilation-fractional-crystallization process, including the possibility that plagioclase-rich restite was formed in the parent magma source with a significant contribution from the old crust. The mobility of elements such as Zn, Cu, Pb, Ag, Au, As, and Co complicates the determination of their primary abundances. The partitioning behavior of REEs, the geochemical signatures of chalcophile elements, and their associations with VMS deposits, underscores the complex interaction between igneous processes and subsequent hydrothermal alteration.

Ore Remobilization History of the Metamorphosed Rävliden North Volcanogenic Massive Sulfide Deposit, Skellefte District, Sweden

Abstract The Skellefte district in northern Sweden hosts many volcanogenic massive sulfide (VMS) deposits and is considered one of the most important European mining districts for Cu, Zn, Pb, Ag, and Au. The volcanic and sedimentary rocks that the VMS deposits are hosted in were deformed during the Svecokarelian orogeny, with three documented regional deformation phases. These events imparted a distinct attitude and geometry to the deposits, their host succession, and discordant zones of synvolcanic hydrothermal alteration. Few studies have investigated the detailed deformation effects on the sulfide minerals. In this contribution, we document the structural characteristics and remobilization history of mineralization at the Rävliden North Zn-Pb-Cu-Ag deposit—one of the most important recent discoveries in the district consisting of 8.5 million tonnes (Mt) grading 1.01% Cu, 3.45% Zn, 0.53% Pb, 78.60 g/t Ag, and 0.23 g/t Au. At Rävliden, massive to semimassive sphalerite-rich mineralization with lesser pyrrhotite, galena, pyrite, and silver minerals occurs structurally above stringer-type mineralization dominated by chalcopyrite, pyrrhotite, and pyrite. These mineralization types exhibit evidence of deformation and remobilization such as (1) sulfide-alignment parallel to tectonic foliations; (2) rounded wall-rock tectonoclasts in a ductile deformed sulfide matrix (“ball ore” or durchbewegt ore); and (3) sulfides in tension gashes, strain shadows, piercement veins, and late, straight veinlets crosscutting tectonic fabrics. These features are attributed to polyphase deformation during the D1, D2, and D3 events at temperature ranging from 200° to 550°C. Remobilization of sulfides was mostly within the bounds of the main mineralization (i.e., 10–100 m), with few local external occurrences. A combination of solid-state and fluid-assisted remobilization processes are inferred. Rare brittle veinlets and zeolite-cemented breccias with sphalerite, galena, and silver minerals occur in the stratigraphic hanging wall, where they crosscut all Svecokarelian structures. This mineralization type is highly reminiscent of Phanerozoic low-T vein- and breccia-hosted Pb-Zn deposits of the Lycksele-Storuman area west of Rävliden North, which have been linked to far-field effects associated with the opening of the Iapetus Ocean (0.7–0.5 Ga). We suggest that this Zn-Pb mineralizing event led to the formation of the late sulfide-zeolite veinlets and breccias at Rävliden North, and that elements such as Ag and Sb within this mineralization were locally remobilized from Rävliden.

Corundum in Sulfide Ore at the Thompson Mine, Manitoba, Canada: An Unusual Occurrence of Cr- and Ni-Bearing Corundum

Abstract A novel type of corundum host environment is described from the Thompson Mine, northern Manitoba, where corundum occurs within a high-grade metamorphic reaction zone between boudinaged metaperidotite bodies, sulfide ore, and Al-rich pelitic schist of the Pipe Formation (Ospwagan Group). Zoned corundum porphyroblasts, up to 20 mm across, contain coevally formed sulfide inclusions, zircon, rutile, abundant exsolved rutile needles, and secondary sulfide inclusions formed within fractures. Retrograde alteration products of corundum include greenish muscovite (in contact with the schist) and diaspore (in contact with sulfides). The median concentrations of trace elements in Thompson corundum are as follows (in µg/g): 119 Mg, 1720 Ti, 69.9 V, 390 Cr, 8.2 Mn, 1924 Fe, 9.1 Ni, and 106 Ga. The geochemical signature of Thompson corundum (enrichment in Fe, Cr, and Ni) resembles that of ruby in other metamorphic and metasomatic mafic-ultramafic-hosted deposits, and the Cr concentration is comparable to the low range of rubies. Thompson corundum contains high Ni concentrations relative to most Cr-enriched corundum occurrences, a result of formation in an exceptionally Ni-rich environment. The high abundance of exsolved rutile inclusions imparts a dominantly brownish-gray color to the corundum, which precludes it from being of gem quality. Chromium-bearing corundum has been suggested as a possible indicator mineral for metamorphosed massive sulfide deposits, however, it is an indirect indicator that risks yielding false positives. Further investigation into Ni concentrations in corundum, a potential indicator of formation in a Ni-rich environment, is recommended.

In Situ Sulfur Isotope Geochemistry Using Secondary Ion Mass Spectrometry of Sulfides in the ABM Replacement-Style Volcanogenic Massive Sulfide Deposit, Finlayson Lake District, Yukon, Canada

Abstract The ABM deposit is a bimodal-felsic, replacement-style volcanogenic massive sulfide deposit located in the Finlayson Lake district, Yukon, Canada, that is hosted by back-arc-affinity felsic volcanic rocks of the Yukon-Tanana terrane. Massive sulfide mineralization occurs as a series of stacked and stratabound lenses subparallel to the volcanic stratigraphy, surrounded by an envelope of pervasive white mica and chlorite alteration. Three major mineral assemblages occur: (1) a pyrite-sphalerite assemblage enriched in Zn-Pb-As-Sb-Ag-Au that formed at temperatures ∼200–270 °C, (2) a pyrite-chalcopyrite-magnetite-pyrrhotite assemblage enriched in Cu-Bi-Se-Co that formed at temperatures ∼300–350 °C, and (3) a chalcopyrite-pyrrhotite-pyrite stringer assemblage formed at temperatures >300 °C. In situ analysis of the sulfur isotopic ratios (δ34S) using secondary ion mass spectrometry has been performed on sulfides (pyrite, pyrrhotite, chalcopyrite, galena, and arsenopyrite) from samples representative of the major mineral assemblages. The δ34S results range between +4.0 and +12.5‰. The pyrite-sphalerite assemblage has an average δ34S value of +6.6 ± 1.8‰ (n = 31), whereas the higher temperature assemblages have an average δ34S value of +9.9 ± 1.4‰ (n = 59). Examination of the δ34S values of adjacent mineral pairs shows that the sulfides were formed under disequilibrium conditions and were not significantly altered or re-equilibrated by greenschist facies metamorphism that affected the ABM deposit post-volcanogenic massive sulfide formation. The observed range of δ34S values suggests that H2S derived from thermochemical sulfate reduction of seawater sulfate and/or an igneous sulfur source as the likeliest sources of S for the sulfides in the ABM deposit. Modeling of thermochemical sulfate reduction of contemporaneous Late Devonian seawater sulfate (δ34S ∼ +25‰) at temperatures estimated for the fluids forming the ABM deposit mineral assemblages (200–350 °C) shows that the reduction of 5–30% of the seawater sulfate would result in isotopic signatures similar to those observed at the ABM deposit. This model also explains the distribution of δ34S values across the mineral assemblages, as thermochemical sulfate reduction at higher temperatures (350 °C) results in more isotopically positive δ34S values. Modeling of mixing lines between thermochemical sulfate reduction at different temperatures and an igneous sulfur source suggests that leaching of magmatic/volcanic rocks also acted as a source of sulfur and was a likely a major contributor (70–95%) to the hydrothermal fluid system at the ABM deposit.

Factor analysis in residual soils of the Iberian Pyrite Belt (Spain): comparison between raw data, log-transformation data and compositional data

The Iberian Pyrite Belt (IPB) is a metallogenic province in SW Spain and Portugal hosting the largest concentration of massive sulfide deposits worldwide. Exploration campaigns in both the Spanish and Portuguese sectors of the IPB have increased recently due to the rise in metal prices. Within this framework, distinguishing geochemical features associated with natural phenomena and isolating geogenic anomalies from anthropogenic ones can pose a challenge. This contribution uses the residual soil geochemical database of the IPB (Spain) to examine numerous variables, encompassing major, minor and trace elements. Some of these variables commonly exhibit high correlations owing to consistent geochemical behaviour. However, the influence of anthropogenic factors tends to elevate data variability, occasionally masking the natural relationships that govern their distributions. We apply different treatments of data to develop factor analysis using log-transformed data, and centred log-ratio (clr) transformed data to compare and improve the geochemical interpretation of this important zone. Factor analysis has been developed with these results to compare with previously published research on factor analysis in raw data. Factor score interpolated maps were also generated using both lognormal and clr-transformed data to visualize better the distribution and the different geochemical associations in the IPB. This study shows the importance of the different data treatments and the improvement of the clr-transformed multivariate analysis to reduce the dilution or overestimation of the results of some elements that cause erroneous interpretations of the data.

Application of Machine Learning to Research on Trace Elemental Characteristics of Metal Sulfides in Se-Te Bearing Deposits

This study focuses on exploring the indication and importance of selenium (Se) and tellurium (Te) in distinguishing different genetic types of ore deposits. Traditional views suggest that dispersed elements are unable to form independent deposits, but are hosted within deposits of other elements as associated elements. Based on this, the study collected trace elemental data of pyrite, sphalerite, and chalcopyrite in various types of Se-Te bearing deposits. The optimal end-elements for distinguishing different genetic type deposits were recognized by principal component analysis (PCA) and the silhouette coefficient method, and discriminant diagrams were drawn. However, support vector machine (SVM) calculation of the decision boundary shows low accuracy, revealing the limitations in binary discriminant visualization for ore deposit type discrimination. Consequently, two machine learning algorithms, random forest (RF) and SVM, were used to construct ore genetic type classification models on the basis of trace elemental data for the three types of metal sulfides. The results indicate that the RF classification model for pyrite exhibits the best performance, achieving an accuracy of 94.5% and avoiding overfitting errors. In detail, according to the feature importance analysis, Se exhibits higher Shapley Additive Explanations (SHAP) values in volcanogenic massive sulfide (VMS) and epithermal deposits, especially the latter, where Se is the most crucial distinguishing element. By comparison, Te shows a significant contribution to distinguishing Carlin-type deposits. Conversely, in porphyry- and skarn-type deposits, the contributions of Se and Te were relatively lower. In conclusion, the application of machine learning methods provides a novel approach for ore genetic type classification and discrimination research, enabling more accurate identification of ore genetic types and contributing to the exploration and development of mineral resources.

Tellurium Transport and Enrichment in Volcanogenic Massive Sulfide Deposits: Numerical Simulations of Vent Fluids and Comparison to Modern Sea-Floor Sulfides

Abstract Volcanogenic massive sulfide deposits may represent a significant future source of Te, which is a critical element important for the green energy transition. Tellurium is enriched in these settings by up to 10,000 times over its crustal abundance, indicating that fluids in sea-floor hydrothermal systems may transport and precipitate Te. The major element composition of these hydrothermal fluids is controlled by fluid-rock interaction and is well documented based on experimental, modeling, and natural studies; however, controls on Te mobility are still unknown. To better understand Te enrichment in this deposit type, numerical simulations of the mafic-hosted Vienna Woods and the felsic-hosted Fenway sea-floor vents in the Manus basin were performed to predict Te mobility in modern sea-floor hydrothermal vent fluids and Te deposition during sulfide formation. These simulations demonstrate that the mobility of Te in sea-floor hydrothermal systems is primarily controlled by fluid redox and temperature. Tellurium mobility is low in reduced hydrothermal fluids, whereas mobility of this metal is high at oxidized conditions at temperatures above 250°C. Numerical simulations of the reduced vent fluids of the mafic-hosted Vienna Woods site at the back-arc spreading center in the Manus basin yielded Te concentrations as low as 0.2 ppt. In contrast, the more oxidized model fluids of the felsic-hosted Fenway site located on Pual Ridge in the eastern Manus basin contain 50 ppt Te. The models suggest that Te enrichment in these systems reflects rock-buffer control on oxygen fugacity, rather than an enriched source of Te. In fact, the mafic volcanic rocks probably contain more Te than felsic volcanic rocks. The association of elevated Te contents in the felsic-hosted Fenway system likely reflects magmatic volatile input resulting in lower pH and higher Eh of the fluids. More generally, analysis of sulfide samples collected from modern sea-floor vent sites confirms that redox buffering by the host rocks is a first-order control on Te mobility in hydrothermal fluids. The Te content of sulfides from sea-floor hydrothermal vents hosted by basalt-dominated host rocks is generally lower than those of sulfides from vents located in felsic volcanic successions. Literature review suggests that this relationship also holds true for volcanogenic massive sulfides hosted in ancient volcanic successions. Results from reactive transport simulations further suggest that Te deposition during sulfide formation is primarily temperature controlled. Modeling shows that tellurium minerals are coprecipitated with other sulfides at high temperatures (275°–350°C), whereas Te deposition is distinctly lower at intermediate (150°–275°C) and low temperatures (100°–150°C). These predictions agree with geochemical analyses of sea-floor sulfides as Te broadly correlates positively with Cu and Au enrichment in felsic-hosted systems. The findings of this study provide an important baseline for future studies on the behavior of Te in hydrothermal systems and the processes controlling enrichment of this critical mineral in polymetallic sulfide ores.