Early Sulfide Research Articles

Distribution of Co, Te, Se in the porphyry copper systems: A case study of the Tonglvshan deposit, Eastern China

Porphyry copper systems contain porphyry Cu, skarn, carbonate-replacement and epithermal deposits, and presently supply nearly all the Te and Se, and have the potential to produce Co as by-product in the future. However, few studies have investigated the distribution of Co, Te, and Se in the specific porphyry-skarn deposit. Detailed mineralogical and geochemical analyses were conducted to investigate the distribution of Co, Te, and Se across porphyry, skarn, and carbonate-replacement ore types in the Tonglvshan porphyry-skarn Cu-Fe-Au deposit, Eastern China. The early sulfide stage in three ore types is characterized by Co-bearing pyrite (Py1a, Co up to 1.3 wt%) + droplet-like tetradymite ± hessite ± cattierite. The texture transition from coarse-grained, pore-free to porous Py1a in porphyry and skarn type ores suggests a shift from stable physico-chemical conditions to gentle fluid boiling, resulting in the precipitation of Co-and Te-bearing minerals. In contrast, fine-grained euhedral Py1a in carbonate-replacement type ores implies rapid cooling from high-temperature fluid interaction with marble.The late sulfide stage, which only occurs in skarn and carbonate-replacement type ores, is characterized by Co-rich pyrite (Py2) + carrollite + hessite + Bi-sulfosalts. In skarn type ores, tetradymite-kawazulite solid solution (TKSS) + hessite + native Te + naumannite reflects intense boiling, leading to an increase in fO2 and pH that precipitates Py2b (Co up to 19.2 wt%) and carrollite, while Te and Se may precipitate through vapor phase condensation. Conversely, the presence of fine-grained carrollite, zoned Py2a, sphalerite, and galena in carbonate-replacement type ore suggests that rapid cooling and increasing pH, resulting from fluid mixing, played a significant role in the precipitation Co and Te. Furthermore, the porous texture resulting from coupled dissolution-reprecipitation (CDR) during the late sulfide stage also provided favorable conditions for the formation of micro-nano sized critical metal particles.

Application of geological and short wavelength infrared (SWIR) spectroscopy mapping in the Mailong gold deposit, East Kunlun: Implications for exploration targeting

Widespread regolith cover makes it difficult to identify the anomalous size of their mineralogical or geochemical footprint at the surface in gold exploration. Short wavelength infrared (SWIR) spectroscopy with effective identification of clays and other hydrous minerals shows potential application in gold exploration. The detailed geological and short wavelength infrared (SWIR) spectroscopy mapping was conducted in the newly-discovered orogenic-type Mailong gold deposit (13.06 t @ 6.29 g/t Au), East Kunlun, to determine alteration stage and mineral assemblages and discuss the potential values of SWIR spectral in gold exploration.In the Mailong area, magmatic rocks consist of granodiorite, biotite granodiorite, plagiogranite and mafic dikes, and the gold mineralization shows a close spatial and temporal relationship with mafic dikes. The earliest chloritization (chlorite-quartz) is widely distributed in granodiorite, biotite granodiorite and plagiogranite. The following potassic alteration (hydrothermal K-feldspar and quartz) is developed along high-angle fault/fracture, which cut through granodiorite, biotite granodiorite and plagiogranite. The subsequent sulfide alteration (chlorite-muscovite-sulfide-carbonate) overprints the former potassic and chloritization alteration, and shows spatial association with mafic dikes. Native gold occurs in fracture arsenopyrite or associated with minerals such as pyrite, and chalcopyrite during the early sulfide stage. Supergene alteration is characterized by limonite and malachite. At Mailong, the SWIR data indicate that the most abundant alteration minerals (chlorite, white micas and ankerite) mainly occurred in the northern area. White mica Al-OH absorption occurs at longer wavelengths (Pos2200 = 2202.5 ∼ 2203 nm) and higher Illite crystallinity (IC = 1.2 ∼ 3.1) probably reflecting a higher temperature and pH conduit at the bottom of ZK0001 and ZK0801. The sharp shift of IC values near the bottom reflects the control of fault. This area is also situated at the V-shaped intersections of the three granitic intrusions and structural transection, indicating more of a possible hydrothermal fluid channel than a mineralization center. Low-grade Au mineralization (Au = 0.1 ∼ 0.5 g/t) is mainly distributed within hydrothermal channels with higher Pos2200 (mainly 2022.5 ∼ 2203 nm) and IC values (mainly 1.2 ∼ 3.1), while high-grade Au endowment associated with mafic dikes has low Pos2200 (mainly 2201 ∼ 2202.5 nm) and IC values (mainly 0.43 ∼ 1.2). Meanwhile, an equation of distance = -15*IC + 31 (R2 = 0.47) can be summarized for low-grade orebodies vectoring. Integrating geological mapping and spectral data, target areas for high-grade ore bodies can be outlined using the criteria of white mica, shorter wavelength of Al-OH absorption position (Pos2200 = 2201 ∼ 2202.5 nm), lower IC values (IC = 0.43 ∼ 1.2), and chlorite Fe-OH absorption position Pos2250 (>2247 nm) along with occurrences of mafic dikes. This study demonstrates that utilizing the detailed SWIR identification in conjunction with accurate geological mapping has great potential for greenfield exploration of orogenic gold deposits.

Potential controls on magmatic Ni-Cu sulfide mineralization in orogenic belts: Constraints from mineral compositions of the Huangshandong and Erhongwa intrusions in eastern Tianshan, NW China

Numerous Permian mafic-ultramafic intrusions are situated in the eastern Tianshan Orogen at the southern margin of the Central Asian Orogenic Belt. These intrusions demonstrate a diverse range of magmatic Ni-Cu sulfide mineralization. Notably, the Huangshandong intrusion hosts a large Ni-Cu sulfide deposit, whereas the Erhongwa intrusion lacks any economically significant sulfide mineralization. Both intrusions exhibit similar lithologies and mainly consist of lherzolite, gabbro, gabbronorite and diorite.To elucidate the controlling factors influencing the disparity in mineralization between two intrusions, analyses were conducted on the compositions of olivine, spinel, pyroxene and amphibole. Olivine grains from the Erhongwa lherzolite have lower Ni (361–943 ppm) contents than those from Huangshandong layered lherzolite (Ni 684–864 ppm) and Huangshandong massive lherzolite (Ni 1218 to 1878 ppm). This discrepancy may be attributed to early sulfide separation occurring at greater depths. Modeling results indicated that for the Huangshandong mantle source, 1 % slab-derived melts and 2 % slab-derived fluids were incorporated; conversely, for the Erhongwa mantle source, approximately 2.5 % slab-derived melts and 0.5 % slab-derived fluids were added.Parental magmas of the Erhongwa intrusion exhibit higher oxygen fugacity and water contents than those of the Huangshandong intrusion. Specifically, the magma of the Erhongwa intrusion undergoes magma evolution within a shallow magma chamber, whereas the magma of the Huangshandong intrusion gains sulfide saturation within a deep magma chamber. This research suggests that factors including mantle source features, suitable timing for sulfide separation, and depth of magma chamber are essential for Ni-Cu sulfide mineralization in mafic-ultramafic intrusions in convergent margin setting.

Genesis of the Shaquanzi Zn–Pb deposit in the Eastern Tianshan, NW China: Constraints from geology, fluid inclusion and isotope geochemistry

The Shaquanzi Zn–Pb deposit, located in the Central Tianshan Terrane, is mainly hosted by siliceous slates and carbonaceous marbles of the Mesoproterozoic Kawabulake Group, and its mineralization / alteration can be divided into skarn period (I: early skarn stage, II: late skarn stage), quartz-sulfide period (III: early sulfide stage, IV: late sulfide stage and V: quartz-calcite stage) and supergene period (VI: supergene alteration stage). The W-type fluid inclusions (FIs) were identified in the garnet, chlorite, quartz, and calcite in skarn and quartz-sulfide periods. Detailed fluid inclusion study shows temperature of fluids decreased from Stage I (510–520 °C) through, Stage III (481–507 °C), Stage IV (248–417 °C, peak at 280–400 °C) to Stage V (148–260 °C, peak at 200–220 °C), with salinities of 20.8–22.2 wt% NaCl eqv., 19.8–29.1 wt% NaCl eqv., 10.6–27.8 wt% NaCl eqv. (peaks at 20–23 wt%), and 21.6–29.9 wt% NaCl eqv. (peak at 23–27 wt%), respectively, indicating that the ore-forming fluids consisted of a high-medium salinity and Na-Mg-Fe-Ca-rich fluid system, and may have evolved from high-medium temperature to medium temperature. The H–O isotopic compositions varied from Stage III (δ18OH2O = 7.7 ‰–9.0 ‰ and δDH2O = − 105 ‰ to − 91 ‰) through Stage IV (δ18OH2O = 2.6 ‰ to 4.3 ‰ and δDH2O = − 114 ‰ to − 111 ‰) to Stage V (δ18OH2O = − 4.2 ‰ to − 3.7 ‰ and δDH2O = − 119 ‰ to − 96 ‰), suggesting that the ore-forming fluid sources may have evolved from magmatic fluids to meteoric water. The average δ34SH2O values of the early sulfide, late sulfide, and quartz-calcite stages are 5.7 ‰, 8.5 ‰ and 14.0 ‰, respectively, indicating that the sulfur in the early stage was mainly derived from magmatic hydrothermal sulfur, while the increase of the δ34SH2O values in the late stages is likely to be sourced from the Kawabulake Group through water–rock reaction. Above all, we propose that the Shaquanzi may have been a skarn-type Zn–Pb deposit.

EVIDENCES OF MINERAL MELTING IN THE ORES OF THE SVETLINSK GOLD DEPOSIT, SOUTH URALS, RUSSIA

For the large Svetlinsk gold deposit (South Urals) evidences of partial melting of minerals and possible participation of polymetallic melts in the concentration and redistribution of gold and other metals are given. Finding of bismuth and antimony minerals in ores, among which there are gold minerals new to the deposit (pampaloite, montbrayite and aurostibite), specific mineral intergrowths (polymineral Sb–Bi–Pb–Te–Ag–Au drop inclusions), enrichment of early sulphides with Low-Melting-point Chalcophile Elements (LMCE), high formation temperatures for ore assemblages (up to 400°C), as well as the occurring metamorphism of amphibolite facies indicate the possibility of the formation of such melts. Polymetallic melts at the deposit could be formed both by partial melting of early sulphides and directly from hydrothermal fluids. The signs of melting also include simplectites of calaverite and native gold in the marginal parts of the large montbrayite grain.

Earlier stage, higher temperature, and deeper space facilitate indium precipitation in a skarn system, as exemplified by the Baoshan Pb-Zn polymetallic deposit, South China

Indium (In), one of the strategic critical metal elements, is preferred to be enriched in the skarn system, but the enrichment regularity in terms of temporal and spatial distribution in a specific skarn Pb-Zn deposit remains unclear. To address the problem, we conducted a systematic geological, mineralogical, and trace element geochemical investigation on the Baoshan In-rich Pb-Zn polymetallic deposit, Hunan Province. This deposit is situated in the central part of the famous Nanling W-Sn-Pb-Zn polymetallic metallogeny belt, South China. Three ore districts in the Baoshan deposit with distinct economic element associations are divided, including the Central District (dominated by Cu-Mo), West District (dominated by Pb-Zn), and North District (dominated by Pb-Zn). They comprise a typical skarn system, including the outcropped granodiorite porphyry, typical skarn mineral assemblages, and Pb-Zn-hosting Carboniferous limestone. We systematically sampled the representative Pb-Zn ores in two ore districts (West and North) and three underground levels (-270 m, −230 m, and −190 m). Four types of sphalerites with different mineral associations and mineralogical characteristics were identified, that is, Sp1a and Sp1b (formed in the early sulfide stage), as well as Sp2a and Sp2b (formed in the late sulfide stage). Our EPMA (Electron Probe Micro-Analyzer) and LA-ICP-MS (Laser Ablation Inductively Coupled Plasma Mass Spectrometer) analyses reveal the four types of sphalerite have distinct chemical compositions. Such as, the mean value of indium is 3524 ppm for Sp1a, 142 ppm for Sp1b, 48.03 ppm for Sp2a, and 87.98 ppm for Sp2b in a decreasing order, and a similar trend of calculated temperatures ranging from 336 to 135 °C using GGIMFis thermometers can be obtained. Further LA-ICP-MS trace elements mapping show that the core of Sp1a is relatively enriched in more In, Cu, Sn, and Ag contents. Spatially, the sphalerites in the deep contain a higher indium content (mean = 1581 ppm) than those in the shallow (107.20 ppm) in the vertical profile. In the planar, indium is more enriched in the West District (mean = 1090 ppm) than in the North District (60.92 ppm). The indium distribution regularity reflects that the metals-carrying magmatic hydrothermal fluids flow from Central District, through the West District, to the North District. Collectively, we conclude that indium prefers to be enriched in the earlier stages, higher temperature, and deeper space during the sphalerite crystallization in the Baoshan skarn system, and therefore highlight the deep space of Baoshan West District is a promising target for indium exploration. This new finding maybe shed light on the scientific understanding on indium enrichment and associated exploration strategies in the similar skarn Pb-Zn metallogenic systems.

Genesis of the Lamasu large skarn Cu deposit, northern Xinjiang: Constraints from garnet U–Pb dating, micro‐textural and geochemical analyses

The Lamasu deposit is the first large copper (Cu) deposit with ~0.6 Mt Cu reserve in the Chinese Western Tianshan Orogen (NW China). The Cu orebodies are mainly hosted in the exoskarn of the Proterozoic Kusongmuqieke Group. Now, the metallogenic mechanism of newly discovered skarn Cu orebodies (0.5 Mt Cu) remains poorly constrained. In this study, we conducted LA‐ICP‐MS U–Pb isotope dating, EPMA and LA‐ICP‐MS geochemical analyses on different generations of garnet from Lamasu to elucidate the magmatic hydrothermal evolution and its timing. Garnets from the Lamasu exoskarn can be divided into three types: reddish‐brown coarse‐grained Grt‐I, light brown fine‐grained Grt‐II and yellowish‐green heterogranular Grt‐III, with U–Pb age of 389.1 ± 2.0 Ma, 387.1 ± 1.8 Ma and 387.0 ± 2.3 Ma, respectively. These dates represent the oldest Cu mineralization age in the Chinese Western Tianshan, coeval with the Middle Devonian subduction of the North Tianshan oceanic plate. Grt‐I to Grt‐III particles are mainly andradite with minor grossularite, and they have different REE compositions. The Grt‐I has total REE contents (∑REE) of 101.47 to 262.87 ppm, with steeply right‐inclining REE distribution patterns (LREE/HREE of 3.81 to 68.50) and positive Eu anomaly. The Grt‐II core has ∑REE of 163.49–249.52 ppm, LREE/HREE of 2.00–4.71, and negative Eu anomaly. The Grt‐II rim has ∑REE of 46.34–99.99 ppm, with LREE/HREE of 18.06–177.23, and positive Eu anomaly. The ∑REE of Grt‐III range from 31.71 to 219.02 ppm, with flat REE distribution pattern and positive Eu anomaly, and the LREE/HREE ranges from 2.16 to 9.07. These garnets have similar trace element compositions, featured by LILE‐depletions (e.g., Rb, Ba and Sr) and HFSE enrichments (e.g., Th, U, Nb and Ce). Micro‐texture and geochemical composition of garnets indicate that the Lamasu magmatic hydrothermal system could have changed from an open to a closed environment, and from infiltration metasomatism to diffusive metasomatism, which formed Grt‐I, Grt‐II and Grt‐III successively. These garnets generally formed in a relatively oxidized fluid environment, which inhibited early sulphide precipitation and favoured for Cu enrichment during the ore fluid evolution.

Минеральный состав руд месторождения Бесапантау

The results of mineralogical studies of the Besapantau deposit, typical of the Muruntau ore field (Central Kyzylkum), belonging to the low-sulfide gold-quartz geological-industrial type, are discussed. The most productive for gold is the early sulfide (pyrite-arsenopyrite) stage of mineralization. The minerals associated with gold and silver include pyrite, arsenopyrite, galena, fahlore, sulfoantimonides, and tellurides. Native gold varies in composition from electrum to very fine gold. Silver is present in the forms: native, gold-bearing, hessite, argentite, stephanite, pyrargyrite. Arsenopyrite can serve as an effective search indicator for gold in the conditions of forms, and also as the Central Kyzylkum, and the content of arsenic in ores can serve as a criterion for the degree of gold enrichment.

Formation of Fe-Ti oxide and Ni-Co sulfide ores by concentric tube flow and hydrous metal-rich melt recharge into the cooling crystal mush: Example from the Hongge intrusion in Panxi region, SW China

The Panxi (ultra-)mafic intrusions are relatively small compared with world-class ore-related (ultra-)mafic intrusions, but they host several super-large Fe-Ti oxide deposits and few small Cu-Ni (PGE) sulfide deposits. The mechanisms that concentrate huge amounts of oxide minerals into these small intrusions and form the distinct oxide and sulfide mineralization remain poorly understood. Here, we investigate the magma dynamics that produced extensive Fe-Ti oxide and coexisting Ni-Co sulfide mineralization in the Hongge intrusion of Panxi region, based on detailed field cross-cutting relations and petrographic observations, bulk-ore/rock geochemistry, and in-situ LA-ICP-MS magnetite trace element analyses. The Fe-Ti oxide ores include magnetite-poor (<60 vol%) disseminated and magnetite-rich (>60 vol%) massive types, with the former further divided into the gabbro-hosted (GH) and (olivine-)pyroxenite-hosted (OPH) subtypes. The GH oxide ores have Cr-poor (median 86.9 ppm) magnetite and abundant apatite interstitial to silicate minerals. In contrast, the OPH and massive oxide ores have Cr-rich (median 13,956 ppm) magnetite that envelops resorbed silicate minerals. Principal component analyses of bulk-ore and magnetite elemental contents reveal genetic links between the OPH and massive oxide ores, but remarkable genetic distinction from the GH oxide ores. Considering the overall lopolith-shape orebody geometry of several branch intrusions, the GH oxide ore formation may have involved spontaneous development of concentric tube flow zones within the cooling crystal mush. However, the lower P but much higher Cr-Cu-Co-Ni contents than the GH oxide ores and the sharp intrusion of massive oxide ores into the OPH oxide ores suggests that the OPH and massive oxide ores were probably formed by upward percolation and later intrusion of hydrous Fe-rich melts from a deep-seated magma reservoir into semi-solidified and fossilized mush, respectively. In addition, sulfide ores occur mainly as irregular/lenticular aggregates in massive oxide ores and are depleted in Cu and platinum group elements (PGEs), indicating early, deep-level sulfide segregation that scavenged the Cu and PGEs from the magmas. Hence, we envisage that the assimilation of S-deficient wall-rocks into basaltic magmas may have induced the early sulfide saturation and retain the majority of Fe for later precipitation as principal oxide and minor PGE-Cu-depleted sulfide ores.

Geology, sulphide geochemistry and geochronology of the Romsås Ni-Cu-Co mineralisation, Norway: Implications for ore formation and regional prospectivity

The Romsås intrusion, located in the southern portion of the Idefjorden lithotectonic unit, is part of a cluster of small to medium-sized mafic intrusive bodies which host NiCu sulphide mineralisation, referred to as the Indre Østfold metallogenic area. The Romsås is an almost 1 km-long intrusion with rounded shape, comprising undifferentiated quartz-norite with local orbicular texture. The assemblage, comprising cumulus orthopyroxene and plagioclase, is partly recrystallised and altered, thus orthopyroxene is partly replaced by amphibole, whereas plagioclase is locally replaced by epidote. Locally, garnet, amphibole, plagioclase and magnetite define a granoblastic texture as product of amphibolite-facies metamorphism. Several sulphide-rich lenses, normally up to 5 m wide, occur within the Romsås intrusion and display a sharp contact with the host noritic rocks. The textures vary from disseminated, net-textured and massive sulphides. The sulphide assemblage is homogeneous within the deposit and consists mainly of pyrrhotite, followed by pentlandite, and minor chalcopyrite, with variable alteration of pentlandite.This contribution provides the first systematic characterisation of the Romsås Ni-Cu-Co mineralisation and constraints for its formation and geodynamic setting. We have measured the concentrations of S, PGE, TABS+ (Te, As, Bi, Sb and Se) and other chalcophile elements in both whole rock and sulphide minerals from different ore textures, and UPb and Hf isotope systematics in zircon. The Ni and Cu concentrations in 100% sulphides are around 2% and 1%, respectively. The PGE concentrations in all sulphide-bearing samples are low, generally below 0.3 ppm, with Pt and Pd displaying a broad positive correlation and Pt/Pd ratios varying from 1 to 2. Different ore types are modelled to have formed from a mantle-derived parental magma with higher Cu/Pd ratios and lower Pd contents than mantle values, interpreted as the result of 5% prior crystallisation under sulphide-saturated conditions. Negative mantle-normalised Nb anomalies relative to Th, As and Sb suggest around 10% of assimilation of a component similar to lower crust by the parental magmas. Moreover, S/Se ratios greater than mantle values likely reflect the combined effect of Se depletion during early sulphide removal and external S addition upon crustal assimilation. The Romsås Ni-Cu-Co mineralisation likely formed as a result of sulphide segregation in response to external S addition during several magma pulses. The composition of the sulphide ores can be modelled by an R-factor of around 500. A significant budget of the chalcophile elements is not hosted by sulphide minerals and must be thus accounted for other discrete phases, such as platinum-group minerals. Nevertheless, trace elements distribution in sulphides supports only local remobilisation of chalcophile elements and records compositions comparable to sulphides from pristine NiCu deposits worldwide. Sulphide alteration may have led to exsolution of a parcel of chalcophile elements from sulphide lattice. A UPb zircon crystallisation age of 1551 ± 10 Ma, εHft values between ca. 3.5 and 6, and regional geological considerations suggest that the intrusion formed as part of an arc or back-arc rift setting in the Idefjorden lithotectonic unit. The Romsås sulphide mineralisation represents another example of magmatic sulphide deposit formed at an arc-related geodynamic setting, normally unconventional for the formation of this type of deposit. Therefore, our findings support that arc-related settings in Idefjorden lithotectonic unit, southern Norway, should also be regarded as potential for the formation of Ni-Cu-PGE deposits.

Chalcophile element systematics of Mariana Trough basalts and implications for sulphide saturation evolution of intra-oceanic back-arc magmatic systems

ABSTRACT Magmatic sulphides largely control the behaviour of chalcophile elements in evolving magmas and also play critical roles in ore-forming processes at convergent plate margins. Magmas at the back-arc spreading centre of Mariana Trough are less affected by slab-derived fluids than Mariana arc basalts. However, whether the evolution of chalcophile elements in Mariana Trough magmas resembles or differs from those in arc magmas is poorly known. Based on the detailed petrological and geochemical studies, we present high-precision analyses of whole-rock chalcophile element (S, Cu, Ag, Re, Pd, Pt, Ru, Ir) contents for a suit of basaltic lavas (n = 15) from the central Mariana Trough. The occurrence of sulphides in high-Mg olivine crystals (Fo80) indicates that at least one episode of sulphide saturation occurred during early-stage magmatic evolution. The sulphur contents of most basalts were not significantly affected by degassing processes due to low oxidation state and high hydrostatic pressures. Instead, progressive fractionation of liquid sulphide with magmatic evolution is the dominant process, as reflected by sulphide petrography, the decrease in Cu, Ag, Pd, and Pt contents, and concomitant increase in Cu/Pd ratios (22,500–708,500), as well as nearly constant Cu/Ag (mean of 3137 ± 848, 1s) with decreasing MgO. We attribute early sulphide saturation of Mariana Trough basalts to their generation and evolution under relatively reducing conditions, with the limited effect of slab components. Combined with data from other island arc and back-arc lavas, we further show that the extent of adding slab-derived components, regardless of specific arc and back-arc tectonic settings, are determinants of the sulphide evolution and chalcophile element behaviour in magmatic systems above intra-oceanic subduction zones. Early magmatic sulphide saturation at central Mariana Trough would result in barren magmatic systems that are not suitable for the large-scale Cu-Au mineralization at the seafloor.

Black shales and mesozonal quartz vein‐hosted Au: The Truchas Syncline, Spain and the Harlech Dome, Wales, a comparative study

A comparative study of quartz vein‐hosted gold occurrences associated with Palaeozoic metapelites in two areas of Wales and Spain combines new, previously unpublished and published data. Metamorphic grade is greenschist in both areas, but very low‐grade indicators in the host metapelites distance the environment from the greenschist/amphibolite transition zone required for some orogenic gold occurrences. Basin fertility for Au is indicated by the presence of auriferous pyrites in the protolith black shales in Spain. Only minor igneous activity has taken place in both study areas. Mineral parageneses are similar, with early sulphide phases characterized by As/Co and later auriferous phases by Cu/Pb/Zn sulphides. Mesozonal P–T conditions apply at deposition in both terranes. In Spain, mineralisation typically occurs in quartzites near to the metapelites, but not where the veins are in contact with them, and extensional faulting appears to be a stronger control over mineralisation than geochemical interaction with metapelite wall‐rocks. In Wales, both structural and geochemical factors (C content of the wall‐rocks and coupled oxidation of NH4 ions substituted in wall‐rock phyllosilicates to produce CH4 and N2) could have a role in Au deposition. In both areas, minor cross‐fault systems between larger faults are typical hosts of the mineralisation. Assignment is made to different subtypes of the orogenic gold model but these subtypes share the characteristic of a local source. This has implications for exploration methodology in epizonal/anchizonal metapelite‐dominated terranes, where indicators of basin fertility for Au within the protolith itself assume importance.

The Origin of Magmas and Metals at the Submarine Brothers Volcano, Kermadec Arc, New Zealand

Abstract International Ocean Discovery Program (IODP) Expedition 376 cored the submarine Brothers volcano of the Kermadec arc to provide insights into the third dimension and the evolution of the volcano and its associated ore-forming systems. We present new petrological and geochemical data on dacitic rocks drilled from Brothers as well as mafic rocks collected at two adjacent ridges. These data include major and trace element compositions of whole rocks, including many economically important metals and metalloids such as Cu, Ag, Pt, Au, Mo, As, Sb, Tl, and Bi, plus Sr-Nd-Pb isotope compositions as well as in situ analyses of glasses and minerals. We show that the basalts and basaltic andesites erupted at the volcanic ridges near Brothers represent potential mafic analogues to the dacites that make up Brothers volcano. Mantle melting and ore potential of the associated magmas are locally enhanced by raised mantle potential temperatures and a high flux of subducted components originating from the partially subducted Hikurangi Plateau. As a result, the parental melts at Brothers are enriched in ore metals and metalloids relative to mid-ocean ridge basalts (MORBs), and a high melt oxidation state (Δ log fO2 of +1.5 fayalite-magnetite-quartz [FMQ]) suppresses early sulfide saturation. However, solid sulfide crystallization occurs late during magma differentiation, with the result that the dacitic lavas at Brothers volcano are strongly depleted in Cu but only moderately depleted in Ag and Au. The dacites at Brothers thus have a high fertility for many metals and metalloids (e.g., As, Sb, Bi), and fluids exsolving from the cooling magma have a high ore-forming potential.

A Role for Crustal Assimilation in the Formation of Copper-Rich Reservoirs at the Base of Continental Arcs

Abstract Understanding the behavior of chalcophile elements during the evolution of arc magmas is critical to refining models for the formation and distribution of porphyry copper deposits used in mineral exploration. Because magmas in continental arcs undergo copper depletion during their early differentiation, a widely held hypothesis posits that the removed copper is locked at the base of the crust in copper-rich cumulates that form due to early sulfide saturation. Testing this hypothesis requires direct evidence for such copper-rich reservoirs and a comprehensive understanding of the mechanisms driving sulfide saturation. Interaction between oxidized magmas and reducing crustal material in island arcs has been shown to be an efficient process causing sulfide saturation. However, the extent to which crustal assimilation impacts the flux of chalcophile elements during magmatism in thick continental arcs remains to be established. Here, we provide a deep perspective into these problems by studying a suite of subarc cumulate rocks from the Acadian orogen, New England (USA). These cumulates record the imprint of subduction zone magmatism and represent the residues left behind during the genesis of intermediate to evolved Acadian magmas (ca. 410 Ma). We find that the most primitive Acadian cumulates are enriched in copper (up to ~730 µg g–1) hosted by sulfide phases, providing direct evidence for the formation of lower crustal copper-rich reservoirs. The Acadian cumulates reveal a wide range of δ34S values, from –4.9‰ in the ultramafic rocks to 8‰ in the most evolved mafic rocks. The negative δ34S values observed in the most primitive and copper-rich cumulates (avg –3‰) reflect the assimilation of isotopically light sulfur from surrounding sulfidic and graphite-bearing metasedimentary rocks (δ34S of –19 to –12‰), whereas the more evolved cumulates with positive δ34S signatures may have formed from different magma batches that experienced less sediment assimilation. The assimilation of these reducing metasedimentary rocks caused a critical drop in oxygen fugacity (~DFMQ –2.5 to –1.9; FMQ = fayalite-quartz-magnetite buffer) in the evolving magmas, ultimately leading to extensive sulfide saturation and the consequent formation of copper-rich subarc cumulates. Assimilation-driven sulfide saturation may be a common process at the root of thickened arc crusts that triggers the formation of lower crustal copper-rich reservoirs, which play a pivotal role in the fate of copper during arc magmatism. Thus, deeply buried reducing metasedimentary crustal material at the base of continental arcs can act as a barrier to the magmatic flux of chalcophile elements and may play a crucial role in the genesis and distribution of porphyry copper deposits.

Role of magma differentiation depth in controlling the Au grade of giant porphyry deposits

Porphyry deposits are the world's most important source of Cu and a major source of Au. It has been recognized that low Au grades generally characterize porphyry deposits in thick continental arcs, like the Andes, where the magmas are likely to differentiate at depth. In contrast, Au-rich porphyries are mainly found in thin island arcs, for example, those of the southwest Pacific, or associated with short extensional periods in continental arcs, where the magmas are likely to experience relatively shallow differentiation. However, the key factors that control this difference remain debated. This study shows that the Au grade of giant porphyry deposits and La/Yb ratios of the ore-associated suites are negatively correlated (r=∼0.7, p=10−7). We attribute the negative correlation to be mainly due to varying sulfide saturation histories, modulated by the depth of magma differentiation.Magmas differentiating in deep crustal reservoirs are likely to reach sulfide saturation early due to high pressure and early depletion of FeO (calc-alkaline trend). Early sulfide saturation causes most Au to be held in cumulus sulfides, making it unavailable to enter ore-forming fluid released in the upper crust, resulting in Au-poor porphyry systems. In contrast, magmas evolving in shallow reservoirs are likely to experience late sulfide saturation because of the high sulfur solubility induced by low pressure and the high FeO content of the melts (tholeiitic trend). Late sulfide saturation enhances the potential of a magmatic system to form Au-rich porphyry deposits due to the high Au content of the magma at voluminous fluid saturation and efficient Au transfer from melt to the ore-forming fluids via sulfide-fluid interaction. The link between average magma differentiation depth and Au content is supported by platinum-group element geochemistry of the porphyry ore-forming suites, which shows that the magmas differentiating at shallower depths (lower La/Yb) reach sulfide saturation later and therefore have higher Au concentrations than those that differentiate at deeper levels (higher La/Yb). Numerical models for ore-associated magmas with different sulfide saturation histories indicate that variations in the Au grades of giant porphyry deposits can be explained by the variations in the timing of sulfide saturation. Based on the results, we propose that Au concentration in the magma, modulated by average magma differentiation depth and sulfide saturation history, is one of the critical factors controlling the Au grade of giant porphyry Cu deposits.

Refertilization of depleted mantle peridotite in the Nagaland–Manipur ophiolite, north‐east India: Constraints from PGE, mineral, and whole‐rock geochemistry

This paper discusses whole‐rock geochemistry, mineral chemistry, and platinum group element (PGE) systematics of depleted mantle rocks (harzburgite and dunite) from the northern part of Nagaland–Manipur Ophiolite (NMO), north‐east India, to comprehend their source features, fractionation behaviour of PGE during magmatic evolution, and its tectonic origin. The studied ultramafic rocks are characterized by a low concentration of CaO (0.57–0.71 wt%), Al2O3 (0.18–0.92 wt%) with ∑REE of 1.135–2.702 ppm and high concentrations of MgO (38.70–44.21 wt%), Cr (1,843–4,572 ppm), and Ni (894–4,138 ppm). They show U‐shaped REE patterns [LREE and HREE enrichment (La/Sm)N = 1.85–4.11, (Dy/Yb)N = 0.51–0.85]. Olivine ranges Fo 88.18 to Fo92.23, whereas Cpx and Opx range En44.84 to En47.89 and En86.37 to En93.37 respectively. The chrome spinel Cr# [Cr/(Cr + Al)] and Mg# [Mg/(Mg + Fe2+)] are 0.47–0.83 and 0.31–0.60, respectively, which indicates recrystallization from a boninitic magma in a Supra‐Subduction Zone setting. Conventional thermometry indicates the equilibration temperatures of the dunite sample yielded high temperatures of ~850°C, suggesting their formation due to later interaction with high‐temperature percolating melts. The PGE contents in harzburgite are low (125.6–142.8 ppb) as compared to the dunite (248–360 ppb). They have high PPGE/IPGE and negative Pt* (Pt/Pt* = 0.73) anomaly, which is characteristic of re‐entry of PPGE into the system via reaction with percolating basaltic melt in the mantle wedge. Significantly higher concentration of PPGEs than IPGEs in the samples, indicating recrystallization of PPGEs with early sulphide fractionation. The presence of significant Rh and Pd enhancements relative to Pt in all samples suggests that Pt was removed during PGE fractionation. This could be one of the reasons for both harzburgite and dunite's sulphide undersaturation. PGE distribution in NMO ultramafic rocks was therefore validated as being governed by sulphide saturation in parental magma and altered not only by partial melting but also by fractionation during their production in the Supra‐Subduction Zone environment.

Enrichment mechanisms and occurrence regularity of critical minerals resources in the Yaojialing Zn skarn polymetallic deposit, Tongling district, eastern China

Critical minerals resources are widely used in emerging industries, and their mineralization characteristics and metallogenic regularity are of high importance. Skarn deposits are one of the important sources of critical minerals resources. Yaojialing deposit is a typical large skarn zinc polymetallic deposit in Tongling district of the Middle and Lower Yangtze River metallogenic belt. The ore bodies are mainly lenticular and veined occurrence along the proximal skarn zone and structural or lithologic contacts, respectively. We recognize five hydrothermal stages in the deposit: skarn stage, oxide stage, early sulfide stage, late sulfide stage and carbonate stage. The early and late sulfide stages are the main ore-forming stages. In addition to the production of zinc, gold and copper, the deposit also contains critical element resources such as cadmium, cobalt, selenium, and tellurium. Taking the Yaojialing deposit as an example, this paper shows the occurrence and distribution of critical minerals resources in a typical skarn deposit by using scanning electron microscope, TESCAN integrated mineral analyzer (TIMA), and sulfide LA-ICP MS analysis. Although there are no cadmium minerals in Yaojialing deposit, cadmium can incorporated in the sphalerite lattice, and sphalerite in veins has elevated cadmium content (average 5478.78 ppm). Tellurium content in various sulfides is very low, and it does not enter into the sulfide lattice. It mainly forms tellurobismuthite, hessite and tetradymite, which occur in Cu-Zn ore formed in the early sulfide stage, there are 227 tetradymite grains in a single rock section. Selenium occurs as naumannite in vein ore in the distal of the deposit; selenium can also incorporated the lattice of chalcopyrite and sphalerite, and the selenium content is elevated in sphalerite formed in the early sulfide stage (average 226.80 ppm). The cobalt mineral glaucodot is only found in skarn ore; cobalt easily incorporated the lattice of pyrite and sphalerite, and pyrite and sphalerite formed in the early sulfide stage are enriched in cobalt (average 1962.18 ppm). The characteristics of trace elements in pyrite and sphalerite show that temperature is the main factor affecting the distribution of critical minerals resources, high temperature is conducive to the enrichment of cobalt, selenium and tellurium, while low temperature is conducive to the enrichment of cadmium. Cadmium, cobalt, selenium, and tellurium have high content in specific parts of the deposit, which makes them potentially amenable to recovery.

Mineral Paragenesis, formation stages and trace elements in sulfides of the Olympiada gold deposit (Yenisei Ridge, Russia)

The mineral sequence and LA-ICP-MS study of the trace-elements distribution in chalcogenides (arsenopyrite, pyrite, pyrrhotite, sphalerite, chalcopyrite, ullmannite, tetrahedrite, berthierite, stibnite, gudmundite, jamesonite) of the Olympiada gold ore deposit (Yenisei Ridge, Russia) are presented. The deposit was formed in three stages, separated by tectonic breaks. Early (I) corresponds to the paragenesis of acicular arsenopyrite + pyrite + pyrrhotite. At the stage of base-metal sulfides (II), the deposition of the bulk of chalcopyrite, sphalerite and galena occurred. Mineral associations of these stages determined the gold-arsenic (Au-As) type of ores. The stage of late sulfides (III) is characterized by the paragenesis of antimony minerals (stibnite + berthierite + gudmundite) and corresponds to the gold-antimony (Au-Sb) ore type. Commercial concentrations of gold were formed at the early sulfides stage in the lattice bonded and nanosize mode in acicular arsenopyrite (12.5–1,512 ppm). The progress of the ore deposition process with the formation of late polymetallic and stibnite-berthierite mineralization led to recrystallization of early sulfides (prismatic arsenopyrite Au ∼ 36.4 ppm → dipyramidal arsenopyrite Au ∼ 0.5 ppm), remobilization and re-deposition of gold in a native form. Pyrite of the deposit does not contain significant amounts of gold (∼0.4 ppm). Silver is absent in early sulfides, but is concentrated in tetrahedrite (348.0–3,811 ppm), jamesonite (0.1–7.7 ppm), berthierite (0.1–2.3 ppm) and stibnite (0.2–2.0 ppm) of the later stage (III). Early sulfides (stage I) are characterized by the As-Au-W-Se-Te geochemical association; polymetallic sulfides (stage II) — by the Cu-Zn-Pb-Cd-In association; and late sulfides (stage III) — by the Sb-Co-Ni-Te-Bi-Pb-Hg-Ag association.

Genesis of the sediment-hosted Haerdaban Zn-Pb deposit, Western Tianshan, NW China: Constraints from textural, compositional and sulfur isotope variations of sulfides

The sediment-hosted Haerdaban Zn-Pb deposit is a newly discovered Zn-Pb deposit in the Sailimu terrane, Western Tianshan (NW China), containing ca. 0.64 Mt of ore at 6.19 wt% Zn and 1.09 wt% Pb. The mineralization consists mainly of veins, breccias and semi-massive sulfide ores within the dolomitic limestone and calcareous slate. Using LA-ICP-MS, this study investigates trace element and sulfur isotope composition of sulfide to constrain the genesis of the deposit. Four pyrite types were identified by variations in texture and composition. Porous pyrite (Py1) shows a significant enrichment in Mn, Ag, Sb, Tl, Ba, Pb, Cu, and Zn, whereas the pyrite overgrowth (Py2) and euhedral pyrite (Py3) are enriched in Co and As, but depleted in all other trace elements. This compositional trend is attributed to the release of trace elements from pyrite during recrystallization from a porous to massive texture. Pyrite (Py4) associated with sphalerite is inclusion-rich, but exhibits a depletion in most trace elements, except Ni and Sb. The underlying carbonaceous sediments are interpreted as a source of Ni, Sb and other metals for the ore-forming fluids. Sphalerite displays a wide variety of colors from dark brown to pale yellow, primarily related to variations in Fe contents. The overall Fe contents (0.25 to 6.12 wt%), Cd contents (524 to 1875 ppm) and Zn/Cd ratios (320 to 1258) in sphalerite are compatible with those of SEDEX Zn-Pb deposit. The contents of other elements in sphalerite are generally low. Calculated temperatures using trace element contents in sphalerite (GGIMFis geothermometer) range from 163 °C to 309 °C, indicating progressive cooling of ore-forming fluid. Pyrite, sphalerite and galena display a wide range of δ34S values from +3.9 to +18.3‰. The association of lower positive δ34S values (+3.9 to +8.8‰) and epithermal suite elements (Ni, As, Sb, and Tl) enrichment in porous pyrite indicate that sulfur in early sulfides was derived from thermochemical sulfate reduction (TSR) with a possible magmatic input. The dominant population of heavier δ34S values (+13.8 to +18.3‰) of massive sulfide support TSR as the main source of sulfur. The intermediate δ34S values (+7.0 to +13.0‰) of vein sulfide are likely a mixing of TSR-derived sulfur with light sulfur leached from diagenetic pyrite. The current data support the classification of Haerdaban as a metamorphosed SEDEX Zn-Pb deposit, where the main mineralization was the product of remobilization and upgrading of early exhalative ores during hydrothermal events.

Variable Modes of Formation for Tonalite–Trondhjemite–Granodiorite–Diorite (TTG)-related Porphyry-type Cu ± Au Deposits in the Neoarchean Southern Abitibi Subprovince (Canada): Evidence from Petrochronology and Oxybarometry

Abstract Most known porphyry Cu ± Au deposits are associated with moderately oxidized and sulfur-rich, calc-alkaline to mildly alkalic arc-related magmas in the Phanerozoic. In contrast, sodium-enriched tonalite–trondhjemite–granodiorite–diorite (TTG) magmas predominant in the Archean are hypothesized to be unoxidized and sulfur-poor, which together preclude porphyry Cu deposit formation. Here, we test this hypothesis by interrogating the causative magmas for the ~2·7 Ga TTG-related Côté Gold, St-Jude, and Clifford porphyry-type Cu ± Au deposit settings in the Neoarchean southern Abitibi subprovince. New and previously published geochronological results constrain the age of emplacement of the causative magmas at ~2·74 Ga, ~2·70 Ga, and ~ 2·69 Ga, respectively. The dioritic and trondhjemitic magmas associated with Côté Gold and St-Jude evolved along a plagioclase-dominated fractionation trend, in contrast to amphibole-dominated fractionation for tonalitic magma at Clifford. Analyses of zircon grains from the Côté Gold, St-Jude, and Clifford igneous rocks yielded εHf(t) ± SD values of 4·5 ± 0·3, 4·2 ± 0·6, and 4·3 ± 0·4, and δ18O ± SD values of 5·40 ± 0·11 ‰, 3·91 ± 0·13 ‰, and 4·83 ± 0·12 ‰, respectively. These isotopic signatures indicate that, although these magmas are mantle-sourced with minimal crustal contamination, for the St-Jude and Clifford settings the magmas or their sources may have undergone variable alteration by heated seawater or meteoric fluids. Primary barometric minerals (i.e. zircon, amphibole, apatite, and magnetite–ilmenite) that survived variable alteration and metamorphism (up to greenschist facies) were used for estimating fO2 of the causative magmas. Estimation of magmatic fO2 values, reported relative to the fayalite–magnetite–quartz buffer as ΔFMQ, using zircon geochemistry indicates that the fO2 values of the St-Jude, Côté Gold, and Clifford magmas increase from ΔFMQ –0·3 ± 0·6 to ΔFMQ +0·8 ± 0·4 and to ΔFMQ +1·2 ± 0·4, respectively. In contrast, amphibole chemistry yielded systematically higher fO2 values of ΔFMQ +1·6 ± 0·3 and ΔFMQ +2·6 ± 0·1 for Côté Gold and Clifford, respectively, which are consistent with previous studies that indicate that amphibole may overestimate the fO2 of intrusive rocks by up to 1 log unit. Micro X-ray absorption near edge structure (μ-XANES) spectrometric determination of sulfur (i.e. S6+/ΣS) in primary apatite yielded ≥ΔFMQ −0·3 and ΔFMQ +1·4–1·8 for St-Jude and Clifford, respectively. The magnetite–ilmenite mineral pairs from the Clifford tonalite yielded ΔFMQ +3·3 ± 1·3 at equilibrium temperatures of 634 ± 21 °C, recording the redox state of the late stage of magma crystallization. Electron probe microanalyses revealed that apatite grains from Clifford are enriched in S (up to 0·1 wt%) relative to those of Côté Gold and St-Jude (below the detection limit), which is attributed to either relatively oxidized or sulfur-rich features of the Clifford tonalite. We interpret these results to indicate that the deposits at Côté Gold and Clifford formed from mildly (~ΔFMQ +0·8 ± 0·4) to moderately (~ΔFMQ +1·5) oxidized magmas where voluminous early sulfide saturation was probably limited, whereas the St-Jude deposit represents a rare case whereby the ingress of externally derived hydrothermal fluids facilitated metal fertility in a relatively reduced magma chamber (~ΔFMQ +0). Furthermore, we conclude that variable modes of formation for these deposits and, in addition, the apparent rarity of porphyry-type Cu–Au deposits in the Archean may be attributed to either local restriction of favorable metallogenic conditions, and/or preservation, or an exploration bias.