Sulfide Segregation Research Articles

Mechanisms of Co enrichment in the Zhubu Ni–Co–PGE deposit in the Emeishan LIP, SW China: Constraints from mineral geochemistry and Fe–S isotopes of sulfides

The Zhubu Ni–Co–PGE sulfide deposit in the Permian Emeishan Large Igneous Province (LIP), SW China is hosted by a mafic–ultramafic intrusion that comprises two morphologically distinct ore-forming spaces: a central, layered sequence that represents a magma chamber surrounded by a marginal sub-vertical conduit zone. The marginal conduit zone contains significant Ni–Co–PGE sulfide mineralization, suggesting that high volumes of sulfide-bearing silicate melt flowed through the magma conduit system. Determining the hosts of Co is key to understanding the Co enrichment process in the Zhubu deposit, as well as in the Emeishan LIP as a whole. We assess this here using the geochemistry and Fe–S isotope compositions of sulfides in the Zhubu deposit. Cobalt is mainly concentrated in pentlandite sulfide in the websterite, with Co contents increasing in the order pyrrhotite < chalcopyrite < pyrite < pentlandite < violarite; the abundance of violarite, however, is notably lower than that of the other sulfides. The Co contents of pentlandite, pyrite, and chalcopyrite are negatively correlated with their Ni and Fe contents, suggesting that Co substitutes isomorphically for Ni and Fe in the sulfide structure. The δ56Fe values of sulfides increase in the order pyrrhotite < chalcopyrite < pentlandite < pyrite resulted from kinetic fractionation of Fe isotopes. The δ56Fe values of pentlandite and chalcopyrite in lherzolite are higher than those in websterite, implying that lherzolite and websterite formed in compositionally distinct magmas, Fe isotope compositions become heavier with crystal fractionation. The δ34S values of sulfides increase in the order pyrrhotite < pentlandite < chalcopyrite < pyrite, similar to the fractionation sequence of sulfide melts, suggesting that externally derived S was added to the magma and contributed to its sulfide saturation. The Co contents of chalcopyrite and pyrite vary positively with δ56Fe values, and negatively with δ34S values, indicating that the addition of externally derived S and resulting sulfide segregation were critical to Co enrichment.

Copper isotope fractionation during magmatic evolution in a convergent tectonic setting: Constraints from sulfide Cu-S isotopes and whole-rock PGE of the Xiarihamu Ni-Cu sulfide deposit

Nickel and cobalt are potentially critical metals in many countries because of their great significance for national security and economic development, and they are mainly derived from magmatic Ni-Cu‑platinum-group element (PGE) sulfide ore deposits hosted in mafic-ultramafic intrusions. Although Cu isotopes have been used to trace the metallogenic processes in Ni-Cu-(PGE) sulfide deposits, the Cu isotopic fractionation mechanism during magma generation and evolution in convergent tectonic settings is still debated. The Xiarihamu magmatic NiCu sulfide deposit, located in the East Kunlun orogenic belt, northern Tibetan Plateau, is the world's largest known magmatic NiCu sulfide deposit in an orogenic setting. Here we report the whole-rock element and sulfide CuS isotope compositions of samples from the Xiarihamu deposit. The δ65Cu and δ34S values of the sulfide grains from the massive, heavily disseminated, and disseminated sulfide ores range from 0.19 ‰ to 0.79 ‰, and from 4.2 ‰ to 9.4 ‰, respectively. Most of the samples have δ65Cu values higher than normal mantle values, except for two samples with δ65Cu values within the mantle composition range. The whole rock S/Se ratios range from 3200 to 22,500, and the Cu/Pd ratios range from 330 to 820,000, which are also mainly higher than the corresponding mantle values. Modeling calculations of the δ65Cu, S/Se, and Cu/Pd values reveal that the sulfide liquid to silicate melt mass ratio (R factor) is not the main reason for the observed δ65Cu variations in the Xiarihamu deposit. The variations in the Cu/Pd ratios of the whole-rock samples, and the sulfide δ65Cu and δ34S values with depth indicate that sulfide segregation and crustal contamination can reasonably jointly produce the Cu isotope variations in the Xiarihamu deposit, and the variations of samples from different parts of the deposit are caused by variations in these controlling factors. Therefore, Cu isotope fractionation in convergent tectonic settings is mainly caused by magma evolution. The complicated controlling factors of the Cu and S isotopes indicate that the correlation between δ65Cu and δ34S values may not be helpful in evaluating the metallogenic potential of Ni-Cu-(PGE) sulfide deposits. Cu isotopes can be used to ascertain the migration path of magmas.

Platinum-Group Elements and Nb-Ta geochemistry of the Deccan basalts from Kumbharli and other Ghat sections and the Koyna Seismic Zone, Maharashtra (India): Crustal contamination and implication for sulfide saturation of the magma

The Deccan basalts from Kumbharli, Nadlapur, Bijaynagar, Hazarmacchi, and Surli Ghat sections (surface samples) and the Koyna borehole-7 (KBH-7, sub-surface samples) from Maharashtra (western India) demonstrate a two-stage crystallization process. Olivine and chromite were crystallized earlier in a shallow crustal magma chamber while clinopyroxene and plagioclase phenocrysts were crystallized in the sub-volcanic conduits forming the crystal mush, and carried to the surface by the evolved Fe-Ti-rich ascending basaltic magma. The high modal abundance of plagioclase at the top and clinopyroxene at the bottom part of the Kumbharli Ghat section is responsible for an increase in Sr and a decrease in Sc content towards the upper flows. The surface and sub-surface basalt samples contain Pd = 5–31 ppb, Pt = 4–15 ppb, Ir = 1–4 ppb, Ru = 1–3 ppb, and Rh = 3–5 ppb. Negative relations of Pd/Ir, Pd/Ru, and Pd/Rh with MgO from both sets of samples indicate partitioning of Ir, Ru, and Rh to early fractionated cumulus chromite (or olivine). Magnetite is a late crystallizing phase from the evolved Fe-Ti-rich basaltic magma. With an increasing modal abundance of magnetite, there is an increase of FeO total , TiO 2 , and V with Pd indicating fractionation of Pd by magnetite. Geochemical characters show that the surface basalt samples are less contaminated compared to the sub-surface KBH-7 basalts. High Nb (6.8–13.6 ppm) and low Ta (0.2–0.37 ppm) content and elevated Nb/Ta ratios of the surface samples from the ghat sections indicate the possible interaction of the basaltic magma with the carbonate metasomatized subcontinental lithospheric mantle (SCLM). On the other hand, a high degree of partial melting with limited crustal contamination can also elevate the Nb/Ta ratios of the basalts from the ghat sections. Deccan basalts from the study areas do not bear the signature of sulfide supersaturation and subsequent immiscible sulfide segregation. This is evidenced by their high chalcophile element concentrations (Ni = 79–103 ppm, Cu = 121–259 ppm) and ratios like Cu/Zr (≥ 1), Ni/MgO (13.7–21.8) with low Cu/Pd (2140–29938) compared to other Ni-Cu (PGE) sulfide mineralized continental flood basalts. The lack of crustal sulfur in the various contaminants is perhaps the main reason for this sulfide-undersaturated character of the Deccan basalts of the current study.

Occurrence and enrichment mechanism of Co in Fe-Ti oxide deposits: A case study of the world-class Panzhihua deposit in SW China

The Panzhihua deposit is the one of the largest Fe-Ti oxide deposits in the world and holds 10,000 to 20,000 tons of Co resource with grades varying from 0.01 % to 0.02 %. Detailed field geological investigations and major and trace element analyses, were conducted to reveal occurrence of Co and Ni and their enrichment mechanism. Co and Ni are predominantly enriched in massive magnetite ores (average 277 ppm Co, 281 ppm Ni) of the Lower zone in the Panzhihua intrusion. Co occurs as three types:(1) independent minerals such as cobalt pentlandite (Co3.96-6.98Ni0.85-2.62Fe1.36-2.53S8) and linnaeite (Co1.65-1.88Ni0.99-1.05Fe0.15-0.37S4); (2) isomorphic state substituting for Fe, Ni and/or Mg in pentlandite (Co0.53-0.55Ni4.57-4.65Fe3.80-3.83S8), Co-bearing pyrite (Co0.09-0.12Fe0.89-0.93S2), pyrrhotite (Co 111–1964 ppm), olivine (Co 161–184 ppm), pyrite (Co 3–272 ppm), titanomagnetite (Co 57–181 ppm), ilmenite (Co 57–110 ppm), clinopyroxeneclinopyroxene (Co 34–40 ppm); (3) microscopic sulfide inclusions in chalcopyrite. Sulfide segregation and crystallization are principal mechanisms of Co enrichment. The results offers valuable insights into understanding Co mineralization, resource assessment, and comprehensive utilization in magmatic Fe-Ti oxide deposits.

Osmium and oxygen isotope constraints on magma-crust interactions and the transport of copper at the roots of arcs

The formation of copper-rich cumulates at the base of arc crusts has been proposed as a key process modulating the geochemical evolution of the continental crust and the genesis of giant ore deposits of copper. Despite the importance of these phenomena, the degree to which the lower crustal evolution of magmatic systems is influenced by open-system interaction and the assimilation of pre-existing crustal materials remains unclear. To tackle this issue, we provide direct isotopic constraints on the evolution of deep magmatic systems in arcs by measuring the osmium and oxygen isotope composition of hydrous copper-rich (∼730 μg·g−1 Cu) ultramafic cumulates formed at the base of the Acadian orogen (∼40 km deep) in the New England Appalachians (northeastern USA). The radiogenic 187Os/188Os initial ratios (ranging from 0.31 to 0.67) and the elevated δ18O values (8.97 ± 0.42 ‰ for orthopyroxene; 9.25 ± 0.26 ‰ for phlogopite) suggest a significant role of open-system magmatic differentiation, involving crustal assimilation, in the formation of these cumulates. Modeling of the 187Os/188Os and δ18O composition of the cumulates suggests that the observed isotopic compositions result from the initial evolution of parental magmas under sulfide-undersaturated conditions, followed by saturation after approximately 15% to 20% of assimilation and fractional crystallization progression. These results suggest that the assimilation of crustal material led to a drop in the magmatic system's fO2 (∼ΔFMQ < −1), triggering sulfide segregation and the formation of copper-rich cumulates. Our findings align with the hypothesis that magma-crust interactions can lead to the formation of lower crustal domains enriched with Cu, which may constitute a pre-stage in the formation of some porphyry copper deposits, particularly in collisional orogens.

Co-Ni distribution and Re-Os isotopic age of the Wuxing complex in the Central Asian orogenic Belt: Implications for sulfide mineralization in Alaskan-type complexes

Alaskan-type mafic–ultramafic complexes have been recognized as potential hosts of magmatic Ni-Cu sulfide deposits. However, the distribution and controlling factors of ore-forming metal elements like Co and Ni within these complexes remain poorly understood. This study offers comprehensive petrological observations and quantifies the Co and Ni contents of silicate minerals and sulfides in the Wuxing complex, the oldest Alaskan-type complex hosting a distinctive PGE-rich Ni-Cu sulfide deposit in the Central Asian Orogenic Belt. The Co-rich minerals, including cobaltite and pentlandite, occur as inclusions or interstitial grains in other mineral phases. Among the sulfide assemblages (pyrrhotite, pentlandite and chalcopyrite), pentlandite exhibits the highest 3.59 ∼ 5.98 wt.% of Co and 28.7 ∼ 32.7 wt.% of Ni contents, with the Co contents being 2 to 10 times higher than those in magmatic Ni-Cu sulfide deposits. Clinopyroxene and hornblende in the Wuxing complex display lower Co and Ni contents compared to those in sulfide-free rocks of typical Alaskan-type complexes. This could be ascribed to the reduction in Co and Ni contents in evolved magmas following sulfide segregation. Additionally, lack of olivine and chromite crystallization would elevate Co and Ni contents in silicate magma and promote the sulfide mineralization in the Wuxing complex. The Re-Os isotopic dating in ore samples at 596 Ma, combined with previously zircon U-Pb ages of 510 ∼ 517 Ma, reveals that long-term magmatism would facilitate mineralization in the Wuxing complex. Our investigations provide a new insight of mineral crystallization for understanding of magmatic Ni-Cu-PGE sulfide mineralization in Alaskan-type complexes.

Micron-to-nanoscale investigation of Cu-Fe-Ni sulfide inclusions within laurite (Ru, Os)S2 from chromitites

AbstractThis paper provides a top-down nanoscale analysis of Cu-Ni-Fe sulfide inclusions in laurite from the Taitao ophiolite (Chile) and the Kevitsa mafic-ultramafic igneous intrusion (Finland). High-resolution transmission electron microscopy (HRTEM) reveal that Cu-Ni-Fe sulfide inclusions are euhedral to (sub)-anhedral (i.e., droplet-like) and form single, biphasic or polyphasic grains, made up of different polymorphs, polytypes and polysomes even within a single sulfide crystal. Tetragonal (I4$$\stackrel{-}{2}$$d) and cubic (F$$\stackrel{-}{4}$$3m) chalcopyrite (CuFeS2) host frequent fringes of bornite (Cu5FeS4; cubic F$$\stackrel{-}{4}$$3m and/or orthorhombic Pbca) ± talnakhite (Cu9(Fe, Ni)8S16; cubic I$$\stackrel{-}{4}$$3m) ± pyrrhotite (Fe1 − xS; monoclinic C2/c polytype 4C and orthorhombic Cmca polytype 11C) ± pentlandite ((Ni, Fe)9S8; cubic Fm3m). Pentlandite hosts fringes of pyrrhotite, bornite and/or talnakhite. Laurite and Cu-Fe-Ni sulfide inclusions display coherent, semi-coherent and incoherent crystallographic orientation relationships (COR), defined by perfect edge-to-edge matching, as well as slight (2–4º) to significant (45º) lattice misfit. These COR suggest diverse mechanisms of crystal growth of Cu-Fe-Ni sulfide melt mechanically trapped by growing laurite. Meanwhile, the mutual COR within the sulfide inclusions discloses: (1) Fe-Ni-S melt solidified into MSS re-equilibrated after cooling into pyrrhotite ± pentlandite, (2) Cu-Ni-Fe-S melts crystallized into the quaternary solid solution spanning the compositional range between heazlewoodite [(Ni, Fe)3±xS2] (Hzss) and ISS [(Cu1±x, Fe1±y)S2]. Additionally, nanocrystallites (50–100 nm) of Pt-S and iridarsenite (IrAsS) accompanying the sulfide inclusions spotlight the segregation of PGE-rich sulfide and arsenide melt earlier and/or contemporarily to laurite crystallization from the silicate magmas. Cobaltite (CoAsS)-gersdorffite (NiAsS) epitaxially overgrown on laurite further supports the segregation of arsenide melts at early stages of chromitite formation.

Cobalt and nickel distribution and controlling factors in the Bushveld layered complex

The Bushveld Complex is the largest known layered intrusion in the world and has been extensively studied. However, there remains an absence of systematic investigations of cobalt (Co) and nickel (Ni) distribution at various scales. Elements Co and Ni behave varying degrees of compatibility within chromite, silicates, and sulfides, making them effective proxies for elucidating chemical competition and interaction among these minerals. This study aims to characterize Co and Ni distribution in olivine, pyroxenes, chromite, and whole rocks from different seams of the Bushveld Complex and to reveal their controlling factors. Our results indicate large variations of whole-rock Co and Ni concentrations, with a decreasing sequence of dunites (Co: 156–222 ppm; Ni: 2208–2750 ppm) > harzburgites (Co: 87.8–174 ppm; Ni: 152–2050 ppm) > pyroxenites (Co: 58.7–143 ppm; Ni: 387–1947 ppm) > norites (Co: 16.0–113 ppm; Ni: 153–646 ppm) > anorthosites (Co: 3.20–16.3 ppm; Ni: 19.7–97.2 ppm). In general, olivine has higher Ni contents (717–4496 ppm) and lower Co (105–239 ppm) than chromite (Ni: 524–1948 ppm; Co: 236–563 ppm). Pyroxenes have apparently low Co (orthopyroxene: 39.7–184 ppm; clinopyroxene: 17.2–114 ppm) and Ni contents (orthopyroxene: 224–1195 ppm; clinopyroxene: 177–831 ppm). Chromite in chromitites has lower Co content than that in other rocks. The whole-rock and mineral Co and Ni variations in the stratigraphic profile are closely related with lithology, mineral assemblages and element partition coefficients in minerals. The Co contents in the chromite and pyroxenes vary alternately with the chromitites and rock seams, with lower Co contents in ore samples than that in silicate rocks. Whole rocks and mineral separates in the Merensky Reef exhibit the highest Ni contents (whole-rock: up to 4000 ppm; orthopyroxene: 1035–1195 ppm; clinopyroxene: 730–831 ppm; chromite: 1760–1948 ppm), which are likely attributed to sulfide segregation and diffusion between sulfides and other minerals. In addition, the sulfide segregation may also be a main factor resulting in Co-Ni decoupling in pyroxenes from the Main Zone of the Bushveld Complex.

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.

Underplated melts control sulfide segregation at the continental crust-mantle transition

Exposures of the Earth’s crust-mantle transition are scarce, thus, limiting our knowledge about the formation of subcontinental underplate cumulates, and their significance for metal storage and migration. Here, we investigated chalcophile metals to track sulfide crystallization within the Contact Series, an <150-m-thick pyroxenite-gabbronorite sequence, formed by mantle-derived melts, highlighting the boundary between the Balmuccia mantle peridotite and gabbronoritic Mafic Complex of the Ivrea-Verbano Zone. Within the Contact Series, numerous sulfides crystallized in response to the differentiation of mantle-derived underplated melts. Such sulfide-controlled metal differentiation resulted in anomalous Cu contents (up to ~380 ppm), compared to reference mantle (~19 ppm) and crustal samples (~1 ppm). We propose that the assimilation of continental crust material is a critical mechanism driving sulfide segregation and sulfide-controlled metal storage. Our results evidence that sulfides are trapped in the underplated mafic-ultramafic cumulates and that their enrichment in Cu may provide essential implications for crustal metallogeny.

Contrasting Cu isotopes in mid-ocean ridge basalts and lower oceanic crust: Insights into the oceanic crustal magma plumbing systems

Magma plumbing systems exert strong controls on the formation and evolution of the oceanic crust during crust accretion. However, plumbing system dynamics based largely on mid-ocean ridge basalts (MORBs) are extremely difficult to constrain because the MORBs are aggregated melts and original information may have been blurred. Copper isotopic compositions of lower crustal gabbroic cumulates effectively archive early-stage histories because sulfides constitute the dominant Cu budget of gabbroic cumulates and are largely isolated from subsequent magma filtering processes. Here, we present Cu isotopes of a suite of gabbroic cumulates from the ultraslow-spreading Southwest Indian Ridge (Hole U1473A), and MORBs from the South Mid-Atlantic Ridge and East Pacific Rise. The δ65Cu of the MORBs from this study (+0.04 ‰ to +0.19 ‰) match those of previous MORB analyses, indicating uniform δ65Cu at various spreading rates. In contrast, the δ65Cu of gabbroic rocks vary significantly (−1.14 ‰ to 0.87 ‰), exceeding by far the range known for peridotites. The Cu budget of these gabbroic rocks is hosted in sulfides and the mantle-like S isotopic compositions of sulfides indicate their origin of igneous processes. These results thus suggest that magma accumulation and sulfide segregation would lead to notable Cu isotopic fractionation in the lower oceanic crust. We propose that repeated recharging of primitive melts and efficient mixing of melts within the plumbing system can buffer the removal of early 63Cu-rich sulfides from sulfide-saturated MORBs. The discrepancy in δ65Cu between lower oceanic crust and MORBs is a natural consequence of continuous replenishment that occurs concurrently with melt-rock interaction, mixing, crystallization and extraction, irrespective of the oceanic settings. The consistent δ65Cu in MORBs (0.09 ± 0.08 ‰) and komatiites (0.06 ± 0.06 ‰) further indicates that their Cu isotopes reflect the mean mantle source composition, providing a robust δ65Cu for bulk silicate Earth (BSE) of 0.08 ± 0.08 ‰ (2sd). Accordingly, we propose that in open sub-ridge plumbing systems, other incompatible element isotopes and ratios of elements with similar incompatibility in MORBs as Cu isotopes suggest, could also represent mean mantle source compositions.

Emplacement and ore potential of the Permian Pobei mafic–ultramafic complex, NE Tarim, NW China

A number of mafic–ultramafic intrusions with variable degrees of Ni-Cu sulfide mineralization occur in the northeastern Tarim Block and East Tianshan Orogenic Belt (NW China). Among them, the Pobei complex is composed of a gabbro body intruded by several ultramafic bodies including Poyi and Poshi. These bodies have similar mineralogy and chemical compositions and were derived from a common magma. Olivine crystals from the Poyi and Poshi bodies generally have high Fo contents with the highest Fo value of 89.5 and Ni up to 3300 ppm Ni, indicative of crystallizing from Ni-undepleted, high-Mg basaltic magmas. Sr-Nd-Pb isotopic compositions show that more mafic rocks show relatively low degrees of crustal contamination, whereas more evolved rocks experienced higher degrees of contamination, especially in the upper part of the complex. Olivine crystals from both the Poyi and Poshi bodies show sharp decrease of Ni with decreasing Fo values, indicating sulfide segregation in these two bodies. Gabbros may have potential of reef-type chromite mineralization at the deep level, and V-bearing magnetite mineralization at higher stratigraphic level corresponding to the current surface level, but the potential of PGE mineralization is low. We propose that the ultramafic bodies of the Pobei complex may have been formed from the injection of olivine- and sulfide-laden crystal slurry from the bottom of a large magma chamber. The Ni-Cu mineralization was triggered by the crustal contamination. The Pobei complex was formed by the multiple intrusions of magmas to form the current complex.

Controls on the metal tenors of sulfide ores in the Jinchuan Ni–Cu–PGE sulfide deposit, NW China: Implications for the formation of distinct textural types of sulfide ores in magma conduits

The giant Jinchuan Ni–Cu–platinum-group element (PGE) sulfide deposit is a magma conduit system comprising four main intrusive units termed segments III, I, II-W, and II-E. The deposit comprises disseminated, net-textured, massive sulfide, and Cu-rich sulfide ores, with variations in metal tenors occurring among these different ore types and among the segments. Controls on these metal tenor variations must be linked to metallogenic processes, but this remains poorly constrained. To asses this, we systematically compared metal tenors (Ni, Cu, and the PGE) of ores from two perspectives — i) different ore types in each segment and ii) a single ore type across all four segments. Two major styles of metal tenor variations are documented. Style 1: Segments III and I have higher metal tenors than segments II-W and II-E for any given type of ore. Based on sulfide segregation models, this variation is interpreted to be related to variable degrees of early removal of sulfide liquid from the magmas that formed the four segments. Style 2: Disseminated ores in segments III and I have higher metal tenors than the other ore types, whereas all of the ore types in segments II-W and II-E have similar metal tenors. This is interpreted to be the result of the disseminated ores in segments III and I having formed from sulfide liquids that experienced higher R factors than the sulfide liquids that formed the other ore types, whereas all of the ores in segments II-W and II-E formed from sulfide liquids that experienced similar R factors. This difference suggests that the different ore types in segments III and I formed via early percolation and accumulation of sulfide liquids (the net-textured and massive ores) followed by the capture of disseminated, high R factor sulfides (the disseminated ore), whereas the different ore types in segments II-W and II-E likely formed by the physical percolation of originally disseminated sulfide liquid through the inter-crystal pore space. This study demonstrates that both sulfide ore texture and their metal-tenor variations are critical to characterizing ore-forming processes in dynamic magma conduits.

X-ray Computed Tomography of PGE-Rich Anorthosite from the Main Reef of the Yoko–Dovyren Layered Massif

For the first time, we present results of a detailed X-ray computed tomography of mineralized anorthosite from the main low-sulfide PGE-rich horizon of the Yoko–Dovyren intrusion in Southern Siberia. These studies were carried out in three stages with the acquisition of information on different scales. At the first stage, a 5 × 6 cm size sample was scanned with a resolution as high as 200 µm; at the second stage, two 10 mm cores were drilled out of its most sulfide-rich zones, in which probable platinum group minerals (PGM) were found; the third stage included drilling out 3 mm cores in the areas potentially enriched in PGMs. Such a systematic study made it possible to visualize the distribution of sulfide in the volume of the plagioclase matrix, as well as to establish the spatial relationships of sulfides and PGMs. The mineralized layers of the anorthosite are characterized by a heterogeneous distribution of sulfides within 1 cm, while their contents do not exceed 10 vol.%. Most PGMs look like sub-isometric ones, as they are confined to the edges of sulfide segregations, less often occurring inside them; their size does not exceed 135 µm. Based on the results of stereological reconstructions, two small polished mounts were prepared that exposed the two largest grains of the probable PGMs. According to the results of SEM studies, one grain 35 µm in diameter in association with chalcopyrite and epidote at the margin of a sulfide segregation was identified as moncheite, and an elongated 135 µm long grain in the intergrowth with cubanite was identified as electrum.

Accessory mineralisations in lherzolites of Northern Kraka massif (South Urals)

The findings of platinum group metal mineralization (PGM) and the distribution of platinum group elements (PGE) in lherzolites of the Northern Kraka massif are described. The total contents of PGE are approximately two orders of magnitude lower than those in chondrite and are close to pyrolite, relative to which the studied lherzolites are enriched in Pd and depleted in Ru. In segregations of PGMs, the presence of all PGEs (except rhodium) in various proportions was established. All found grains are divided into three contrasting types: the refractory triad Os–Ir–Ru, essentially platinum with the participation of Pd, and Cu–Pd. Almost all found PGM grains are localized either in the peripheral parts of grains of altered sulfides (heazlewoodite, pentlandite) or in the silicate matrix in the immediate vicinity of sulfide segregations. Based on the mineral associations and PGE distribution, a probable genesis of segregations has been suggested. Associations of Cu–Pd and Pd–Pt(+Cu) composition most likely formed during the crystallization of sulfides from the extracted partial melts. This is indicated by their close association with clinopyroxenes and the presence of relatively fusible platinoids and copper. The associations of Pt–Ir and Os–Ir–Ru(+Pt) composition are most likely restitic, formed in place of primary mantle sulfides as a result of extraction of more fusible elements and further desulphurization. The isolation of platinoids as their own mineral phases is associated with the influence of superimposed low-temperature processes – subsolidus redistribution during cooling and subsequent serpentinization.

Role of volatiles in intrusion emplacement and sulfide deposition in the supergiant Norilsk-Talnakh Ni-Cu-PGE ore deposits

Abstract The Norilsk-Talnakh orebodies in Siberia are some of the largest examples on Earth of magmatic Ni–Cu–platinum group element (PGE) deposits, formed by segregation of immiscible sulfide melts from silicate magmas. They show distinctive features attributable to degassing of a magmatic vapor phase during ore formation, including: vesiculation of the host intrusions, widespread intrusion breccias, and extensive hydrofracturing, skarns, and metasomatic replacement in the country rocks. Much of the magmatic sulfide was generated by assimilation of anhydrite and carbonaceous material, leading to injection of a suspension of fine sulfide droplets attached to gas bubbles into propagating tube-like host sills (“chonoliths”). Catastrophic vapor phase exsolution associated with a drop in magma overpressure at the transition from vertical to horizontal magma flow enabled explosive propagation of chonoliths, rapid “harvesting” and gravity deposition of the characteristic coarse sulfide globules that form much of the ore, and extensive magmatic fluid interaction with country rocks.

Synergistic effect of AgBiS2 segregated NaV3O8 nanostructures in direct conversion X-ray sensors

Synergistic nanostructures possess enriched electrical and optical properties compared to conventional nanostructures. 1D-3D synergized nanostructure was implied to elucidate the performance of the X-ray sensor for the first time. Current research in X-ray detection only focuses on implementing high attenuating material based on oxides/ perovskites in developing X-ray sensors. Herein we approached tailoring the performance of an X-ray sensor with a synergistic nanostructure composed of sodium vanadium oxide (NaV3O8) with substantial grain boundary (GB) segregation of silver bismuth sulfide (AgBiS2), enabling the structured arrangement of nanostructured grains at the surface of NaV3O8 nanorods. Then, it was coated as a thick film on top of the interdigitated electrodes by glass rod sliding technique to readout the dose-dependent X-ray sensing capability. From the X-ray impinged photocurrent characteristics, the sensor with 75 wt% AgBiS2 segregated NaV3O8 exhibits superior sensitivity 82.6 nC mGy-1 cm-2 and low-noise equivalent dose rate 1.04 mGy Hz-0.5 for 2.49 mGy s-1 than other compositions. These experimental findings explore the implication of synergistic nanostructures as active layers in direct conversion X-rays sensors for improved charge extraction and enhancement in X-ray impinged photocurrent at low dose rates.

Characterizing the supra- and subsolidus processes that generated the Current PGE-Cu-Ni deposit, Thunder Bay North Intrusive Complex, Canada: insights from trace elements and multiple S isotopes of sulfides.

The online version contains supplementary material available at 10.1007/s00126-023-01193-9.

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.

Copper isotope fractionation during magma differentiation: Evidence from lavas on the East Pacific Rise at 10°30′N

Redox-driven copper (Cu) isotope fractionation has been widely observed in low-temperature weathering and hydrothermal processes. However, how Cu isotopes may fractionate during magmatic processes remain unknown. To address this issue, we studied MORB samples from the East Pacific Rise (EPR) at 10°30′N to explore the Cu isotope behavior during magma differentiation. These samples are globally ideal because they are generated from a uniformly depleted sub-ridge mantle source but have experienced varying extents of fractional crystallization and sulfide segregation with large variations of MgO (1.76–7.38 wt%) and Cu (16.0–75.2 μg/g). Lavas with MgO ≥ 4.9 wt% involving olivine, clinopyroxene and plagioclase as the major liquidus minerals show homogeneous δ65Cu of 0.05 ± 0.03‰, suggesting little Cu isotope fractionation at this stage of magma differentiation. However, after Fe-Ti oxides appear on the liquidus, melt δ65Cu values first decrease rapidly to –0.41‰ at MgO of 3.9 wt% and then increase with the most evolved sample having δ65Cu of 0.08‰. Such a significant Cu isotope fractionation during magma differentiation has never been reported before. We suggest the large Cu isotope variation at MgO < 4.9 wt% reflect a redox change of MORB melt resulting from fractional crystallization of Fe-Ti oxides. The crystallization of ilmenite (Fe2+TiO3), which is the first Fe-Ti oxide phase during MORB differentiation, causes a sudden increase of Fe3+/∑Fe in the residual melt and drives the redox reaction Fe3+ + Cu1+ → Fe2+ + Cu2+. As a result, sulfides segregated from the MORB melts have high Cu2+ content and heavy Cu isotope compositions with Δ65CuSulfide-Silicate melt > 0 because of the preferential bonding of heavy Cu isotopes (65Cu vs. 63Cu) with Cu2+, whose fractionation rapidly decreases δ65Cu of the residual melts. The increase of Fe3+/∑Fe will quickly drive the melt to be saturated in titanomagnetite (magnetite-Ulvöspinel solid solutions), whose crystallization decreases melt Fe3+/∑Fe and drives the redox reaction Fe2+ + Cu2+ → Fe3+ + Cu1+. As a result, the segregated sulfides after titanomagnetite saturation have decreasing Cu2+ content. These sulfides are also predicted to have low Ni content and exhibit Δ65CuSulfide-Silicate melt < 0, whose segregation raises δ65Cu in the residual melts. Therefore, we suggest a significant influence of redox states of Cu and abundance of Ni in the segregated sulfides on the Cu isotope fractionation during MORB differentiation. During mantle melting for MORB at ΔFMQ < 0, Cu isotope fractionation between melt and mantle sulfide is inferred to be limited, and the upper mantle has primitive MORB-like δ65Cu of 0.06 ± 0.05‰.