Sulfide Saturation Research Articles

Sulfide saturation in reduced magmas during generation of the Gangdese juvenile lower crust: Implications for porphyry Cu–Au mineralization in the Gangdese belt, Tibet

Sulfide saturation in reduced magmas during generation of the Gangdese juvenile lower crust: Implications for porphyry Cu–Au mineralization in the Gangdese belt, Tibet

Magmatic evolution of the Kolumbo submarine volcano and its implication to seafloor massive sulfide formation

Seafloor massive sulfides form in various marine hydrothermal settings, particularly within volcanic arcs, where magmatic fluids may contribute to the metal budget of the hydrothermal system. In this study, we focus on the Kolumbo volcano, a submarine volcanic edifice in the central Hellenic Volcanic Arc hosting an active hydrothermal system. Diffuse sulfate-sulfide chimneys form a Zn-Pb massive sulfide mineralization with elevated As, Ag, Au, Hg, Sb, and Tl contents. These elements have similar behavior during magmatic degassing and are common in arc-related hydrothermal systems. Trace-element data of igneous magnetite, combined with whole rock geochemistry and numerical modelling, highlights the behavior of chalcophile and siderophile elements during magmatic differentiation. We report that, despite early magmatic sulfide saturation, chalcophile element contents in the magma do not decrease until water saturation and degassing has occurred. The conservation of chalcophile elements in the magma during magmatic differentiation suggests that most of the magmatic sulfides do not fractionate. By contrast, upon degassing, As, Ag, Au, Cu, Hg, Sb, Sn, Pb, and Zn become depleted in the magma, likely partitioning into the volatile phase, either from the melt or during sulfide oxidation by volatiles. After degassing, the residual chalcophile elements in the melt are incorporated into magnetite. Trace-element data of magnetite enables identifying sulfide saturation during magmatic differentiation and discrimination between pre- and post-degassing magnetite. Our study highlights how magmatic degassing contributes to the metal budget in magmatic-hydrothermal systems that form seafloor massive sulfides and shows that igneous magnetite geochemistry is a powerful tool for tracking metal-mobilizing processes during magmatic differentiation.

Sulfide saturation and resorption modulates sulfur and metal availability during the 2014–15 Holuhraun eruption, Iceland

Mafic magmas may experience multiple stages of sulfide saturation and resorption during ascent and differentiation. Quenched tephra erupted during the 2014–15 Holuhraun eruption preserve abundant evidence for sulfide resorption, offering a rare opportunity to explore the sulfide life cycle from nucleation to resorption. Specifically, we combine detailed textural and chemical analyses of sulfides and silicate melts with geochemical models of sulfide saturation and degassing. This integrative approach demonstrates that sulfides began nucleating in melts with ~8 wt% MgO, persisted during fractionation to 6.5 wt% MgO, before resorbing heterogeneously in response to sulfur degassing. Sulfides are preserved preferentially in confined geometries within and between crystals, suggesting that kinetic effects impeded sulfur loss from the melt and maintained local sulfide saturation on eruption. The proportion of sulfides exhibiting breakdown textures increases throughout the eruption, coincident with decreasing magma discharge, indicating that sulfide resorption and degassing are kinetically limited. Sulfides likely modulate the emission of sulfur and chalcophile elements to the atmosphere and surface environment, with implications for assessing the environmental impacts and societal hazards of basaltic fissure eruptions.

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.

Platinum-Group Element Geochemistry of Igneous Rocks in the Chongjiang Cu–Mo–Au Deposit, Southern Tibet: Implications for the Formation of Post-Collisional Porphyry Cu Deposits

Abstract The timing and extent of sulfide saturation have been suggested as controlling factors in the formation of economically significant porphyry Cu deposits in subduction zone settings. However, details on the sulfide saturation history in post-collisional porphyry systems remain ambiguous. Accordingly, we have characterized the whole-rock geochemistry, including platinum-group elements (PGE), of igneous intrusions in the post-collisional Chongjiang porphyry Cu–Mo–Au deposit (southern Tibet) and utilize this data in conjunction with zircon U–Pb geochronological results and sulfide chemistry to assess the timing of sulfide saturation, the nature and amount of magmatic sulfide produced. The Chongjiang intrusions (monzogranite, biotite monzogranite porphyry, granodiorite, dacite porphyry, and quartz diorite porphyry) and mafic microgranular enclaves (MMEs) have zircon U–Pb ages of 14.2 to 12.8 Ma. Covariations in whole-rock major and trace elements among the Chongjiang intrusions and MMEs, together with similarities in their Sr–Nd and zircon Hf isotope compositions, indicate that they are co-magmatic and crystallized from a juvenile lower crustal melt that mixed with mafic melt derived from the lithospheric mantle; this hybrid melt subsequently evolved via fractional crystallization. Trace-element ratios in zircon and temperature − ∆FMQ estimates of the different intrusions suggest that they all crystallized from oxidized (average ∆FMQ = 1.9–2.6) and water-rich magmas. Palladium contents and Pd/Pt ratios in the Chongjiang igneous intrusions increase with decreasing MgO up to 3.9 wt % MgO, after which they abruptly decrease. The initial increase in Pd/Pt ratios likely results from the fractionation of a Pt-rich mineral (e.g. Pt–Fe alloy). The decrease in Pd contents and Pd/Pt ratios at 3.9 wt % MgO likely results from sulfide saturation during magma evolution, but prior to volatile exsolution, which occurred at approximately 1.4 to 2.4 wt % MgO. The presence of magmatic sulfide inclusions in amphibole and magnetite in samples with 3.9 wt % MgO, and the geochemical compositions of sulfide inclusions suggest that they represented trapped sulfide liquid and intermediate solid solution. Results of Monte Carlo simulations demonstrate that 0.003 to 0.009 wt % magmatic sulfide is required to have fractionated from the magma to explain the decrease in Pd contents at 3.9 wt % MgO. Highly chalcophile elements, such as Pd, will be sequestered by the magmatic sulfide that saturates at depth, decreasing their concentrations in the residual silicate melt, whereas concentrations of the less chalcophile elements, such as Cu, Mo, and even Au, will not be as significantly affected. Consequently, sufficient concentrations of Cu–Mo–Au will remain in the residual melt and, upon reaching volatile saturation, can be transported by the vapor phase to form porphyry Cu–Mo–Au deposits. In the case of the Chongjiang deposit, sulfide saturation was likely triggered by the high pressures and/or depletion of FeO caused by the thick (~70 km) crust beneath the Gangdese belt. This contribution presents evidence of sulfide saturation in post-collisional magmatic systems, and demonstrates that the amount of magmatic sulfide produced is a critical factor in controlling the formation of post-collisional porphyry Cu deposits.

Vanadium rich Fe-Ti oxide and Cu-sulphide mineralization in Paleoproterozoic Mangikhuta volcanics, Central Indian Craton: metallogenic and petrogenetic implications

This study reports for the first time, Fe-Ti-V oxide and Cu-sulphide mineralization in Paleoproterozoic Mangikhuta basalt Formation, central Indian craton. Electron microprobe and laser ablation analyses of Fe-oxides reveal high FeO (45–69 wt %), TiO2 (19–53 wt %), V (1860 - 4990 ppm), Zr (394–3130 ppm), Nb (55–285 ppm) and Zn (324–668 ppm). Interelemental relationships of Fe-oxides reveal their magmatic origin. High concentration of lithophile elements in Fe-oxides besides V and Ni trends in incompatible element plots indicate their origin from mafic melt. High Cu content (269 and 314 ppm) in the host basalt samples along with chalcopyrite mineralization observed during ore petrography indicates sulphide saturation of Mangikhuta magma. The chondrite normalized rare earth element (REE) plots of the host rock samples are overall similar to the earlier reported Mangikhuta REE patterns, which indicates genetic relation of Fe-oxides and Cu-sulphides with Mangikhuta volcanism. Fe-oxide and Cu-sulphide mineralization in Mangikhuta basalt is related to hydrous and oxygen rich arc related mafic melt intrusion into the Khairagarh back arc basin. Sulphide saturation in Mangikhuta basalt was initiated due to precipitation of Fe-oxides from the evolved melt whereas addition of fresh batch of hydrous and oxygen rich melt derived from the arc-related mantle source increased oxygen fugacity of residual melt that resulted in alternate phases of high oxygen and Sulphur fugacity and precipitation of Fe-oxide and Cu-sulphides from the melt.

Geochemical Thermometry of Ore-Bearing Gabbronorites from an Apophysis of the Yoko-Dovyren Massif: Composition, Amount of Olivine, and Conditions of Sulfide Saturation in the Parental Magma

Geochemical Thermometry of Ore-Bearing Gabbronorites from an Apophysis of the Yoko-Dovyren Massif: Composition, Amount of Olivine, and Conditions of Sulfide Saturation in the Parental Magma

Sulfide compositions of young Chang’e-5 basalts and implications for sulfur isotopes in lunar basalt sources

Sulfides are accessory phases in lunar rocks butare important forunderstanding lunar interior processes as well as impacts on the lunar surface.Whether or not the lunar mantle had achieved sulfide saturation during magma ocean evolution and displays homogeneous sulfur isotopes remains under debate. TheChang’e-5 (CE-5) mission returned young (2.0 Ga) basalts from a mare terrain in thenorthern Oceanus Procellarum.Here we study chemical and sulfur isotopic compositions (δ34SV-CDT) of sulfides from CE-5 basaltic fragments and combine them with δ34S of other young (3.1–3.0 Ga) lunar low-Ti basalt (NWA 10597 and NWA 4734) and gabbro meteorites (NWA 6950) to compare them with Apollo low-Ti and high-Ti mare basalts. The sulfides in basaltic fragments of CE-5 are troilites (FeS) with lowabundances ofNi, Co, and Cu(e.g., Ni < 0.04 wt% and Ni/Co < 0.3). Textures and chemical compositions indicate that most troilites arelate-stage crystallization products fromthe highly evolvedCE-5 basalts. Several troilites occur in the matrices of impactite clasts and are intergrown with Fe–Ni metal(12–36 wt% Ni, Ni/Co of 12–39). These troilites are distinct from the major population of troilites withnoticeably higher Ni abundances (mostly > 0.2 wt% with Ni/Co of 1–3) andreconcile with the addition of meteoritic materials into the impact melts.The δ34SV-CDTof large troilite grains (>10 μm) from the CE-5 basaltic fragments and lunar meteorites were obtained by high-precision, high-spatial-resolution femtosecond laser ablation MC-ICP-MS which achieved external uncertainty (0.65 ‰, 2SD at 8-μm laser spots) like nano-SIMS. Sulfur degassing during surficial effusive lava flow likely led to a slightdecrease inδ34S (by ∼ 1 ‰) for some basaltic fragments; however, such effects were limited to the scale of bulk rock samples, consistent with previous results. The mean δ34Sof troilites in CE-5 basaltic fragments (0.35 ± 0.25 ‰, 2SE, n = 45) is similar to those of ancient (3.8–3.1 Ga old) Apollo low-Ti and high-Ti mare basalts and the young gabbro cumulate NWA 6950 (0.56 ± 0.21 ‰, 2SE, n = 10). The paired NWA 10597 and NWA 4734 show consistent δ34S, lower than most values by ∼ 0.5 ‰. Current data thus indicate that most mantle sources of lunar basalts would be homogeneous for δ34S(0.6 ± 0.3 ‰) and minor regions may be different. The overall homogenous δ34S from different mantle sources with variably low sulfur contents supports sulfide-undersaturated accumulation of the lunar magma ocean, which was inherited from strong volatile loss and evaporative fractionation during the formation of the Moon.

Sulfide-sulfate metasomatism and nickel release in the suprasubduction mantle

Metasomatic replacement of olivine by orthopyroxene under the influence of SiO2-rich melts is a widespread process in mantle conditions responsible for the formation of pyroxenite from mantle peridotite. However, the behavior of nickel in this process remains unclear. The reaction of Ni-containing olivine with silica- and sulfur-rich metasomatic agents in the suprasubduction mantle may release nickel from olivine and subsequently form a rock containing orthopyroxene and nickeliferous sulfides. Xenoliths of mantle wedge harzburgite from the Shiveluch volcano (Kamchatka continental arc) contain abundant globules of Ni-rich MSS, pentlandite and smaller amount of copper sulfides, totaling up to 0.75 wt.% (∼2600 ppm S2–), in association with Ca-sulfates (up to 7900 ppm S6+). The process accounting for the observed mineral association can be described via simplified reactions (the coefficients are approximate): (Mg,Fe,Ni)2SiO4 + 2xH+ +SiO2 = 2(Mg,Fe)SiO3 + xNi2+ + xH2O; Ni2+ + S2– = NiS. The influx of both oxidized and reduced sulfur may account for the coexistence of sulfide and sulfate phases. The presence of low-Ti chrome spinel with high Fe(II)/Fe(III) ratios, low Al, Ca and Ti in olivine, and no evidence of deserpentinization confirms the mantle origin of the sulfide/sulfate-bearing xenoliths. The mean isotopic composition of sulfur in the sulfide-sulfate assemblage, δ34S = +4.5‰, supports the contribution of slab-derived sulfur. The accumulations of Ni-(Cu)-rich sulfides and Ca-sulfate in metasomatized peridotites can serve as an intermediate host for sulfur and chalcophile metals, thereby generating magmas containing sulfur at the level of sulfide saturation and simultaneously enriched in Ni and Cu during the subsequent partial melting of the mantle.

Pd-Ag-Au Minerals in Clinopyroxenites of the Kachkanar Ural–Alaskan-Type Complex (Middle Urals, Russia)

The study of noble metal minerals of the Ural–Alaskan-type (UA-type) complexes has been traditionally focused on their platinum-bearing dunites and chromitites, while clinopyroxenites have been poorly considered. In this study, we report the first detailed data on the noble metal mineral assemblage in clinopyroxenites of the Kachkanar intrusion, which is a part of a UA-type complex and is renowned for its huge Ti-magnetite deposits. High concentrations of Pd, Au and Ag are closely linked to Cu-sulfide mineralization in amphibole clinopyroxenites, in which they form Pd-Ag-Au minerals: keithconnite Pd3−xTe, sopcheite Ag4Pd3Te4, stutzite Ag5−xTe3, hessite Ag2Te, merenskyite PdTe, kotulskite Pd(Te,Bi), temagamite Pd3HgTe, atheneite (Pd,Hg)3As, potarite PdHg, electrum AuAg and Hg-bearing native silver. Among those, six mineral phases are first reported for clinopyroxenites of the Ural platinum belt. Our evidence supports a petrological model, suggesting that during fractionation of high-Ca primitive magmas at high oxygen fugacity, Pt, Os, Ir, Ru and Rh accumulate in early olivine–chromite cumulates, while Pd, Au and Ag reside in the melt until sulfide saturation occurs and then concentrate in sulfide mineralization. Subsequently, this sulfide mineralization is likely affected by cumulate degassing, which results in a partial resorption of the sulfides and Pd, Au and Ag remobilization by fluid. Second-stage concentration of the sulfides and the chalcophile noble metals in the amphibole-rich rocks may occur when H2O from the fluid reacts with pyroxenes to form amphiboles, and the fluid becomes oversaturated with sulfides and chalcophile elements.

Tectono-magmatic factors for porphyry Cu-(Mo-Au) deposits formation: A case study from Pishtene ore deposit, Western Srednogorie, Bulgaria

Porphyry ore deposits are the source of much of the copper, molybdenum, gold and silver. Porphyry hydrothermal systems typically form in magmatic arcs above subduction zones. In this article, some key factors that may be involved in the formation of the Pishtene porphyry deposit in Western Srednogorie are outlined. The first process is the generation of magma in sub-arc mantle and enrichment of metals, water and other fluids. Next stage is а cyclic crystal fractionation in deep crustal magma chamber. There are a lot of other factors, such as a sulphide saturation, metal partitioning, precipitation of ore minerals, magmatic-hydrothermal evolution, erosional and weathering processes, but they are not discussed in this study.

Predicting sulfide precipitation in magma oceans on Earth, Mars and the Moon using machine learning

The sulfur content at sulfide saturation (SCSS) of a silicate melt can regulate the stability of sulfides and, therefore, chalcophile elements’ behaviors in planetary magma oceans. Many studies have reported high-pressure experiments to determine SCSS using either linear or exponential regressions to parameterize the thermodynamics of the system. Although these empirical equations describe the effects of different parameters on SCSS, they perform poorly when predicting laboratory measurements. Here, we compiled 542 published analyses of experiments performed on a range of sulfide and silicate compositions at varying P-T conditions (<24 GPa, <2673 K). Using empirical equations, linear regression, Random Forest algorithms, and a hybrid algorithm employing empirical fits to P-T conditions and the Random Forest algorithm for compositions, we developed several SCSS models and compared them to laboratory measurements. The Random Forest and hybrid models (R2 = 0.82–0.91, mean average error [MAE] < 746 ppmw S, residual mean standard error [RMSE] < 972 ppmw S), significantly outperform previous empirical models (R2 = 0.28–0.69, MAE = 622–1,170 ppmw S, RMSE = 1,070–1,744 ppmw S), whereas linear regression performs moderately well, i.e., between the classic and machine learning models. We applied our hybrid model to predict SCSS during magma ocean solidification on Earth, Mars, and the Moon, and we compared our model results to expected S contents in the residual magma oceans calculated by mass balance. Our results confirm that during early accretion, sulfides precipitated from magma oceans and into the outer cores of Earth and Mars, but not the Moon. Subsequently, once the respective magma oceans began precipitating minerals with increasingly FeO-rich and SiO2-, Al2O3-, and MgO-depleted compositions, the increasing S concentration in the residual magma was offset by temperature and compositional effects on SCSS, preventing sulfide precipitation during intermediate stages of crystallization. Sulfides precipitated late during magma ocean crystallization, but failed to percolate through the underlying crystalline mantle, significantly contributing to the modern bulk-silicate sulfur abundances of Earth, Mars, and the Moon. Our calculations suggest that late-stage sulfide precipitation occurred at shallow depths of 120–220 km, 40–320 km, and < 10 km in the magma oceans of Earth, Mars, and the Moon, respectively.

Sources of Cu-Rich Sulfide Mineralization and high-Ni Olivine of the Rudnaya Dyke (Imangda Junction, Norilsk Region): Based on Compositional, Isotope and Model Data

The Rudnaya dyke of the Imangda ore junction is composed of the weakly differentiated olivine-bearing to olivine gabbrodolerites with sulfide globules and disseminated sulfides of (pentlandite-pyrrhotite)-chalcopyrite-cubanite composition. Along with cogenetic sulfide mineralization, dyke’s gabbrodolerites contain xenoliths of hornfelsed basalts, abundant amygdales and rare grains of zoned Ol-1 Fo90-47 with 0.5–0.06 wt % NiO that coexist with subhedral olivine Fo74-36 of the second generation. Modeling in the COMAGMAT and alphaMELTS programs showed that high-Mg olivine 1 with Cr-spinel inclusions could not be crystallized from a Fe-enriched tholeiitic magma that is parental for the dyke with 4.8–7.3 wt % MgO and 11.6–16.7 wt % total Fe2O3. The trend of variations and high Ni up to 0.5 wt. % in the cores of xenocrystic olivine Fo90-76 in contrast to maximum Fo83 and 0.4 wt. % NiO in olivine from the ore-bearing intrusions and picritic basalts of the Norilsk region point toward the presence of picritic cumulates, which magma had not exchanged with sulfide liquid. Platinum group element (PGE) abundances increase (up to 2.2 ppm) with Cu/Ni in the whole rocks as well as with proportions of pentlandite in a sulfide association. A specific chalcophile metal distribution, which is characterized by Ni, Os and Ir minima, elevated Cu/Ni (5–15) and Cu/Pd (3200–10 900) as well as lower both PGE tenor of sulfides (2–65 ppm) and Pd content in pentlandite (175 ppm) compared to typical of ore-bearing intrusions, suggests that Cu-rich sulfide mineralization was not mechanically captured from highly fractionated sulfide fractions of ore-bearing magmas but is cogenetic with a magma of the dyke. Sulfide saturation, near-simultaneous with fluid saturation and degassing, was achieved due to assimilation of sedimentary sulfur and volatiles from Devonian evaporites in the dyke conduit that is supported by the heavy S isotope composition of dyke’s sulfides with the average δ34S = 14.7 ±1.1‰ (n = 31), close to the values in sulfides from the endocontact zones of the ore-bearing Imangda intrusions hosted by Devonian strata. The initial isotopic characteristics of dyke’s rocks (Sri 0.70517–0.70532, ɛNd from –0.4 to 0.8) imply its comagmatic origin with the Norilsk-type intrusions whereas the overall data do not exclude even its spatial connection with an upper crustal conduit system of the ore-bearing magmas.

Enrichment of cobalt in the Xiarihamu Ni-Co sulfide deposit in the East Kunlun orogenic belt, Western China: Constraints from distribution of cobalt in sulfides and Fe and S isotopes of sulfides

The Xiarihamu Ni-Co sulfide deposit in the East Kunlun orogenic belt (EKOB), western China, is the largest magmatic Ni-Cu-(Co) sulfide deposit found in the orogenic belts worldwide. The geochemical behavior of Co during the evolution of sulfide melt is key to understand the enrichment process of Co in the Xiarihamu deposit, however remains unclear. In this study, the Co contents of sulfide inclusions enclosed within olivine and pyroxene and those of the sulfides interstitial to olivine and pyroxene in the Xiarihamu deposit were examinated by the Scanning Electron Microscopy (SEM) -Energy Dispersive Spectroscopy (EDS) and Electron Probe Microanalyzer (EPMA). The Fe and S isotopic compositions of the sulfides were measured in situ by LA-MC-ICPMS. The results show that Co contents increase from silicate to sulfide and arsenide minerals, and from chalcopyrite to pyrrhotite and pentlandite in the sulfides. High Co contents in pentlandite of pyroxenite (av. 2.79 %) and gabbro (av. 7.34 %) indicate that Co is enriched in the pentlandite of pyroxenite in different stage of magma. The pyrrhotite and pentlandite show positive correlation of Co with Fe and Ni, and suggested isomorphic substitution of Co for Fe and Ni. The δ56Fe values increase from pyrrhotite to pentlandite due to kinetic fractionation of Fe isotopes of Fe valent and bond length/strength, because pyrrhotite has longer bond and weaker bond strength of Fe-S than pentlandite, and display lighter Fe isotopic compositions. The δ56Fe values of pentlandite increase substantially from host peridotite to pyroxenite, which could be related to subsolidus fractional crystallization processes of monosulfide solid solution (MSS). The sulfide segregated and crystallized early from the MSS is richen in light Fe isotope. The sulfides in gabbro have high δ34S values, similar to δ34S of the sulfides in the country rocks of Proterozoic granitic gneiss, indicating a continuous addition of external sulfur into magma chamber. The δ34S and δ56Fe values of the sulfides approximately increase with increasing Co contents. Higher δ56Fe and δ34S values and Co contents of pentlandite in the pyroxenite suggest that the Co enrichment is mainly associated with sulfide saturation of magmas by crustal contamination.

Lower Talnakh Type Intrusions of the Norilsk Ore Region

Troctolites, olivine and picrite gabbrodolerites account for up to 75% of the Lower Talnakh type intrusions in places of their increased thickness whereas reduced thickness sections consist of olivine-free and olivine-bearing gabbrodolerites. Differentiation is not obvious within these high-Mg cumulates, although the content of TiO2 and alkalis increases towards the upper endocontacts. The transitions between the rock types are gradational, and the composition of low Ni olivine in different rocks (Fo70–83, 0.01–0.2 wt % NiO) overlap significantly. Clinopyroxene (Fs7–13, Mg# 68–89) is characterized by both the lowest contents and variation ranges of Cr2O3 (0.01–0.5 wt %) and TiO2 (0.05–1.0 wt %) among all types of the intrusions of the Norilsk complex that is consistent with the Cr-depleted (0.002–0.051 wt % Cr2O3) bulk rock compositions. Later orthopyroxene (Fs15–30) is crystallised by the reaction of the residual melt with early olivine. Plagioclase forms porphyritic phenocrysts and their intergrowths along with ophitic laths as well as dominates in schlieren and fragments of leucocratic rocks in taxitic and picritic gabbrodolerites with a poorly sorted layered texture. In olivine-rich rocks, sulfides are represented by the association of troilite ± hexagonal pyrrhotite + Fe- and Co-rich pentlandite + Fe-enriched chalcopyrite (± putoranite, talnakhite) ± cubanite. In the upper and lower parts of the intrusions, the association of hexagonal pyrrhotite + chalcopyrite + pentlandite occurs, while monoclinic pyrrhotite + chalcopyrite + Ni-enriched pentlandite are formed in the endo- and exocontacts. The concentration of base (0.077–0.21 wt % Ni, 0.05–0.38 wt % Cu) and platinum metals (0.03–0.26 to 0.40 g/t total PGE) in mineralized rocks is very low. Upon small amounts of sulfides and extremely low base and platinum metal tenors, the heterogeneous S isotopic composition of Lower Talnakh type sulfides (mainly 3.8–8.6‰, but up to 11.8%) most likely reflects the achievement of repeated sulfide saturation during the assimilation of sulfate S by magma that has previously experienced loss of chalcophile metals into a coexisting sulfide fluid at depth. The Sr-Nd isotopic compositions of the Lower Talnakh intrusions (Sri – from 0.7073 to 0.7087 and εNd(Т) from –1.8 at –5.9 recalculated to 250 Ma) show the predominant contamination with Proterozoic material, in contrast to the ore-bearing intrusions, which Sr-Nd isotope compositions indicate contamination with upper crustal sedimentary matter of the Paleozoic age.

Sulfate recycling at subduction zones indicated by sulfur isotope systematics of Mesozoic ultramafic island arc cumulates in the North American Cordillera

The isotopic composition of sulfur in convergent margin-related orthomagmatic sulfides is critical to the debate on: 1) petrological mechanisms of sulfide saturation in relatively oxidized magmatic systems, and 2) the relative contribution of subducted sulfate to the overall sulfur budget of the sub-arc mantle. Magmatic sulfides that crystallize in deep-seated plutonic rocks are less susceptible to isotopic fractionation arising from magmatic degassing and are thus better suited for studies of primary S-isotope compositions of arc magmas than their extensively degassed volcanic counterparts. Isotopic compositions of chalcopyrite and pyrrhotite, which crystallized from trapped immiscible sulfide melt, and secondary fibrous pyrite after pyrrhotite in the Polaris Alaskan-type ultramafic-mafic intrusion (Early Jurassic) of the North American Cordillera were determined by secondary ion mass spectrometry. Chalcopyrite grains from five olivine clinopyroxenites are fresh and homogeneous and they have uniform near-chondritic δ34S values (-0.19 +0.48/-0.32‰; n = 97). In contrast, pyrrhotite (δ34S = -1.6 +2.8/-0.6; n = 34) and secondary pyrite (δ34S = -2.7 +1.8/-4.4‰; n = 21) grains display subchondritic but highly variable δ34S. The marked difference in measured δ34S of different sulfide phases attests to the critical advantage of using in-situ microanalytical techniques over whole-rock isotopic analysis. Pyrite grains from hornfelsed volcanogenic country rocks have elevated S-isotope values (δ34S = +7.4 +1.3/-1.7‰; n = 11). The near- to subchondritic isotopic compositions of sulfides from the Polaris intrusion demonstrate that wall-rock assimilation played a minor role and that sulfur in the Polaris magmas is largely magmatic. Fibrous textures and variable, but negative, δ34S of pyrrhotite and pyrite indicate post-magmatic mobility of sulfur due to low-temperature alteration by hydrothermal fluids. The narrow range of chalcopyrite δ34S, however, indicates that it remained unaffected by hydrothermal processes and equilibrated under uniform magmatic physicochemical conditions. Assuming sulfide liquid immiscibility at T ≥ 800 °C, geochemical modeling of S-isotope fractionation indicates that the Polaris parental magmas had suprachondritic δ34S between +1‰ (at log fO2 = FMQ+1) and +5‰ (at log fO2 =FMQ+2), consistent with the contribution of subducted sulfate to the sub-arc mantle.

The Roles of Various Types of Crustal Contamination in the Genesis of the Jinchuan Magmatic Ni-Cu-PGE Deposit: New Mineralogical and C-S-Sr-Nd Isotope Constraints

Abstract Addition of crustal sulfur to the Jinchuan magma or oxidation of the magma associated with carbonate assimilation has been considered to be the main cause of sulfide saturation in the magma by two opposing groups of researchers. To address this controversy, we have carried out an integrated mineralogical and C-S-Sr-Nd isotope study of the Jinchuan magmatic Ni-Cu-platinum group element (PGE) sulfide ore deposit. Pure marble, olivine marble, serpentine marble, and hybrid rocks occur in the contact zone. The δ13Ccarb values of the Jinchuan sulfide-bearing ultramafic rocks containing calcite xenocrysts are from –4.7 to –2.9‰, which are similar to or slightly lower than those of the marbles and associated hybrid rocks (–3.9 to 0.8‰) but significantly higher than those of the calcite-barren intrusive rocks (–9.3 to –8.0‰). This, together with the calcite xenocrysts and calcium-silicate minerals in hybrid rocks and some intrusive rocks, indicates that carbonate assimilation took place during magma-carbonate interaction. Only less than several hundred ppm of the CO2 gas produced in the reaction zone could be added to the Jinchuan magma. Such a trace amount of additional CO2 was rapidly swamped by the much greater mass of FeO in the magma, resulting in little change in the FeO/Fe2O3 of the magma, and thereby negligible change of magma redox state. This is evident from similar calculated fO2 values for the calcite-bearing (~QFM+0.7) and calcite-barren (~QFM+0.6) intrusive rocks. The new results rule out the possibility that sulfide saturation in the Jinchuan magma resulted from in situ carbonate assimilation. The Sr-Nd isotope data from this study and previous studies are consistent with up to 20% bulk contamination with siliceous crustal materials at depth, followed by minor amounts of in situ carbonate assimilation by the Jinchuan magma. Our new sulfur isotope data expand the range of δ34S for the Jinchuan deposit significantly. The new range is from −7.6 to 3.0‰, with an average of −1.8‰, which is generally lower than the mantle value (0 ± 2‰). The new result supports the premise that crustal sulfur was involved in the genesis of the Jinchuan deposit. Very high, crustal-like S/Se ratios (as high as 8080) for some of the samples from the deposit provide additional support for the interpretation. The country rocks in the vicinity of the Jinchuan deposit analyzed to date have δ34S values varying from −4.0 to 11.3‰, with an average of 2.9‰, which is higher than both the mantle value and the average value of the Jinchuan deposit, suggesting that the Jinchuan magma acquired some crustal sulfur at depth, likely concurrent with the siliceous assimilation. Numerical modeling of δ34S-S/Se of sulfide ores and country rocks further illustrates that the observed variations of δ34S and S/Se ratios are related to the assimilation of S-rich rocks located at depth, followed by progressive dilution of the contaminated δ34S-S/Se signature. Based on the new results, we conclude that contamination with siliceous crustal materials as well as addition of crustal sulfur at depth played a critical role in triggering sulfide saturation in the Jinchuan magma.

Compositional variations of magnetite in different sulfide ore types in the Jinchuan Ni-Cu-PGE sulfide deposit, NW China: Insights into the mineralizing processes of conduit-type systems

The trace-element composition of magnetite in Ni–Cu–platinum-group element (PGE) sulfide deposits is influenced by magmatic evolution, fractional crystallization of sulfide liquid, and post-magmatic processes, and, therefore, may record ore-forming processes. The Jinchuan Ni–Cu–(PGE) sulfide deposit in NW China contains a variety of sulfide ore types. Despite the capabilities of magnetite to serve as a petrogenetic indicator, its textural–compositional variability in these different sulfide ore types has received little attention. Five types of magnetite with distinct textures and chemical composition are identified in this deposit: (1) Cr-magnetite that crystallized from silicate magma, (2) reactional magnetite produced by the diffusion of oxygen from sulfide liquid to silicate melt, magnetite that crystallized from (3) MSS and (4) ISS, and (5) magnetite that precipitated from hydrothermal fluids. The compositional variability of Cr-magnetite in net-textured and disseminated ores records fractionation of multiple pulses of silicate magmas in a conduit system. Particularly, the higher Ni/Cr and lower V content of Cr-magnetite in disseminated ores relative to those in net-textured ores suggests that the silicate magmas from which the disseminated ores formed were more evolved and had higher fO2 than the magmas from which the net-textured ores formed. Compositional differences between Cr-magnetite and MSS magnetite suggest that magnetite that crystallized from sulfide liquids has higher Ni/Cr ratio, and lower concentrations of lithophile and chalcophile elements. Thus, magmatic magnetite with such compositional features is indicative of sulfide saturation in Ni–Cu–(PGE) sulfide deposits. Compositional differences between MSS and ISS magnetite record fractional crystallization of sulfide liquid. Particularly, the lower V content of ISS magnetite relative to that of MSS magnetite suggests an increase in fO2 during fractionation of the sulfide liquid. Accordingly, this results in greater diffusion of oxygen between the sulfide liquid and surrounding silicate magma, and the preferential occurrence of reactional magnetite in Cu-rich ores. Hydrothermal magnetite records the interaction of magmatic sulfides with oxidized hydrothermal fluids. Based on the lowest chalcophile element contents of this type of magnetite, this interaction did not affect the metal budget of the sulfide ores. Lastly, the similar chalcophile element contents, and overall similar multi-element variation patterns of MSS magnetite in disseminated and massive ores demonstrates that the sulfide liquid that formed the different ore types may have had similar chalcophile element contents. Therefore, the massive ores likely formed by the draining and coalescance of originally disseminated sulfide liquid in a mush zone. Taken together, the compositional variability of texturally distinct magnetite at Jinchuan document a range of magmatic–hydrothermal processes that formed and modified this mineralized system. This contribution continues to highlight the potential for magnetite to serve as a petrogenetic indicator for magmatic Ni-Cu-PGE deposits globally.

The geology, geochemistry, and magmatic evolution of the Legris Lake mafic–ultramafic complex, Ontario, Canada

The Archean Legris Lake mafic–ultramafic complex (LLC) is spatially (~ 12 km east) and temporally (2690.59 ± 0.77 Ma) associated with the world-class Lac des Iles (LDI) palladium deposit. Modeling of whole-rock major-element compositions suggests that this complex, previously interpreted as gabbroic, is gabbronoritic in composition, adding to the likely association between LDI and the LLC. Mantle normalized trace-element profiles and modeled parental melt compositions from the cumulate lithologies indicate initial melt extraction from a metasomatized mantle source in an arc setting and subsequent crystallization of olivine, orthopyroxene, and plagioclase at depth following assimilation of SiO2 and S from tonalitic country rock. External S assimilation contributed to sulfide saturation at depth prior to or during emplacement, but sulfide melt entrainment in intruding magmas and its retention at the site of emplacement was variable. These interpretations are supported by (1) variations in Cu/Pd ratios between PGE-rich and PGE-poor lithologies, (2) the strongly negative Eu/Eu* of paragenetically early lithologies, (3) the overlap between whole-rock εNd(T) values of LLC lithologies and Wabigoon tonalite, and (4) the positive δ34S and uniformly non-zero ∆33S values of magmatic sulfides. During emplacement the intruding melts also assimilated metasedimentary country rock. This effect likely became more pervasive during later stages and resulted in additional melt fractionation and inheritance of the trace-element signature of the metasedimentary country rock by the intruding magmas. This assimilation does not, however, seem to have been an important driver of sulfide saturation in this system.

Tectonomagmatic setting and magmatic Cu-PGE metallogeny during the late Neoproterozoic in the Eastern Kunlun Orogen, NW China: Insights from the Hatu Cu-Pt-Pd-bearing mafic-ultramafic intrusion

The Hatu Intrusion is the first late Neoproterozoic Cu-PGE-bearing mafic–ultramafic intrusion in the Eastern Kunlun Orogen. The No. I intrusion with the largest scale and best mineralization delineated six Cu-Pt-Pd ore/mineralized bodies with Cu and Pt + Pd grades of 0.44–1.10% and 0.30–1.00 g/t, respectively. Chalcopyrite-bornite-(pyrrholite) is a common sulfide assemblage that disseminates in ultramafic rocks (e.g., olivine websterite, liherzolite) enriched in chrysolyte (Fo = 76–81) and orthopyroxene (En = 68–69). Zircons from the gabbro show magmatic zircons with blurred oscillatory zoning and Th/U ratios of 0.31–0.71 and yield a weighted mean age of 556 ± 4 Ma, indicating mafic–ultramafic magmatism with Cu-PGE mineralization in the late Neoproterozoic. The Hatu Intrusion exhibits the properties of continental basalt (e.g., 87Sr/86Sr = 0.71317–0.72541, 143Nd/144Nd = 0.51202–0.51246, and Ta/Hf = 0.19–1.16), indicating the geodynamic setting of terminal continental rift-related extension in response to continuous magmatism under the Rodinia supercontinent break-up in the late Neoproterozoic. The primary magma originated from low-degree (∼15–20%) partial melting of slightly metasomatized depleted mantle without accumulating sufficiently radiogenic isotopes, resulting in zircon positive εHf(t) values (5.2–15.0) and some geochemical properties of arc magma. The mafic–ultramafic rocks have Sr-Nd-Pb isotope compositions between depleted mantle and II-type enriched mantle with negative εNd(t) values (-12.4 – −1.7), and their S/Se ratios are 1628–7189, among which most samples (S/Se = 4534–7189) are higher than that of mantle (S/Se = 2850–4350); the δ34S values of sulfide are 0.7–2.6 ‰ and slightly greater than that of depleted mantle (δ34S = -1.8‰). The above geochemical and isotopic signals reveal the contribution of crustal sulfur to the Hatu Intrusion, which is enough to trigger sulfide saturation of Cu-Pt-Pd.