The Cu---Fe---Ni sulfide component of the amphibole-rich veins from the Lherz and Freychinède spinel peridotite massifs (Northeastern Pyrenees, France): A comparison with mantle-derived megacrysts from alkali basalts

The orogenic-type spinel peridotite massifs of Lherz and Freychinède (Northeastern Pyrenees, Ariège, France) were tectonically emplaced along the North Pyrenean fault. They have been cross-cut by Cretaceous alkali basalts, a few kilometres below the Moho. These magmas crystallized at about 1.0–1.5 GPa as veins of amphibole-rich pyroxenites, containing garnet, and also occasionally as phlogopite hornblendites. In spite of the low volume of trapped silicate liquid, the veins contain up to 1900 ppm S, up to 140 ppm Cu and up to 10 ppb Pd. Under the microscope, the sulfides occur as isolated inclusions within magmatic phases (orthopyroxene, clinopyroxene, amphibole, garnet, spinel, ilmenite), irrespective of parting, cleavage or exsolution planes, or as interstitial grains among the major phases, showing signs of textural equilibration. The sulfide inclusions are interpreted as resulting from entrapment of an immiscible sulfide liquid during magmatic crystallization of the veins. However, a detailed comparison with sulfide inclusions from Cpx- and Al-augite megacrysts entrained in continental basalts shows that post-trapping structural and compositional rearrangements have probaly occurred, in response to cooling, deformation and recrystallization of the veins in the lithospheric mantle.

Except in the thinnest veins where subsolidus re-equilibration of the Ni partitioning has occurred between the veins and their host peridotites, the sulfide inclusions are predominantly composed of slightly nickeliferous pyrrhotite, coexisting with subordinate amounts of pentlandite and chalcopyrite. Bulk chemistry recomputed from modal proportions and microprobe analyses of each individual sulfide in 500 inclusions is as follows: 54% Fe, 5.5% Ni, 2.0% Cu and 38.0% S. A calculation combining this composition and the experimentally determined distribution coefficients for Ni and Cu between sulfide melt and silicate melt leads to < 200 ppm Ni and > 85 ppm Cu in the silicate melt at the time at which the sulfide liquid became immiscible. It is concluded that the alkalic basaltic magma parent to the amphibole-rich veins reached sulfide saturation at depth of 30–40 km, i.e. after some differentiation occurred in the uppermost lithospheric mantle.     

A laser ablation ICP-MS study of platinum-group and chalcophile elements in base metal sulfide minerals of the Jinchuan Ni–Cu sulfide deposit,NW China

The paper presents concentrations of the platinum-group and chalcophile elements in the base metal sulfides (BMS) from the Jinchuan Ni–Cu sulfide deposit determined by laser ablation-inductively coupled plasma-mass spectrometry. Mass balance calculations reveal that pentlandite hosts a large proportion of Co, Ni and Pd (> 65%), and that pentlandite and pyrrhotite accommodate significant proportions of Re, Os, Ru, Rh, and Ag (~ 35–90%), whereas chalcopyrite contains a small amount of Ag (~ 10%) but negligible platinum-group elements. Iridium and Pt are not concentrated in the BMS and mostly occur in As-rich platinum-group minerals. The enrichments of Co, Ni, Re, Os, Ru, and Rh in pentlandite and pyrrhotite, and Cu in chalcopyrite are consistent with the fractionation of sulfide liquid and exsolution of pentlandite and pyrrhotite from the mono-sulfide solid solution (MSS). The Ir-bearing minerals exsolved from the MSS, depleting pentlandite and pyrrhotite in Ir, whereas sperrylite exsolved from the residual sulfide liquid on cooling. Diffusion of Pd from residual sulfide liquid into pentlandite during its exsolution from the MSS and crystallization of Pt-bearing minerals in the residual sulfide liquid resulted in the enrichment of Pd in pentlandite and decoupling between Pd and Pt in the Jinchuan net-textured and massive ores.     

CuFeNiS mineral assemblages in upper-mantle peridotites from the Table Mountain and Blow-Me-Down Mountain ophiolite massifs (Bay of Islands area,Newfoundland): Their relationships with fluids and silicate melts

Plastically deformed ultramafic rocks in the Table Mountain and Blow-Me-Down Mountain ophiolites comprise a basal unit of slightly depleted Iherzolites, an intermediate sequence of strongly depleted harzburgites and an upper zone of dunites, also referred to as a transition zone intensively percolated by basaltic melts or magmatic fluids. Thirty-five samples including all of the above rock types have been investigated on 100 polished thin sections for CuFeNiS mineral assemblages. Most of them contain traces of CuFeNi sulfides, native metals and locally Ni arsenide. Compositional features of opaque assemblages as well as their textural sites in the rocks indicate that the present CuFeNiS minerals derive from an upper-mantle sulfide component through extensive subsolidus re-equilibration down to 100°C. The primitive component (predominant pentlandite, minor pyrrhotite and chalcopyrite) is preserved as sulfide inclusions in chromites of the transition zone, due to a subsolidus re-equilibration in a closed system. On the contrary, sulfide assemblages interstitial to silicates and spinel have extensively reacted with reducing serpentinizing fluids to produce sulfur-deficient sulfides such as heazlewoodite and mackinawite and native metals (native copper and awaruite). Microscale variations of redox conditions and the removal of Fe from the silicate during serpentinization may account for the peculiar “grain-by-grain” equilibrium state of intergranular assemblages. In spite of low-temperature alteration, a gradual depletion in sulfide component has been recognized from the basal lherzolites to the intermediate harzburgites while the sulfide content gradually increases in the transition zone (up to 0.2% by volume). The first pattern is consistent with the low-melting nature of the sulfide component in mantle melting processes. Microstructural criteria such as the absence of sulfide inclusions in olivine neoblasts demonstrate that the sulfide component postdates plastic deformation of the transition zone. The sulfide-enrichment pattern is thus ascribed to the percolation of a sulfur-saturated basaltic magma into residual dunites.     

Origin of anomalously Ni-rich parental magmas and genesis of the Huangshannan Ni–Cu sulfide deposit,Central Asian Orogenic Belt,Northwestern China

The Huangshannan Ni–Cu sulfide deposit at the southern margin of the Central Asian Orogenic Belt (CAOB) is an important recent discovery in the Eastern Tianshan Region, Northwestern China. The Huangshannan Intrusion is composed of mafic and ultramafic rocks, and its websterite and lherzolite sequences host the sulfide orebodies. Olivine is the dominant mineral in the Huangshannan Intrusion, occurring as olivine inclusions hosted by pyroxene oikocrysts, as olivine crystals in magmatic sulfides, and as poikilitic crystals in the lherzolite. Small olivine inclusions always coexist with large poikilitic olivine crystals in the same sample, resulting in a heterogeneous texture on the scale of the oikocrysts. The Ni abundance ranges from 1540 to 3772 ppm in poikilitic olivine grains, from 2114 to 3740 ppm in olivine grains hosted by sulfide minerals, and from 2043 to 4023 ppm in olivine inclusions hosted by pyroxene oikocrysts. For the three types of olivine, the ranges in forsterite (Fo) content are 78.97–84.92 mol.%, 81.57–84.79 mol.%, and 80.33–84.68 mol.%, respectively. The Ni content of olivine in the lherzolite is anomalously high relative to the range found in most within plate olivine-bearing mafic-ultramafic rocks. The composition of olivine is controlled mainly by that of the parental magma, fractional crystallization and reactions with interstitial silicate and sulfide melts. Both fractional crystallization and reaction with interstitial silicate may cause a decrease in the Ni content of olivine. The possibility that Ni–Fe exchange causes the anomalously high Ni contents in olivine can be excluded because the olivine grains contained in sulfide have similar or lower Ni content than the olivine grains hosted in the silicate rock. Most of the olivine grains are unzoned, and they have anomalously high Ni contents throughout the crystal. Assuming a partition coefficient of Ni between olivine and silicate magma to be 7, the measured Ni content of olivine in the lherzolite (1540–4023 ppm with a mean of 2907 ppm) indicates that the parental magma contains 220–575 ppm (average of 415 ppm) Ni. This value is higher than that found in basaltic magmas that crystallized olivine with similar Fo contents compared to the Huangshannan Intrusion. As mentioned above, the symmetric and reproducible variations in both Fo and Ni contents from core to margin in most of the olivine grains cannot be explained by fractional crystallization and reactions with interstitial silicate or sulfide melts but may reflect the equilibration of the olivine with new fluxes of magma as the chamber was replenished. The anomalously Ni-rich composition of the parental magmas of the Huangshannan Intrusion, relative to those of many other mineralized olivine-bearing mafic-ultramafic intrusions, may be produced by upgrading and scavenging of metals from a previously formed sulfide melts by a moderately Ni-rich magma. The mass-balance calculations of PGE data indicate that the parental magma that formed lherzolite contains 0.04 ppb Os, 0.02 ppb Ir and 0.4 ppb Pd, whereas the parental magma that formed websterite has 0.02 ppb Os, 0.009 ppb Ir and 0.75 ppb Pd. Rayleigh modeling using PGE tenors indicates that the massive sulfides may be produced by monosulfide solid solution (MSS)-sulfide liquid fractionation from the magma that formed the websterite. Rayleigh modeling of Fo and Ni contents of olivine shows that the parental magma that formed the lherzolite has experienced previous sulfide segregation and olivine crystallization.     

亲铜元素的地球化学行为研究进展及其在岩浆硫化物矿床中的应用

亲铜元素在岩浆演化和硫化物熔离过程中的行为是解释岩浆硫化物矿床形成过程的一个窗口,通过实验研究来探讨亲铜元素的地球化学行为,并用于岩浆硫化物矿床的定量化研究是此类矿床今后的一个发展方向。本文总结了硫和亲铜元素在岩浆演化过程中的行为规律,并阐明了在岩浆硫化物矿床中的应用,在如下五个方面分别做了讨论：① 通过实验对玄武质岩浆中S溶解度的研究,总结出引起硫化物饱和的4个控制因素: 岩浆混合、温度迅速降低、壳源混染、快速的结晶分异作用;② 通过Ni在橄榄石和硅酸盐熔浆中的分配,定量模拟了岩浆演化过程中,橄榄石中的Ni含量随着橄榄石成分（Fo）变化的规律;③ 总结了Ni—Cu—PGE—Au在液态硫化物和硅酸盐岩浆中的分配系数,总结了控制分配系数的因素,并探讨了“R因素”对亲铜元素富集的控制机理;④ 橄榄石被硫化物包围时,与硫化物发生交换反应,通过交换反应系数（KD）可以定量估算硫化物熔浆中Ni的含量;⑤ 通过实验得出的亲铜元素在单硫化物固溶体（MSS）和液态硫化物之间的分配,总结了岩浆铜镍硫化物矿床中的分带现象。最后探讨了岩浆硫化物矿床存在的问题和发展方向。     

The sulfides in the garnet pyroxenite xenoliths from Salt Lake Crater, Oahu

Trace amounts of sulfide, ranging from 0?06 to 0?26 volume percent, are present in the garnet pyroxenite xenoliths in nephelinebasalt at Salt Lake Crater, Oahu, Hawaii. Microscopic studyrevealed the existence of three chemically and physically distinctsulfide types, i.e. enclosed, interstitial, and vein sulfides.The enclosed sulfide forms spherical inclusions in primary pyroxene,garnet, ilmenite, and spinel. It has a bi-modal chemical character,which may be in part due to alteration of some of the enclosedsulfide grains by the nepheline basalt host magma, but moreprobably represent Cu-Ni-rich sulfide liquid coexisting withCu-rich monosulfide solid solution. The interstitial sulfideis uni-modal and occurs in the interstices of the primary silicates.It has been subjected to intense chemical alteration by thenepheline basalt host magma. As a result the interstitial sulfidebecame Cu-poor with a varying Ni content, which indicates thatcomplete chemical equilibrium with the basalt host magma hasnot been attained. The vein sulfide, present as fracture fillings, is of late genesisand appears to represent partly altered enclosed sulfide. Thealteration process is the same as that which affected the interstitialsulfide. The mineralogy and chemistry of the enclosed sulfide suggeststhat the xenoliths have been abruptly cooled from about 1000?C, which represents the ejection of the xenoliths from thehost basalt magma.     

Chalcophile element geochemistry of the Boggy Plain zoned pluton, southeastern Australia: a S-saturated barren compositionally diverse magmatic system

The behavior of the platinum group elements (PGE) and Re in felsic magmas is poorly understood due to scarcity of data. We report the concentrations of Ni, Cu, Re, and PGE in the compositionally diverse Boggy Plain zoned pluton (BPZP), which shows a variation of rock type from gabbro through granodiorite and granite to aplite with a SiO₂ range from 52 to 74 wt %. In addition, major silicate and oxide minerals were analyzed for Ni, Cu, and Re, and a systematic sulfide study was carried out to investigate the role of silicate, oxide, and sulfide minerals on chalcophile element geochemistry of the BPZP. Mass balance calculation shows that the whole rock Cu budget hosted by silicate and oxide minerals is <13 wt % and that Cu is dominantly located in sulfide phases, whereas most of the whole rock Ni budget (>70 wt %) is held in major silicate and oxide minerals. Rhenium is dominantly hosted by magnetite and ilmenite. Ovoid-shaped sulfide blebs occur at the boundary between pyroxene phenocrysts and neighboring interstitial phases or within interstitial minerals in the gabbro and the granodiorite. The blebs are composed of pyrrhotite, pyrite, chalcopyrite, and S-bearing Fe-oxide, which contain total trace metals (Co, Ni, Cu, Ag, Pb) up to ~16 wt %. The mineral assemblage, occurrence, shape, and composition of the sulfide blebs are a typical of magmatic sulfide. PGE concentrations in the BPZP vary by more than two orders of magnitude from gabbro (2.7–7.8 ppb Pd, 0.025–0.116 ppb Ir) to aplite (0.05 ppb Pd, 0.001 ppb Ir). Nickel, Cu, Re, and PGE concentrations are positively correlated with MgO in all the rock types although there is a clear discontinuity between the granodiorite and the granite in the trends for Ni, Rh, and Ir when plotted against MgO. Cu/Pd values gradually increase from 6,100 to 52,600 as the MgO content decreases. The sulfide petrology and chalcophile element geochemistry of the BPZP show that sulfide saturation occurred in the late gabbroic stage of magma differentiation. Segregation and distribution of these sulfide blebs controlled Cu and PGE variations within the BPZP rocks although the magma of each rock type may have experienced a different magma evolution history in terms of crustal assimilation and crystal fractionation. The sulfide melt locked in the cumulate rocks must have sequestered a significant portion of the chalcophile elements, which restricted the availability of these metals to magmatic-hydrothermal ore fluids. Therefore, we suggest that the roof rocks that overlay the BPZP were not prospective for magmatic-hydrothermal Cu, Au, or Cu–Au deposits.     

Geochemical structure of the Kivakka layered olivinite-norite-gabbronorite intrusion,North Karelia: Distribution of chalcophile elements

The distribution of elements and their correlations were analyzed throughout the section of the Kivakka intrusion to formulate the geochemical tendencies in the behavior of elements of different groups during formation of layered basic-ultrabasic complexes. (1) It was shown that the distribution of trace elements in the layered series is controlled by their ability or inability to enter isomorphically the cumulus minerals. The distribution of trace elements that occur as isomorphic admixtures in cumulus minerals (Cr, Mn, Zn, Co, Ni, and Ti), regardless of their geochemical type, is correlated with the crystallization order and distribution of minerals in the silicate matrix of the rocks. Elements that practically are not involved into silicates (S, Cu, Ag) show no any systematic variations; i.e., they are not controlled by fractionation of major rock-forming mineral. Their behavior is driven by the appearance of individual phase—sulfide melt, whose localization, formation time, and scales of fractionation are determined by saturation of parental melt in sulfide sulfur and general degree of its fractionation. (2) The comparison of cross-section variations of elements that isomorphically substitute for major elements in the Fe-Mg silicates, but differ in chalcophile affinity (in order of increase of chalcophile affinity: Mn → Zn → Co → Ni) reflects the contribution of unmixing and fractionation of sulfide melt during intrusion solidification. This is quantitatively defined primarily by partitioning coefficients of elements between cumulus silicates and magmatic melt, on the one hand, and between magmatic and sulfide melts, on the other hand. (3) The absence of simple correlation between local sulfide-rich horizons and silicate matrix of the rocks and signs of independent fractionation of sulfide melt prevent any attempts to predict the localization and scales of local sulfide mineralization within the layered series on the basis of petrochemical and related criteria. Only tendencies in the distribution of ore elements and sulfur across the section can be used for these purposes.     

Origin of ultramafic inclusions and megacrysts in a monchiquite dyke at Streap,inverness-shire,Scotland

Spinel lherzolite nodules, composed of olivine (Fo_88.7?89.2), clinepyroxene (6.5% Al₂O₃) and Al-rich spinel, and websterite nodules as well as megacrysts of clinopyroxene, orthopyroxene and magnetite occur in a monchiquite at Streap, Scotland. Petrographic data are given and microprobe analyses of coexisting phases in six spinel lherzolite nodules and one websterite nodule are reported, along with analyses of both types of pyroxene megacrysts. The spinel lherzolites show internal chemical homogeneity, and their mineral chemistries suggest equilibrium conditions of 1100–1200°C and 14–23 kb. The websterite nodules are, on the basis of mineral chemistry and petrography, considered to be crustal material. The megacrysts constitute a separate group, differing in composition from analogous phases in associated lherzolites and websterites as well as from monchiquite phenocryst phases, and show systematic chemical variations corresponding to low pressure crystal fractionation processes.     

Chalcophile element partitioning between sulfide phases and hydrous mantle melt: Applications to mantle melting and the formation of ore deposits

Understanding the geochemical behavior of chalcophile elements in magmatic processes is hindered by the limited partition coefficients between sulfide phases and silicate melt, in particular at conditions relevant to partial melting of the hydrated, metasomatized upper mantle. In this study, the partitioning of elements Co, Ni, Cu, Zn, As, Mo, Ag, and Pb between sulfide liquid, monosulfide solid solution (MSS), and hydrous mantle melt has been investigated at 1200 °C/1.5 GPa and oxygen fugacity ranging from FMQ−2 to FMQ+1 in a piston-cylinder apparatus. The determined partition coefficients between sulfide liquid and hydrous mantle melt are: 750–1500 for Cu; 600–1200 for Ni; 35–42 for Co; 35–53 for Pb; and 1–2 for Zn, As, and Mo. The partition coefficients between MSS and hydrous mantle melt are: 380–500 for Cu; 520–750 for Ni; ∼50 for Co; <0.5 for Zn; 0.3–6 for Pb; 0.1–2 for As; 1–2 for Mo; and >34 for Ag. The variation of the data is primarily due to differences in oxygen fugacity. These partitioning data in conjunction with previous data are applied to partial melting of the upper mantle and the formation of magmatic-hydrothermal Cu–Au deposits and magmatic sulfide deposits.I show that the metasomatized arc mantle may no longer contain sulfide after >10–14% melt extraction but is still capable of producing the Cu concentrations in the primitive arc basalts, and that the comparable Cu concentrations in primitive arc basalts and in MORB do not necessarily imply similar oxidation states in their source regions.Previous models proposed for producing Cu- and/or Au-rich magmas have been reassessed, with the conclusions summarized as follows. (1) Partial melting of the oxidized (fO₂ > FMQ), metasomatized arc mantle with sulfide exhaustion at degrees >10–14% may not generate Cu-rich, primitive arc basalts. (2) Partial melting of sulfide-bearing cumulates in the root of thickened lower continental crust or lithospheric mantle does not typically generate Cu- and/or Au-rich magmas, but they do have equivalent potential as normal arc magmas in forming magmatic-hydrothermal Cu–Au deposits in terms of their Cu–Au contents. (3) It is not clear whether partial melting of subducting metabasalts generates Cu-rich adakitic magmas, however adakitic magmas may extract Cu and Au via interaction with mantle peridotite. Furthermore, partial melting of sulfide-bearing cumulates in the deep oceanic crust may be able to generate Cu- and Au-rich magmas. (4) The stabilization of MSS during partial melting may explain the genetic link between Au-Cu mineralization and the metasomatized lithospheric mantle.The chalcophile element tonnage, ratio, and distribution in magmatic sulfide deposits depend on a series of factors. This study reveals that oxygen fugacity also plays an important role in controlling Cu and Ni tonnage and Cu/Ni ratio in magmatic sulfide deposits. Cobalt, Zn, As, Sn, Sb, Mo, Ag, Pb, and Bi concentrations and their ratios in sulfide, due to their different partitioning behavior between sulfide liquid and MSS, can be useful indices for the distribution of platinum-group elements and Au in magmatic sulfide deposits.     

Genesis of the Huangshannan high-Ni tenor magmatic sulfide deposit in the Eastern Tianshan,northwest China: Constraints from PGE geochemistry and Os–S isotopes

The Huangshannan magmatic Ni-Cu sulfide deposit is one of a group of Permian magmatic Ni-Cu deposits located in the southern Central Asian Orogenic belt in the Eastern Tianshan, northwest China. It is characterized by elevated Ni tenor (concentrations in recalculated 100% sulfide) in sulfide within ultramafic rocks (9–19 wt%), with values much higher than other deposits in the region. Sulfides of the Huangshannan deposit are composed of pentlandite, chalcopyrite, and pyrrhotite and the host rock is relatively fresh, indicating that the high-Ni tenor is a primary magmatic feature rather than formed by alteration processes. It is shown that sulfides with high-Ni tenor can be generated by sulfide-olivine equilibrium at an oxygen fugacity of QFM +0.5, for magmas containing 450 ppm Ni and 20% olivine. Ores with >10 wt% sulfur have relatively low PGE and Ni tenors compared to other ores, R factor (mass ratio of silicate to sulfide liquid) modeling of Ni indicates that they formed at moderate R values (150–600). Based on this constraint on R values, ores with <10 wt% sulfides in the Huangshannan deposit can be segregated from a similar parental magma with 0.05 ppb Os, 0.023 ppb Ir, and 0.5 ppb Pd at R values between 600 and 3000. This, coupled with the supra-cotectic proportions of sulfide liquid to cumulus silicates in the Huangshannan ores imply mechanical transport and deposition of sulfide liquid in a magma pathway or conduit, in which sulfides must have interacted with large volumes of silicate magma. Platinum and Pd depletion relative to other platinum group elements (PGEs) are observed in fresh and sulfide-rich samples (S > 4.5 wt%). As sulfide-rich samples are also depleted in Cu, and as interstitial sulfides in those samples are physically interconnected at a scale of several cms, the low Pt and Pd anomalies are attributed to solid Pt and Pd phases crystallization and retention with the monosulfide solid solution (MSS) and Cu-rich sulfide liquid percolation during MSS fractionation. This finding indicates that Pt anomalies in sulfide-rich rocks from magmatic Ni-Cu deposits in the Eastern Tianshan are the result of sulfide fractionation rather than a hydrothermal effect. ¹⁸⁷Os/¹⁸⁸Os_(278Ma) values of the lherzolite samples vary from 0.27 to 0.37 and γOs_(278Ma) values vary from 110 to 189, indicating significant magma interaction with crustal sulfides, rich in radiogenic Os. Well constrained γOs values and δ³⁴S values (−0.4 to 0.8‰) indicate that crustal contamination occurred at depth before the arrival of the magma in the Huangshannan chamber. Regionally, deposits with high-Ni tenor have not been reported other than the Huangshannan deposit; however, many intrusions with high-Ni contents in olivine are present in NW China, such as the Erhongwa, Poyi and Poshi intrusions. Those intrusions are capable of forming high-Ni tenor sulfides due to olivine-sulfide-silicate equilibrium and relative high-Ni content in parent magma, making them attractive exploration targets.     

Microcontinents among the accretionary complexes of the Central Asia Orogenic Belt: In situ Re–Os evidence

Major elements and Re–Os isotope ratios were analysed in situ on individual sulfide grains in spinel peridotite xenoliths hosted by Quaternary intraplate basalts from the Tariat volcanic field, Central Mongolia. The sulfides are dominantly high-temperature (>900 °C) Fe-rich monosulfide solid solution (MSS). Some sulfides with low Ni contents may be residual MSS, whereas other sulfides defining a negative Ni–Cu correlation may be crystallization products of fractionated sulfide melts. The subchondritic ¹⁸⁷Re/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os of some sulfides also indicate they are residual MSS. Os isotope compositions of sulfides reveal the presence of Archean to Proterozoic lithospheric mantle beneath the region. The sulfides have T_RD model ages ranging from 3.0 to 0.2 Ga, with peaks at 1.5–1.3, 1 and 0.7–0.5 Ga. The peak ages are indicative of significant events in the lithospheric mantle at those times. The timing of these events is remarkably consistent with those of the major crust-building events within the Tarvagatay Terrane where the Tariat volcanic field is located. The similarity in the ranges of crustal U–Pb ages and Nd model ages, and our sulfide Os model ages, suggests that the sulfide ages may date metasomatic events in the underlying lithospheric mantle, which were related to tectonothermal events that affected the overlying crust. Radiometric ages from the Tarvagatay Terrane appear to correspond to the Archean model ages from its SCLM counterpart. The last two events (1.1 and 0.7–0.5 Ga) recorded in the Tarvagatay Terrane suggest involvement of the “CAOB mantle” and development of significant juvenile crustal growth in the orogeny.     

铜、镍、铂族元素地球化学性质及其在幔源岩浆起源、演化和岩浆硫化物矿床研究中的意义

Ni、Cu和PGE具有不同于其他微量元素的特殊的地球化学性质,这些特殊的性质使得它们在幔源岩浆起源和演化以及岩浆硫化物矿床的成因研究中具有不可替代的作用。在S不饱和的条件下,Ni、Os、Ir和Ru具有相容元素的特性,而Cu和Pd是强不相容元素,因此,它们在玄武岩浆分离结晶过程中常常发生分异。一旦体系达到S饱和,这些元素则会强烈地进入硫化物熔浆,特别是PGE具有极高的硫化物熔浆/硅酸盐熔浆分配系数,极微量的硫化物熔离便可导致残余岩浆中PGE的显著亏损,因此,PGE是玄武岩浆硫化物熔离作用最敏感的示踪元素。硫化物熔离和成矿实质上是幔源岩浆特殊演化过程的结果,所以,Ni,Cu和PGE的特殊性质可用来探讨岩浆硫化物成矿的关键控制因素。Ni、Cu和PGE具有不同的单硫化物固溶体/硫化物熔浆分配系数,因此,它们也是硫化物熔浆结晶分异的重要示踪元素。本文试图从Ni、Cu和PGE地球化学性质和行为入手,并借助一些研究实例,对它们在幔源岩浆起源和演化以及岩浆硫化物矿床成因研究中的示踪意义进行系统介绍。     

Compositional variations of olivine from the Jinchuan Ni–Cu sulfide deposit,western China: implications for ore genesis

The Jinchuan Ni–Cu sulfide deposit is hosted by an elongated, olivine-rich ultramafic body that is divided by subvertical strike-slip faults into three segments (central, eastern, and western). The central segment is characterized by concentric enrichments of cumulus olivine crystals and interstitial sulfides (pyrrhotite–pentlandite–chalcopyrite intergrowth), whereas the eastern and western segments are characterized by an increase of sulfides toward the lower contacts. In all segments sulfides are concentrated at the expense of intercumulus silicates. Olivine re-crystallization is found to be associated with actinolite alteration in some samples. The compositional variations of primary olivine from the sulfide-poor samples can be explained by a small degree of olivine crystallization (<5%) from a basaltic magma followed by local re-equilibration of the olivine with up to 30% trapped silicate liquid. In the sulfide-bearing samples the compositions of primary olivine record the results of olivine-sulfide Fe–Ni exchange that occurred after the trapped silicate liquid crystallized. Our olivine data indicate that Ni in the original sulfide liquids increased inward in the central segment and laterally away from the lower contact in the eastern segment. Variations in the compositions of sulfide liquids are thought to result from fractional segregation of immiscible sulfide liquid from a basaltic magma in a staging chamber instead of in situ differentiation. High concentrations of olivine crystals (mostly >50 modal%) and sulfide (averaging ~5 wt%) in the rocks are consistent with the interpretation that the Jinchuan deposit was formed by olivine- and sulfide-laden magma successively ascending through a conduit to a higher, now-eroded, level. Sulfide enrichment toward the center in the central segment and toward the lower contact in the eastern and western segments may have, in part, resulted from flow differentiation and gravitational settling during magma ascent, respectively.Editorial handling: P. Lightfoot     

Sulfide oxidation as a process for the formation of copper-rich magmatic sulfides

Typical magmatic sulfides are dominated by pyrrhotite and pentlandite with minor chalcopyrite, and the bulk atomic Cu/Fe ratio of these sulfides is typically less than unity. However, there are rare magmatic sulfide occurrences that are dominated by Cu-rich sulfides (e.g., bornite, digenite, and chalcopyrite, sometimes coexisting with metallic Cu) with atomic Cu/Fe as high as 5. Typically, these types of sulfide assemblages occur in the upper parts of moderately to highly fractionated layered mafic–ultramafic intrusions, a well-known example being the Pd/Au reef in the Upper Middle Zone of the Skaergaard intrusion. Processes proposed to explain why these sulfides are so unusually rich in Cu include fractional crystallization of Fe/(Ni) monosulfide and infiltration of postmagmatic Cu-rich fluids. In this contribution, we explore and experimentally evaluate a third possibility: that Cu-rich magmatic sulfides may be the result of magmatic oxidation. FeS-dominated Ni/Cu-bearing sulfides were equilibrated at variable oxygen fugacities in both open and closed system. Our results show that the Cu/Fe ratio of the sulfide melt increases as a function of oxygen fugacity due to the preferential conversion of FeS into FeO and FeO_1.5, and the resistance of Cu₂S to being converted into an oxide component even at oxygen fugacities characteristic of the sulfide/sulfate transition (above FMQ?+?1). This phenomenon will lead to an increase in the metal/S ratio of a sulfide liquid and will also depress its liquidus temperature. As such, any modeling of the sulfide liquid line of descent in magmatic sulfide complexes needs to address this issue.     

A laser ablation inductively coupled plasma mass spectrometry study of the distribution of chalcophile elements among sulfide phases in sedimentary and magmatic rocks of the Duluth Complex,Minnesota, USA

Nickel-copper sulfide deposits occur in the basal unit of the Partridge River Intrusion, Duluth Complex (Minnesota, USA). Many lines of evidence suggest that these sulfides are formed after assimilation of the proterozoic S-rich black shales, known as the Bedded Pyrrhotite Unit. In addition to S, black shales are enriched in Te, As, Bi, Sb and Sn (TABS) and the basaltic magma of the intrusion is contaminated by the partial melt of the black shales. The TABS are chalcophile and together with the platinum-group elements, Ni and Cu partitioned into the magmatic sulfide liquid that segregated from the Duluth magma. The TABS are important for the formation of platinum-group minerals (PGM) thus their role during crystallization of the base metal sulfide minerals could affect the distribution of the PGE. However, the concentrations of TABS in magmatic Ni-Cu-PGE deposits and their distribution among base metal sulfide minerals are poorly documented. In order to investigate whether the base metal sulfide minerals host TABS in magmatic Ni-Cu-PGE deposits, a petrographic and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) study has been carried out on base metal sulfide and silicate phases of the Partridge River Intrusion, Duluth Complex.Petrographic observations showed that the proportions of the base metal sulfide minerals vary with rock type. The sulfide assemblage of the least metamorphosed Bedded Pyrrhotite Unit from outside the contact metamorphic aureole consists of pyrite with minor pyrrhotite plus chalcopyrite (<5%), whereas within the contact aureole the sulfide assemblage of the Bedded Pyrrhotite Unit rocks consists dominantly of pyrrhotite (>95%) with small amount of chalcopyrite (<2%). The sulfide mineral assemblage in the xenoliths of the Bedded Pyrrhotite Unit and in the mafic rocks of the basal unit contains two additional sulfides, pentlandite and cubanite.Our LA-ICP-MS study shows that sulfides of the Bedded Pyrrhotite Unit are rich in TABS; consistent with these S-rich black shales being the source of TABS that contaminated the mafic magma. Most of the TABS are associated with sulfides and platinum-group minerals in the rocks of the Bedded Pyrrhotite Unit from the contact aureole, the Bedded Pyrrhotite Unit xenoliths and the mafic rocks of the Duluth Complex. In addition to these phases the laser maps show that silicate phases, i.e., orthopyroxene and plagioclase contain Sn and Pb respectively. In contrast, in the least metamorphosed samples of the Bedded Pyrrhotite Unit from outside the contact aureole although the pyrite contains some TABS mass balance calculations indicates that most the TABS are contained in other phases. In these rocks, galena hosts significant amounts of Te, Bi, Sb, Sn and Ag and few very small grains of Sb-rich phases were also observed. The host phases for As were not established but possibly organic compounds may have contributed.     

The Archean komatiite-hosted, PGE-bearing Ni–Cu sulfide deposit at Vaara, eastern Finland: evidence for assimilation of external sulfur and post-depositional desulfurization

Archean komatiites host important resources of Ni, Cu, Co, and PGE, particularly in Western Australia and Canada. In Finland, several small, low-grade sulfide deposits have been found in komatiites, including the ca. 2.8 Ga Vaara deposit in the Archean Suomussalmi greenstone belt. It occurs in the central part of the serpentinized olivine cumulate zone of a komatiitic extrusive body and is composed of disseminated interstitial sulfides consisting of pyrite, pentlandite, millerite, violarite, and chalcopyrite accompanied by abundant magnetite. Although currently subeconomic, the mineralization is interesting due to the very high chalcophile element contents of the sulfide fraction (38 wt% Ni, 3.4 wt% Cu, 0.7 wt% Co, 22.4 ppm Pd, and 9.5 ppm Pt). The sulfides occur in relatively Cr-poor olivine cumulates suggesting involvement of a chromite-undersaturated magma. The parental magma was an Al-undepleted komatiite with an estimated MgO content of at least 24 wt%. In contrast to the common komatiite types in the eastern Finland greenstone belts, the Vaara rocks are moderately enriched in LREE relative to MREE, suggesting that crustal contamination played an important role in the genesis of the Vaara deposit. Multiple sulfur isotope data reveal considerable mass-independent sulfur isotope fractionation both in country rock sedimentary sulfides (Δ³³S ranges from ?0.50 to +2.37?‰) and in the Vaara mineralization (Δ³³S ranges from +0.53 to +0.66?‰), which provides strong evidence for incorporation of crustal sulfur. Extensive replacement of interstitial sulfides by magnetite and the presence of millerite- and violarite-bearing, pyrrhotite-free sulfide assemblages indicate significant post-magmatic, low-temperature hydrothermal oxidation of the primary magmatic pyrrhotite-pentlandite-chalcopyrite assemblages and associated sulfur loss that led to a significant upgrading of the original metal tenors of the Vaara deposit.     

Discovery of Pyrrhotite-Chalcopyrite-Bearing Amphibole Megacrysts in Tongling Area, Anhui Province

Some pyrrhotite-chalcopyrite-bearing amphibole megacrysts (including pyroxene megacrysts) were discovered in Mesozoic augite diorite-porphyrite at Caoshan in Tongling area, Anhui Province. The amphibole megacrysts, belonging mainly to pargasite and magnesiohastingsite, are characteristic of the amphibole composition derived from mantle and crystallized in lower crust. In general, the aggregates of pyrrhotite-chalcopyrite take the shapes of cylinder and sphere. Three occurrences have been recognized in the amphibole megacrysts: parallel linear, bunchy and scattered. The unique cylinder-like shape of the aggregates and remarkable Ni-poor sulfides in Caoshan are distinctively different from the spherical Ni-rich sulfides in pyroxene megacrysts and any other kinds of megacrysts. In terms of composition, the amphibole megacrysts and their sulfides in Caoshan are similar to those in the pyroxenite xenoliths in Qilin, Guangdong Province. In terms of origin, the pyrrhotite-chalcopyrites as exsolution products resulted from the subsolidus re-equilibration of sulfide solid solution within amphibole megacrysts.amphibole megacrysts were first discovered inside and outside China. This discovery is important for the study of regional magma evolution and its associated mineralizations and ore sources as well.     

Sulfides in mantle peridotites from Penghu Islands, Taiwan: Melt percolation, PGE fractionation, and the lithospheric evolution of the South China block

Major elements, highly siderophile elements (HSE) and Re-Os isotope ratios were analysed in situ on individual sulfide grains in spinel peridotite xenoliths hosted by Miocene intraplate basalts from the Penghu Islands, Taiwan. The xenoliths represent texturally and compositionally different mantle domains, and the geochemical characteristics of the sulfides show changes in HSE distribution and Re-Os isotope systematics, produced as their host rocks were metasomatised by percolating fluids/melts. In prophyroclastic and partly metasomatised peridotites from the Kueipi (KP) locality, the sulfides have subchondritic to superchondritic ¹⁸⁷Re/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os ratios. Many of these sulfides reflect fluid/melt interaction with residual MSS and/or crystallization of fractionated sulfide melts, which produced high contents of Cu and PPGEs and high Re/Os; inferred melt/rock ratios are low. In contrast, sulfides in equigranular and extensively metasomatised peridotites from the Tungchiyu (TCY) locality are mainly more sulfur-rich Ni-(Co)-rich MSS, with subchondritic to chondritic ¹⁸⁷Os/¹⁸⁸Os and subchondritic ¹⁸⁷Re/¹⁸⁸Os. These sulfides are interpreted as products of interaction between pre-existing MSS and percolating silicate melts. Melt/rock ratios were high and the percolating melt was less differentiated than the melt that percolated the KP peridotites. Sulfides in a TCY pyroxenite are mainly MSS; they have the lowest HSE contents, subchondritic to superchondritic ¹⁸⁷Os/¹⁸⁸Os and subchondritic ¹⁸⁷Re/¹⁸⁸Os, and may have precipitated from sulfide melts that segregated from basaltic melts under S-saturated conditions. In most sulfides melt percolation appears to have induced fractionation among the HSEs and disturbed Re-Os isotope compositions. Despite the metasomatic effects, rare residual MSS, sulfides that from crystallised sulfide melts and sulfides modified by addition of Re (with no evidence for Os addition) can still provide useful chronological information. Such sulfides yield T_RD age peaks of 1.9, 1.7-1.6, 1.4-1.3 and 0.9-0.8 Ga, which may record the timing of melt extraction and/or metasomatic events in the mantle. These periods are contemporaneous with the major crustal events recorded by U-Pb dates and Nd and Hf model ages in the overlying crust. This close correspondence indicates that the sulfide T_RD ages reflect the timing of lithosphere-scale tectonothermal events (such as melting and metasomatism) that affected both the lithospheric mantle and the overlying crust. The sulfide T_RD ages, taken together with the crustal data, suggest that most of the Cathaysia block had formed at least by Paleo-Proterozoic time, and that some domains are Archean in age.     

Trace elements in sulfide inclusions from Yakutian diamonds

 Sulfide inclusions in diamonds may provide the only pristine samples of mantle sulfides, and they carry important information on the distribution and abundances of chalcophile elements in the deep lithosphere. Trace-element abundances were measured by proton microprobe in >50 sulfide inclusions (SDI) from Yakutian diamonds; about half of these were measured in situ in polished plates of diamonds, providing information on the spatial distribution of compositional variations. Many of the diamonds were identified as peridotitic or eclogitic from the nature of coexisting silicate or oxide inclusions. Known peridotitic diamonds contain SDIs with Ni contents of 22–36%, consistent with equilibration between olivine, monosulfide solid solution (MSS) and sulfide melt, whereas SDIs in eclogitic diamonds contain 0–12% Ni. A group of diamonds without silicate or oxide inclusions has SDIs with 11–18% Ni, and may be derived from pyroxenitic parageneses. Eclogitic SDIs have lower Ni, Cu and Te than peridotitic SDIs; the ranges of the two parageneses overlap for Se, As and Mo. The Mo and Se contents range up to 700 and 300 ppm, respectively; the highest levels are found in peridotitic diamonds. Among the in-situ SDIs, significant Zn and Pb levels are found in those connected by cracks to diamond surfaces, and these elements reflect interaction with kimberlitic melt. Significant levels of Ru (30–1300 ppm) and Rh (10–170 ppm) are found in many peridotitic SDIs; SDIs in one diamond with wustite and olivine inclusions and complex internal structures have high levels of other platinum-group elements (PGEs) as well, and high chondrite-normalized Ir/Pd. Comparison with experimental data on element partitioning between crystals of monosulfide solid solution (MSS) and sulfide melts suggests that most of the inclusions in both parageneses were trapped as MSS, while some high-Cu SDIs with high Pd±Rh may represent fractionated sulfide melts. Spatial variations of SDI composition within single diamonds are consistent with growth histories shown by cathodoluminescence images, in which several stages of growth and resorption have occurred within magmatic environments that evolved during diamond formation. Received: 5 July 1995 / Accepted: 21 February 1996