Sulfide mineralogy and sulfur isotope geochemistry of layered sills in the Deer Lake Complex,Minnesota

The Deer Lake Complex, located in north-central Minnesota, consists of a series of layered peridotite-pyroxenite-gabbro sills. Sulfide minerals occur as fine disseminations throughout pyroxenite and gabbro units, and occur more sporadically in peridotite and basal chilled margin units. Sulfide volume percentage rarely exceeds 0.5. A distinct zonation in sulfide mineralogy and sulfur isotopic composition characterizes the sills. Cobaltian pentlandite is the dominant sulfide mineral in peridotite (pd) units, with Ni-enrichment most likely linked to the serpentinization process. δ³⁴Spd values are variable, ranging from ?3.5 to +2.8‰. Sulfide assemblages in pyroxenite (px) and lower gabbro units consist of chalcopyrite, pyrrhotite, and minor pentlandite. δ³⁴S_px values range from ?1 to +1 ‰. Pyrite is the principal sulfide mineral in upper gabbro (μg) units. Its origin may be related to increased f0₂ conditions of the remaining melt and to reaction between a S-bearing volatile phase and mafic silicates. δ³⁴S_ug values range from 1 to 3.5 ‰. Sulfur isotopic values of chilled margin (2–9 ‰) and peridotite units, together with the erratic spatial distribution of sulfide minerals in these zones, suggests that the parent magma was not initially saturated with sulfur, and that local sulfide concentrations are the result of incorporation of sulfur derived from metasedimentary country rocks. Sulfide saturation was more uniformly reached during pyroxenite formation, with contained sulfur being of magmatic origin. Enrichment in ³⁴S of pyrite from upper gabbro may be explained by buildup of isotopically heavy sulfur following a Rayleigh process, coupled with possible involvement of a SO₂-rich fluid phase during hydrothermal alteration.     

Calculation of sulfur isotope fractionation in sulfides

The increment method has been successfully applied to calculate thermodynamic isotope fractionation factors of oxygen in silicates, oxides, carbonates, and sulfates. In this paper, we modified the increment method to calculate thermodynamic isotope fractionation factors of sulfur in sulfides, based on chemical features of sulfur-metal bonds and crystal features of sulfide minerals. To approximate the bond strength of sulfides, a new constant, known as the Madelung constant, was introduced. The increment method was then extended to calculate the reduced partition function ratios of sphalerite, chalcopyrite, galena, pyrrhotite, greenockite, bornite, cubanite, sulvanite, and violarite, as well as the isotope fractionation factors between them over the temperature range from 0 to 1000 °C. The order of ³⁴S enrichment in these nine minerals is pyrrhotite > greenockite > sphalerite > chalcopyrite > cubanite > sulvanite > bornite > violarite > galena. Our improved method constitutes another model for calculating the thermodynamic isotope fractionation factors of sulfur in sulfides of geochemical interest.     

PGE geochemistry of the Eagle Ni–Cu–(PGE) deposit, Upper Michigan: constraints on ore genesis in a dynamic magma conduit

The Eagle Ni–Cu–(PGE) deposit is hosted in mafic–ultramafic intrusive rocks associated with the Marquette–Baraga dike swarm in northern Michigan. Sulfide mineralization formed in association with picritic magmatism in a dynamic magma conduit during the early stages in the development of the ~1.1?Ga Midcontinent Rift System. Four main types of sulfide mineralization have been recognized within the Eagle deposit: (1) disseminated sulfides in olivine-rich rocks; (2) rocks with semi-massive sulfides located both above and below the massive sulfide zone; (3) massive sulfides; and (4) sulfide veins in sedimentary country rocks. The disseminated, massive and lower semi-massive sulfide zones are typically composed of pyrrhotite, pentlandite and chalcopyrite, whereas the upper semi-massive sulfide ore zone also contains pyrrhotite, pentlandite, and chalcopyrite, but has higher cubanite content. Three distinct types of sulfide mineralization are present in the massive sulfide zone: IPGE-rich, PPGE-rich, and PGE-unfractioned. The lower and upper semi-massive sulfide zones have different PGE compositions. Samples from the lower semi-massive sulfide zone are characterized by unfractionated PGE patterns, whereas those from the upper semi-massive sulfide zone show moderate depletion in IPGE and moderate enrichment in PPGE. The mantle-normalized PGE patterns of unfractionated massive and lower semi-massive sulfides are subparallel to those of the disseminated sulfides. The results of numerical modeling using PGE concentrations recalculated to 100% sulfide (i.e., PGE tenors) and partition coefficients of PGE between sulfide liquid and magma indicate that the disseminated and unfractionated massive sulfide mineralization formed by the accumulation of primary sulfide liquids with similar R factors between 200 and 300. In contrast, the modeled R factor for the lower semi-massive sulfide zone is <100. The fractionated sulfide zones such as those of the IPGE-rich and PPGE-rich massive sulfides and the upper semi-massive sulfide zone can be explained by fractional crystallization of monosulfide solid solution from sulfide liquids. The results of numerical modeling indicate that the sulfide minerals in the upper semi-massive sulfide zone are the products of crystallization of fractionated sulfide liquids derived from a primary sulfide liquid with an R factor similar to that for the disseminated sulfide mineralization. Interestingly, the modeled parental sulfide liquid for the IPGE-rich and PPGE-rich massive sulfide zones has a higher R factor (~400) than that for the unfractionated massive sulfide mineralization. Except one sample which has unusually high IPGE and PPGE contents, all other samples from the Cu-rich sulfide veins in the footwall of the intrusion are highly depleted in IPGE and enriched in PPGE. These signatures are generally consistent with highly fractionated sulfide liquids expelled from crystallizing sulfide liquid. Collectively, our data suggest that at least four primary sulfide liquids with different R factors (<100, 200–300, ~400) were involved in the formation of the Eagle magmatic sulfide deposit. We envision that the immiscible sulfide liquids were transported from depth by multiple pulses of magma passing through the Eagle conduit system. The sulfide liquids were deposited in the widened part of the conduit system due to the decreasing velocity of magma flow. The presence of abundant olivine in some of the sulfide ore zones indicates that the ascending magma also carried olivine crystals. Sulfide saturation was attained in the parental magma due in large part to the assimilation of country rock sulfur at depth.     

Mineralogy and chemistry of Cu-Fe-Ni sulfides in orogenic-type spinel peridotite bodies from Ariege (Northeastern Pyrenees,France)

Mantle-derived peridotite bodies of Ariège are composed of spinel lherzolites and harzburgites ranging from remarkably fresh (less than 5% serpentinized) samples with protogranular texture to secondary foliated samples, which are generally 10%–20% serpentinized. The foliated samples have passed through two cycles of deformation and re-crystallization, the earlier ones occurring at temperatures above 950° C for 15 kbar pressure, the later ones at temperatures between 950° and 750° C for 8–15 kbar. Microscopic investigation of 140 samples reveals an accessoy sulfide component which is more abundant in lherzolie than in harzburgite. This component occurs in two differet textural locations, either as inclusions trapped within silicates during the first stage of re-crystallization or as interstitial grains among silicates. Mineralogy and chemistry of both sulfide occurrences are quite similar, at least in samples less than 5% serpentinized. In these fresh samples, sulfides are composed of complex intergrowths between nickel-rich pentlandite and pyrite, coexisting with minor primary pyrrhotite (Fe₇S₈) and chalcopyrite. Pentlandite and pyrite are interpreted as low-temperature breakdown products of upper mantle monosulfide solid solutions. The mineralogy and chemistry of interstitial sulfides in serpentinized rocks vary in parallel with the degree of serpentinization. In samples less than 10% serpentinized, primary pyrrhotite grades into FeS. In samples more than 10% serpentinized, pyrite is replaced by secondary pyrrhotite, and then disappears totally, whereas the coexisting pentlandite is Fe-enriched and replaced by mackinawite. This sequence of alteration indicates a decrease of sulfur fugacity, resulting from serpentinization of olivine at temperatures below 300° C. This is also the case for the inclusions which have been fractured during the tectonic emplacement of the host peridotites within the crust. The presence of non-equilibrium sulfide assemblages in both cases reflects the sluggishness of solid state reactions at near-surface temperatures. It is inferred from these results that sulfides disseminated within orogenic peridotite massifs are so sensitive to serpentinization that most sulfur fugacity estimates based on fractured inclusions and intergranular sulfides are unreliable.     

The distribution of platinum group elements (PGE) and other chalcophile elements among sulfides from the Creighton Ni–Cu–PGE sulfide deposit, Sudbury, Canada, and the origin of palladium in pentlandite

Concentrations of platinum group elements (PGE), Ag, As, Au, Bi, Cd, Co, Mo, Pb, Re, Sb, Se, Sn, Te, and Zn, have been determined in base metal sulfide (BMS) minerals from the western branch (402 Trough orebodies) of the Creighton Ni–Cu–PGE sulfide deposit, Sudbury, Canada. The sulfide assemblage is dominated by pyrrhotite, with minor pentlandite, chalcopyrite, and pyrite, and they represent monosulfide solid solution (MSS) cumulates. The aim of this study was to establish the distribution of the PGE among the BMS and platinum group minerals (PGM) in order to understand better the petrogenesis of the deposit. Mass balance calculations show that the BMS host all of the Co and Se, a significant proportion (40–90%) of Os, Pd, Ru, Cd, Sn, and Zn, but very little (<35%) of the Ag, Au, Bi, Ir, Mo, Pb, Pt, Rh, Re, Sb, and Te. Osmium and Ru are concentrated in equal proportions in pyrrhotite, pentlandite, and pyrite. Cobalt and Pd (∼1 ppm) are concentrated in pentlandite. Silver, Cd, Sn, Zn, and in rare cases Au and Te, are concentrated in chalcopyrite. Selenium is present in equal proportions in all three BMS. Iridium, Rh, and Pt are present in euhedrally zoned PGE sulfarsenides, which comprise irarsite (IrAsS), hollingworthite (RhAsS), PGE-Ni-rich cobaltite (CoAsS), and subordinate sperrylite (PtAs₂), all of which are hosted predominantly in pyrrhotite and pentlandite. Silver, Au, Bi, Mo, Pb, Re, Sb, and Te are found predominantly in discrete accessory minerals such as electrum (Au–Ag alloy), hessite (Ag₂Te), michenerite (PdBiTe), and rhenium sulfides. The enrichment of Os, Ru, Ni, and Co in pyrrhotite, pentlandite, and pyrite and Ag, Au, Cd, Sn, Te, and Zn in chalcopyrite can be explained by fractional crystallization of MSS from a sulfide liquid followed by exsolution of the sulfides. The early crystallization of the PGE sulfarsenides from the sulfide melt depleted the MSS in Ir and Rh. The bulk of Pd in pentlandite cannot be explained by sulfide fractionation alone because Pd should have partitioned into the residual Cu-rich liquid and be in chalcopyrite or in PGM around chalcopyrite. The variation of Pd among different pentlandite textures provides evidence that Pd diffuses into pentlandite during its exsolution from MSS. The source of Pd was from the small quantity of Pd that partitioned originally into the MSS and a larger quantity of Pd in the nearby Cu-rich portion (intermediate solid solution and/or Pd-bearing PGM). The source of Pd became depleted during the diffusion process, thus later-forming pentlandite (rims of coarse-granular, veinlets, and exsolution flames) contains less Pd than early-forming pentlandite (cores of coarse-granular).     

Ore mineralogy and sulfur isotope study of the massive sulfide deposit of Filon Norte,Tharsis Mine,Spain

The volcanogenic massive sulfide deposit of Filon Norte at Tharsis is hosted by carbonaceous black slate and connected only partly with stockwork veins. The massive ores are usually composed of fine-grained pyrite with subordinate amounts of sphalerite, chalcopyrite, galena and arsenopyrite. Monoclinic pyrrhotite sometimes occurs in massive pyritic ores in the apparently middle and upper horizons of the orebody, and siderite-rich ores are interstratified with compact pyritic ores in the apparently lower horizons. From the occurrence of monoclinic pyrrhotite, together with the FeS contents of sphalerite mostly ranging from 11 to 16 mol %, it is inferred that the sulfide minerals of the massive orebody were precipitated in euxinic muds on the sea-floor at temperatures below 250°C. The negatively shifted, highly variable ³⁴S values of the massive ores and their close similarity to those of the underlying black slates strongly suggest that the sulfide sulfur of the massive orebody and the slates is cognate and biogenic.     

Sulfide evolution in high-temperature to ultrahigh-temperature metamorphic rocks from Lützow–Holm Complex, East Antarctica

The high-temperature (HT) to ultrahigh-temperature (UHT) metamorphic rocks from Lützow–Holm Complex, East Antarctica show a systematic difference between sulfide assemblages in the rock matrix and those found as inclusions in the silicates stable in high-temperatures. Matrix sulfides are commonly pyrite with or without pentlandite and chalcopyrite. On the other hand, inclusion sulfides are pyrrhotite with or without pentlandite and chalcopyrite lamellae. When recalculated into integrated single-phase sulfide compositions, inclusion sulfides from the UHT region showed a wider range of solid–solution composition than the inclusion sulfides from the HT region. The host minerals of the sulfides with extreme solid–solution compositions are those stable at the peak of metamorphism such as orthopyroxene and garnet. One of the most extreme ones is included in orthopyroxene coexisting with sillimanite ± quartz, which is the diagnostic mineral assemblage of UHT metamorphism. These observations suggest that sulfide inclusions preserve their peak metamorphic compositions. Pyrrhotite did not revert to pyrite because of the closed system behavior of sulfur in inclusion sulfides. On the other hand, in the rock matrix where the open system behavior of sulfur is permitted, original sulfides were partly to completely altered by the later fluid activity.     

Sulfide-associated mineral assemblages in the Bushveld Complex, South Africa: platinum-group element enrichment by vapor refining by chloride–carbonate fluids

The petrology of base metal sulfides and associated accessory minerals in rocks away from economically significant ore zones such as the Merensky Reef of the Bushveld Complex has previously received only scant attention, yet this information is critical in the evaluation of models for the formation of Bushveld-type platinum-group element (PGE) deposits. Trace sulfide minerals, primarily pyrite, pyrrhotite, pentlandite, and chalcopyrite are generally less than 100 microns in size, and occur as disseminated interstitial individual grains, as polyphase assemblages, and less commonly as inclusions in pyroxene, plagioclase, and olivine. Pyrite after pyrrhotite is commonly associated with low temperature greenschist alteration haloes around sulfide grains. Pyrrhotite hosted by Cr- and Ti-poor magnetite (Fe₃O₄) occurs in several samples from the Marginal to Lower Critical Zones below the platiniferous Merensky Reef. These grains occur with calcite that is in textural equilibrium with the igneous silicate minerals, occur with Cl-rich apatite, and are interpreted as resulting from high temperature sulfur loss during degassing of interstitial liquid. A quantitative model demonstrates how many of the first-order features of the Bushveld ore metal distribution could have developed by vapor refining of the crystal pile by chloride–carbonate-rich fluids during which sulfur and sulfide are continuously recycled, with sulfur moving from the interior of the crystal pile to the top during vapor degassing.     

Platinum-group element, Gold, Silver and Base Metal distribution in compositionally zoned sulfide droplets from the Medvezky Creek Mine, Noril’sk, Russia

Concentrations of Ag, Au, Cd, Co, Re, Zn and Platinum-group elements (PGE) have been determined in sulfide minerals from zoned sulfide droplets of the Noril’sk 1 Medvezky Creek Mine. The aims of the study were; to establish whether these elements are located in the major sulfide minerals (pentlandite, pyrrhotite, chalcopyrite and cubanite), to establish whether the elements show a preference for a particular sulfide mineral and to investigate the model, which suggests that the zonation in the droplets is caused by the crystal fractionation of monosulfide solid solution (mss). Nickel, Cu, Ag, Re, Os, Ir, Ru, Rh and Pd, were found to be largely located in the major sulfide minerals. In contrast, less than 25% of the Au, Cd, Pt and Zn in the rock was found to be present in these sulfides. Osmium, Ir, Ru, Rh and Re were found to be concentrated in pyrrhotite and pentlandite. Palladium and Co was found to be concentrated in pentlandite. Silver, Cd and Zn concentrations are highest in chalcopyrite and cubanite. Gold and platinum showed no preference for any of the major sulfide minerals. The enrichment of Os, Ir, Ru, Rh and Re in pyrrhotite and pentlandite (exsolution products of mss) and the low levels of these elements in the cubanite and chalcopyrite (exsolution products of intermediate solid solution, iss) support the mss crystal fractionation model, because Os, Ir, Ru, Rh and Re are compatible with mss. The enrichment of Ag, Cd and Zn in chalcopyrite and cubanite also supports the mss fractionation model these minerals are derived from the fractionated liquid and these elements are incompatible with mss and thus should be enriched in the fractionated liquid. Gold and Pt do not partition into either iss or mss and become sufficiently enriched in the final fractionated liquid to crystallize among the iss and mss grains as tellurides, bismithides and alloys. During pentlandite exsolution Pd appears to have diffused from the Cu-rich portion of the droplet into pentlandite.     

PGE mineralization in Archean volcanic systems: geochemical evidence from thick, differentiated mafic-ultramafic flows, Abitibi greenstone belt, Ontario, and implications for exploration

PGE-rich disseminated zones with discrete platinum-group minerals (Pd, Pt and Rh mineral phases) have been discovered in three thick (80–130 m), differentiated (peridotite-gabbro) mafic-ultramafic flows of the Archean Abitibi greenstone belt, Ontario. Three mineralization zones (whole-rock ∑PGE + Au = up to 1000 ppb) occur along four stratigraphic cross sections through a 2 km strike-length of the Boston Creek Flow ferropicritic basalt. Their occurrence most strikingly correlates with lenticular-podiform concentrations of disseminated chalcopyrite (1 %) and clinopyroxene + interstitial magnetite-ilmenite intergrowths (15–20% oxide), high concentrations of related metals (3000 ppm Cu, 3000 ppm S, 1200 ppb Ag, and 1000 ppm V), strong PGE depletion in adjacent rocks and along strike, and lithological and textural complexity in the margins of the central gabbro-diorite layer. The mineralization zone (whole-rock Ir + Pt + Pd + Au = 110 ppb) within Theo's Flow tholeiitic basalt is somewhat similar in occurrence, style, and composition to those within the Boston Creek Flow. In contrast, the mineralization zone (whole-rock Ir + Pt + Pd + Au = 340 ppb) in Fred's Flow komatiitic basalt most strikingly correlates with vesicle-filling intergrowths of pyrrhotite + pentlandite ± chalcopyrite (2 modal %) and high whole-rock concentrations of Ni (2500 ppm), Cu (700 ppm), and S (1.1%) in the upper chilled margin of the flow.Although apparently uneconomic, these flow-hosted PGE mineralization zones are of interest in exploration, because they are more similar in stratigraphie setting, style, and composition to PGE-rich disseminated Fe-Cu sulfide mineralization zones within thick differentiated intrusions than to mineralization zones in other Archean volcanic rocks. The characteristics of the mineralization zones and their host rocks, especially high degrees of PGE enrichment, vertical and horizontal patterns of PGE depletion, and accumulation of clinopyroxene + magnetite-ilmenite intergrowths, indicate a critical genetic role for variations in the regime of melt flowage. The mineralization zones in the Boston Creek and Theo's Flows are interpreted to have formed by simultaneous in situ formation of PGE-rich Fe-Cu sulfide and Fe-Ti oxide from flowing silicate liquid in the margins of internal lava channels. The mineralization zone in Fred's Flow is interpreted to have formed by ponding and coalescence of PGE-enriched sulfurous vapor bubbles in the upper chilled margin during olivine accumulation on the base of a dynamic lava channel. The relative abundance of PGE mineralization zones and high degree of PGE enrichment in the Boston Creek Flow suggest that the most favorable exploration targets are rocks crystallized from late-stage, highly fractionated derivative liquids in large differentiated terropicritic units.     

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 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.     

Mineralogy,parageneses, and phase relations of copper-iron sulfides in the Atlantis II deep,red sea

New investigations are carried out on the mineralogy and mineral chemistry of sulfide assemblages obtained in samples from one core in the hydrothermally active, southwest basin of the Atlantis II deep, Red Sea. The most abundant sulfide phases are the exsolved intermediate solid solution (ISS) and chalcopyrite. Sphalerite, pyrrhotite, marcasite, mackinawite, and presumably wurtzite are also observed. Two distinct groups of paragenesis were encountered: (a) Intermediate solid solution with sphalerite incrustations and intergrowths, and (b) intermediate solid solution barren of sphalerite intergrowths. The first group is confined to the upper part of the Co zone and the SOAN zone (Bäcker and Richter 1973), and the second is present in the entire core 100-3-7. An optically isotropic chalcopyrite is found for the first time as a natural mineral in Atlantis II, Red Sea. Yet its existence as a novel phase needs x-ray confirmation. It exhibits a lower reflectivity than normal chalcopyrite and is isotropic. Chalcopyrite occurs either as a single phase or in association with tetragonal chalcopyrite. Our investigations indicate that the formation of Atlantis II deposits is a result of complex processes. These processes are characterized by compositional changes in the ore-bearing fluids and the change in sulfur fugacity (especially with depth). The presence of exsolved chalcopyrite lamellae in ISS indicates slow cooling below 450°C. However, it is difficult to understand why the cubic chalcopyrite is not converted to the tetragonal form even though the temperature of transformation lies above 450°C (470° – 500°C, Cabri 1973). The Cu/Fe ratio changes in the exsolved chalcopyrite lamellae from core to rim of the composite grains. The ratio is higher in the rims. This suggests that primary inhomogenous ISS grains formed from solutions with a continuous increase in the Cu/Fe ratio. Slow cooling is also required to account for the exsolution of chalcopyrite lamellae in ISS. The low sulfur content in isotropic chalcopyrite is also suggestive of low fs₂. The low S content in the chalcopyrite may be the controlling factor for the sluggish conversion from cubic to tetragonal chalcopyrite. Mackinawite lamellae show the same orientation in ISS and exsolved isotropic chalcopyrite indicating that mackinawite exsolved before the breakdown of ISS. This strongly suggests that mackinawite is stable above 300°C (contrary to experimental results by Zoka et al. 1973). Pyrrhotite was probably formed by the sulfurization of ilvaite. The pyrrhotite grains with several complex successive zones show the sequence of the sulfurization episodes.Metalliferous sediments related to hot brines were discovered in the Red Sea in 1964 (Miller et al. 1966). Since then, several papers have been published on this subject (Degens and Ross 1969, Bäcker and Schoell 1972, Bäcker and Richter 1973, Bignell et al. 1976, Shanks and Bishoff 1977, Weber-Diefenbach 1977, Nöltner 1979, Pottorf 1980, Pottorf and Barnes 1983, Oudin et al. 1984).Complex sulfide phases including intermediate solid solution (ISS), chalcopyrite, and a chalcopyritelike mineral (which exhibits a lower reflectivity than normal chalcopyrite and appears to be isotropic occur in the metalliferous sediments. These phases were found in association with several minerals in different parageneses. In an attempt to understand the origin of the formation of the sulfide-bearing sediments in the Atlantis II deep of the Red Sea, a detailed study of the phase relations of the Cu-Fe sulfide ores of this locality was carried out.     

中国吉林长白山地区地幔捕虏体中硫化物熔体包裹体

Mantle xenoliths are common in the Cenozoic basalts of the Changbaishan District,Jilin Province,China.Sulfide assemblages in mantle minerals can be divided into three types:isolated sulfide grains,sulfide-meh inclusions and filling sulfides in fractures.Sulfide-meh inclusions occur as single-phase sulfides,sulfide-silicate melt,and CO_2-sulfide-silicate melt inclusions. Isolated sulfide grains are mainly composed of pyrrhotite,but cubanite was found occasionally.Sulfide-meh inclusions are mainly composed of pontlandite and MSS,with small amounts of chalcopyrite and talnakhite.The calculated distribution coefficient K_(D3)for lherzolite are similar to that of mean experimental value.The bulk sulfides in lherzolite were in equilibrium with the enclosing minerals, indicating immiscible sulfide melts captured in partial melting of upper mantle.Sulfide in fractures has higher Ni/Fe and(Fe Ni)/S than those of sulfide melt inclusions.They might represent later metasomatizing fluids in the mantle.Ni/Fe and(Fe Ni)/S increase from isolated grains,sulfide inclusions to sulfides in fractures.These changes were not only affected by temperature and pressure,hut by geochemistry of Ni,Fe and Cu,and sulfur fugacity as well.     

Sulfur isotope studies of the felbertal scheelite deposit,eastern alps

The Felbertal scheelite deposit is the largest known strata-bound tungsten concentration. It lies in an up to 400 m thick rock pile in the lowermost part of the volcanic rock sequence, probably of the Early Paleozoic Habach Formation. Both ore fields (eastern and western) have been affected by Variscan and Alpine metamorphism and tectonism, resulting in a remobilization of the ore mineralization. This ore deposit and the neighboring rocks show a strikingly low sulfur content. The eastern field with one major orebody has very little sulfide mineralization. The western field, with 8 orebodies (K1–K8) and two remobilized vein zones (S1 and S2), reveals somewhat more minor sulfide enrichments that are mainly within and around the K1 and K2 orebodies and in some parts of the interlayered schist sequence. Sulfur isotope compositions of 90 sulfide minerals (37 pyrrhotite, 20 chalcopyrite, 19 pyrite and 11 molybdenite and/or WS₂-MoS₂ solid solutions and 3 Pb-Bi sulfosalts, including 7 sulfides within scheelite grains) from 60 ore and host rock samples have been determined with a standard error of less than ±0.2 per mil. All data range from –3.6 to +4.3 ³⁴S. There are small differences in the sulfur isotope values from place to place and in time from the first and second to the third generation. In the western field, the K1 orebody differs from other orebodies (K2, K4, K7) due to isotopically heavier ³⁴S values. The three scheelite generations show differences in the ³⁴S values of the sulfide microphases within scheelite grains, from +1.0 to +4.3 per mil for the first and the second, and from –1.8 to –3.3 per mil for the third generation. Sulfide phases within molybdoscheelites may have crystallized under the same conditions as the other coeval sulfide minerals in the same orebody. They commonly formed later than scheelite. These changes may be explained using data from Ohmoto and Rye (1979): Small changes in temperature, pH, and/or may result in large changes in the ³⁴S values with the precipitation of isotopically heavier sulfides under more reducing conditions. Only four samples with sulfide mineral pairs show isotopic equilibrium. All others display some disequilibrium. We suggest that the sulfides in the ores and surrounding volcanogenic host rocks formed contemporaneously from the same hydrothermal ore fluids, and that the sulfur species in these fluids may have been dominantly H₂S.     

S-33 constraints on the seawater sulfate contribution in modern seafloor hydrothermal vent sulfides

Sulfide sulfur in mid-oceanic ridge hydrothermal vents is derived from leaching of basaltic-sulfide and seawater-derived sulfate that is reduced during high temperature water rock interaction. Conventional sulfur isotope studies, however, are inconclusive about the mass-balance between the two sources because ³⁴S/³²S ratios of vent fluid H₂S and chimney sulfide minerals may reflect not only the mixing ratio but also isotope exchange between sulfate and sulfide. Here, we show that high-precision analysis of S-33 can provide a unique constraint because isotope mixing and isotope exchange result in different Δ³³S (≡δ³³S-0.515 δ³⁴S) values of up to 0.04‰ even if δ³⁴S values are identical. Detection of such small Δ³³S differences is technically feasible by using the SF₆ dual-inlet mass-spectrometry protocol that has been improved to achieve a precision as good as 0.006‰ (2σ).Sulfide minerals (marcasite, pyrite, chalcopyrite, and sphalerite) and vent H₂S collected from four active seafloor hydrothermal vent sites, East Pacific Rise (EPR) 9-10°N, 13°N, and 21°S and Mid-Atlantic Ridge (MAR) 37°N yield Δ³³S values ranging from −0.002 to 0.033 and δ³⁴S from −0.5‰ to 5.3‰. The combined δ³⁴S and Δ³³S systematics reveal that 73 to 89% of vent sulfides are derived from leaching from basaltic sulfide and only 11 to 27% from seawater-derived sulfate. Pyrite from EPR 13°N and marcasite from MAR 37°N are in isotope disequilibrium not only in δ³⁴S but also in Δ³³S with respect to associated sphalerite and chalcopyrite, suggesting non-equilibrium sulfur isotope exchange between seawater sulfate and sulfide during pyrite precipitation. Seafloor hydrothermal vent sulfides are characterized by low Δ³³S values compared with biogenic sulfides, suggesting little or no contribution of sulfide from microbial sulfate reduction into hydrothermal sulfides at sediment-free mid-oceanic ridge systems. We conclude that ³³S is an effective new tracer for interplay among seawater, oceanic crust and microbes in subseafloor hydrothermal sulfur cycles.     

Isocubanite-chalcopyrite intergrowths in the Mid-Atlantic Ridge 26°S hydrothermal vent sulfides

Petrographic, SEM, and EPMA analyses are used to study the micro-textures and mineralogical composition of samples collected by a TV-grab from the 26°S SMAR (southern Mid-Atlantic Ridge) hydrothermal field. The investigated samples include the outermost chimney walls and sulfide debris. Isocubanite-chalcopyrite intergrowths are the major Cu-Fe sulfide phase in the chimney wall samples. These intergrowths include normal chalcopyrite, anomalous chalcopyrite (Cu-poor, Zn- and Fe-rich), normal isocubanite with Cu/Fe < 0.50, and Cu-rich isocubanite with Cu/Fe > 0.50. Anomalous chalcopyrite and Cu-rich isocubanite represent the intermediate phases between stoichiometric chalcopyrite and isocubanite in the Cu-Fe-S system. Anomalous chalcopyrite occurs as cores or thin rims bordering isocubanite, which associated with sphalerite. While Cu-rich isocubanite commonly associates pyrite. Based on textural relationships and microanalytical data of both phases, we interpret the abundant anomalous chalcopyrite and Cu-rich isocubanite as metastable or as high-temperature (~300 °C) rapidly precipitated hydrothermal sulfides. This interpretation advocates the SMAR 26°S hydrothermal field as an immature and short-living system.     

Sulphide and oxide minerals from the Ohmine granitic rocks in Kii Peninsula,central Japan,and their primary paragenetic relations

In the Ohmine granitic rocks of Kii Peninsula, central Japan, ilmenite, rutile, pyrrhotite, pyrite and chalcopyrite commonly occur, but no magnetite is present. Their primary paragenetic relations were confirmed by examining their mode of occurrences as inclusion species in major silicate minerals and the phase relations in the Cu-Fe-S system, though their parageneses changed in cooling of the rocks. This makes it possible to estimate the fugacities of oxygen and sulfur in the granitic rocks based upon their paragenetic relations, and to discuss the nature of volatiles in the granitic rocks. Significant subsolidus reactions for sulfide minerals continued until the rocks cooled below 300° C and took place in two types of mineral grains, in groundmass and as inclusions. The removal of sulfur and copper through the silicate crystals was too easy to preserve the chemistry of sulfides included in silicates.     

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.     

Sulfide mineralogy in the polymetallic cassiterite deposits of Dachang,P.R. China

Several important mineral deposits of Sn, Zn, Cu, Pb, and other metals associated with Devonian sediments and Yanshanian (Cretaceous) granitic rocks are known in the Dachang district (Guangxi). Early genetic hypotheses related the origin of the deposits entirely to the Yanshanian granites. Recently, it was suggested that in Devonian times an earlier syngenetic metal concentration may have occurred, later overprinted by the Yanshanian metallogeny. This contribution is aimed at placing constraints on the physicochemical conditions during the Yanshanian ore formation-remobilization by studying the sulfide chemistry (arsenopyrite, sphalerite, stannite) and fluid inclusion data on the two major deposits in the area, i.e., the polymetallic cassiterite deposit of Changpo and the Zn-Cu skarn deposit of Lamo. Sphalerite and arsenopyrite are quite abundant in both deposits; stannite is minor, but fairly widespread at Changpo, and quite rare at Lamo. They are accompanied by pyrite, pyrrhotite, galena, chalcopyrite, cassiterite, fluorite, and a large variety of other sulfides and sulfosalts. The main compositional data for sphalerite and arsenopyrite are summarized as follows:Changpo: arsenopyrite associated with pyrrhotite 31.4–36.1 at% As; Associated with pyrite 31.9–33.1 at% As; sphalerite associated with pyrrhotite 18.3–22.2 mol% FeS; associated with pyrite 10.6–18.6 mol% FeS.Lamo: arsenopyrite associated with pyrrhotite 32.9–35.3 at% As; associated with pyrite 30.3–31.7 at% As; sphalerite associated with pyrrhotite, 17.2–24.4 mol% FeS; associated with pyrite 4.2–19.6 mol% FeS.Partitioning of Fe and Zn between coexisting sphalerite and stannite from Changpo indicates temperatures of 300°–350°C. For Lamo, the following fluid inclusion data are available: fluorite, salinities of 0–9.5 equiv. wt% NaCl, and homogenization temperatures between 160°C and 250°C; quartz, moderate salinities (0–4.6 equiv. wt% NaCl), and homogenization temperatures of 208°–260°C. Combining the mineralogical evidence with the compositional and fluid inclusion data, it is suggested that the evolution of the environment during the Yanshanian event was characterized by the following parameters: pressure was relatively low (on the order of 1–1.5 kb); temperature may have been as high as 500°C during deposition of the As-richest arsenopyrites, but eventually dropped below 200°–250°C in the latest stages; with an increase in sulfur activity and/or the decrease in temperature pyrrhotite was no longer stable in the latest stages of mineralization.