Copper–Gold Skarn Mineralization at the Karavansalija Ore Zone,Rogozna Mountain,Southwestern Serbia

Karavansalija ore zone is situated in the Serbian part of the Serbo‐Macedonian magmatic and metallogenic belt. The Cu–Au mineralization is hosted mainly by garnet–pyroxene–epidote skarns and shifts to lesser presence towards the nearby quartz–epidotized rocks and the overlying volcanic tuffs. Within the epidosites the sulfide mineralogy is represented by disseminated cobalt‐nickel sulfides from the gersdorfite‐krutovite mineral series and cobaltite, and pyrite–marcasite–chalcopyrite–base metal aggregates. The skarn sulfide mineralization is characterized by chalcopyrite, pyrite, pyrrhotite, bismuth‐phases (bismuthinite and cosalite), arsenopyrite, gersdorffite, and sphalerite. The sulfides can be observed in several types of massive aggregates, depending on the predominant sulfide phases: pyrrhotite‐chalcopyrite aggregates with lesser amount of arsenopyrite and traces of sphalerite, arsenopyrite–bismuthinite–cosalite aggregates with subordinate sphalerite and sphalerite veins with bismuthinite, pyrite and arsenopyrite. In the overlying volcanoclastics, the studied sulfide mineralization is represented mainly by arsenopyrite aggregates with subordinate amounts of pyrite and chalcopyrite. Gold is present rarely as visible aggregate of native gold and also as invisible element included in arsenopyrite. The fluid inclusion microthermometry data suggest homogenization temperature in the range of roughly 150–400°C. Salinities vary in the ranges of 0.5–8.5 wt% NaCl eq for two‐phase low density fluid inclusions and 15–41 wt% NaCl eq for two‐phase high‐salinity and three‐phase high‐salinity fluid inclusions. The broad range of salinity values and the different types of fluid inclusions co‐existing in the same crystals suggest that at least two fluids with different salinities contributed to the formation of the Cu–Au mineralization. Geothermometry, based on EPMA data of arsenopyrite co‐existing with pyrite and pyrrhotite, suggests a temperature range of 240–360°C for the formation of the arsenopyrite, which overlaps well with the data for the formation temperature obtained through fluid inclusion microthermometry. The sulfur isotope data on arsenopyrite, chalcopyrite, pyrite and marcasite from the different sulfide assemblages (ranging from 0.4‰ to +3.9‰ δ³⁴S_CDT with average of 2.29 δ³⁴S_CDT and standard deviation of 1.34 δ³⁴S_CDT) indicates a magmatic source of sulfur for all of the investigated phases. The narrow range of the data points to a common source for all of the investigated sulfides, regardless of the host rock and the paragenesis. The sulfur isotope data shows good overlap with that from nearby base‐metal deposits; therefore the Cu–Au mineralization and the emblematic base‐metal sulfide mineralization from this metallogenic belt likely share same fluid source.     

Sulfide petrology of basal chilled margins in layered sills of the Archean Deer Lake Complex,Minnesota

Sulfide minerals in amounts up to 3 vol% are found in basal, chilled marginal zones of two layered peridotite-pyroxenite-gabbro sills in the Early Precambrian Deer Lake Complex, northcentral Minnesota. The sulfides occur interstitially to silicate minerals, and consist of pyrrhotite with minor exsolved cobaltian pentlandite, chalcopyrite, gersdorffite, and marcasite±pyrite as an alteration product of pyrrhotite.The basal chilled units (3–6 m) of the sills are divisable into three zones based primarily on textures. The lowermost zone is an equigranular basalt, whereas the overlying zone is characterized by skeletal, spinifex-like actinolite after clinopyroxene. The upper zone of the basal margins contains elongate and swallow tail plagioclase, and is barren of sulfide minerals.Electron microprobe analyses of sulfide minerals and modal data suggest that sulfide bulk compositions at 1,100–1,000 ° C represent a pyrrhotite solid solution and a coexisting Cu-rich sulfide liquid. Cooling of the Cu-rich liquid and low temperature transformations are thought to have produced chalcopyrite or chalcopyrite plus pyrrhotite. The sulfide minerals have reequlibrated to temperatures near 300 ° C or less.Analyses of sulfur content and ³⁴S values suggest that assimilation of sulfur from adjacent country rocks was the principal mechanism responsible for anomalous concentrations of sulfides in the basal chilled margins. The distribution of sulfides in the peridotite-pyroxenite-gabbro portions of the sills, and calculations of settling rate preclude an origin involving gravitational settling of immiscible droplets through the magma body.     

南大西洋中脊26°S热液区成矿物质来源探讨

南大西洋中脊的26°S热液区广泛发育多金属硫化物、底泥、枕状熔岩、非活动性烟囱体和活动性烟囱体。为了有效探索硫、铜等成矿物质的来源以及成矿作用过程,分别以玄武岩、烟囱体残片及块状多金属硫化物为研究对象,开展了熔融包裹体、硫同位素和铜同位素研究。结果显示：区内玄武岩新鲜未蚀变且斑晶中产出大量熔融包裹体;熔融包裹体气泡壁附着黄铜矿、黄铁矿及磁铁矿等子矿物,说明在岩浆作用过程中可从熔浆中分离出成矿所需的金属元素和硫,这些成矿元素随着岩浆去气作用进入挥发分中,并随着脱气作用迁移出来。通过对烟囱体残片及块状多金属硫化物中黄铁矿的硫同位素组成进行比对分析,发现26°S热液区内硫化物的硫同位素与大西洋各热液区硫化物的硫同位素变化范围相一致,但δ³⁴S_V-CDT值略低（3.0‰~3.9‰）。低的δ³⁴S_V-CDT值指示硫以岩浆硫源为主,海水硫酸盐还原硫占比低。黄铜矿呈现略微富铜重同位素特征且分馏程度较低,其δ⁶⁵Cu值（0.171‰~0.477‰）趋近于大洋中脊玄武岩的铜同位素值（0）。综合硫同位素及铜同位素特征,表明热液流体经历了岩浆和海水的混合过程,成矿物质主要来自于岩浆热液,成矿作用过程中可能有少量海水混入。     

Petrology,Geochemistry, and Fluid Inclusion Microthermometry of Sphalerite from the Laloki and Federal Flag Strata‐Bound Massive Sulfide Deposits,Papua New Guinea: Implications for Gold Mineralization

The Laloki and Federal Flag deposits are two of the many (over 45) polymetallic massive sulfide deposits that occur in the Astrolabe Mineral Field, Papua New Guinea. New data of the mineralogical compositions, mineral textures, and fluid inclusion studies on sphalerite from Laloki and Federal Flag deposits were investigated to clarify physiochemical conditions of the mineralization at both deposits. The two deposits are located about 2 km apart and they are stratigraphically hosted by siliceous to carbonaceous claystone and rare gray chert of Paleocene–Eocene age. Massive sulfide ore and host rock samples were collected from each deposit for mineralogical, geochemical, and fluid inclusion studies. Mineralization at the Laloki deposit consists of early‐stage massive sulfide mineralization (sphalerite‐barite, chalcopyrite, and pyrite–marcasite) and late‐stage brecciation and remobilization of early‐stage massive sulfides that was accompanied by late‐stage sphalerite mineralization. Occurrence of native gold blebs in early‐stage massive pyrite–marcasite‐chalcopyrite ore with the association of pyrrhotite‐hematite and abundant planktonic foraminifera remnants was due to reduction of hydrothermal fluids by the reaction with organic‐rich sediments and seawater mixing. Precipitation of fine‐grained gold blebs in late‐stage Fe‐rich sphalerite resulted from low temperature and higher salinity ore fluids in sulfur reducing conditions. In contrast, the massive sulfide ores from the Federal Flag deposit contain Fe‐rich sphalerite and subordinate sulfarsenides. Native gold blebs occur as inclusions in Fe‐rich sphalerite, along sphalerite grain boundaries, and in the siliceous‐hematitic matrix. Such occurrences of native gold suggest that gold was initially precipitated from high‐temperature, moderate to highly reduced, low‐sulfur ore fluids. Concentrations of Au and Ag from both Laloki and Federal Flag deposits were within the range (<10 ppm Au and <100 ppm Ag) of massive sulfides at a mid‐ocean ridge setting rather than typical arc‐type massive sulfides. The complex relationship between FeS contents in sphalerite and gold grades of both deposits is probably due to the initial deposition of gold on the seafloor that may have been controlled by factors such as Au complexes, pH, and fO₂ in combination with temperature and sulfur fugacity.     

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.     

Mineralogy,Sulfur Isotope and Fluid Inclusion Studies of Hydrothermal Ore at the Hakurei Deposit,Bayonnaise Knoll,Izu‐Bonin Arc

Sulfide and sulfate ore samples collected from the Hakurei deposit of the Bayonnaise knoll were examined for the occurrence and chemical composition of minerals, including the sulfur isotopes and the microthermometry of fluid inclusions. Massive sulfide ore, mineralized volcanic rock, and anhydrite ore occur in descending order, from the seafloor to the bottom of the cored sample. The massive sulfide ore is dominated by sphalerite and accompanied by tennantite, chalcopyrite, and pyrite with lesser amounts of galena, enargite, and covellite. Amorphous silica is commonly precipitated on the surface of the sulfide minerals. As‐bearing minerals such as tennantite, enargite, and luzonite are common, while galena and Sb‐rich tetrahedrite are scarce. The mineral abundance and chemical composition of the minerals differs from that found in chimneys of the deposit. The sulfur isotope compositions in the minerals are +3.1–5.2‰ for sulfides and +19.6–21.8‰ for sulfate minerals. The homogeneous nature of the sulfur isotopes suggests that sulfur incorporated in the Hakurei deposit came from the reduction of aqueous sulfate in seawater.     

Ore‐Forming Fluids as Sampled by Sulfide‐ and Quartz‐Hosted Fluid Inclusions in the Jinwozi Lode Gold Deposit,Eastern Tianshan Mountains of China

The Jinwozi lode gold deposit in the eastern Tianshan Mountains of China includes auriferous quartz veins and network quartz veins that are exemplified by the Veins 3 and 210, respectively. This paper presents H‐, O‐isotope compositions and gas compositions of fluid inclusions hosted in sulfides and quartz, and S‐, Pb‐isotope compositions of sulfide separates collected from the principal Stage 2 ores in Veins 3 and 210. Fluid inclusions trapped in quartz and sphalerite are pseudo‐secondary and primary. They were trapped from the fluids during the successive or alternate precipitation of quartz with sulfides. H‐ and O‐isotope compositions of fluid inclusion of three pyrite and one quartz separates from Vein 210 plot within the field of degassed melt, which is evidence for the incorporation of magmatic fluid as well with some possibility of contribution of metamorphic water to the hydrothermal system since the two datasets show a higher oxygen isotopic ratio than those of degassed melt. However, δD and δ¹⁸O values of fluid inclusions hosted in sulfides and quartz from Vein 3 are distinctly lower than those from Vein 210. In addition, salinities of fluid inclusion from Vein 3, approximately 3 to 6 wt% NaCl equivalent, are considerably lower than those from Vein 210, which are approximately 8 to 14 wt% NaCl equivalent. Ore‐forming fluids of Veins 3 and 210 have migrated through the relatively high and low levels in the imbricate‐thrust column where rock deformation is characterized by dilatancy or ductile–brittle transition, respectively. Therefore, the ore‐forming fluid of Vein 3 is interpreted to have mixed with greater amounts of meteoric‐derived groundwater than that of Vein 210. Fluid inclusions hosted in sulfides contain considerably higher abundances of gaseous species of CO₂, N₂, H₂S, and so on, than those hosted in quartz. Many of these gaseous species exhibit linear correlations with H₂O. These linear trends are interpreted in terms of mixing between magmatic fluid and groundwater. The relative enrichment of gaseous species in fluid inclusions hosted in sulfides, coupled with the banded ore structure, suggests that the magmatic fluid was involved with the ore‐forming fluid in pulsation. Lead isotope compositions of 21 pyrite and galena separates form a linear trend, suggesting mixing of metallic materials from diverse reservoirs. The δ³⁴S values of pyrite and galena range from +5.6‰ to +7.9‰ and from +3.1‰ to +6.3‰, respectively, indicating sulfur of the Jinwozi deposit has been leached mainly from the granodiorite and partly from the Jinwozi Formation by the circulating ore‐forming fluid.     

Relict sulfides in terrigenous rocks of the Upper Kolyma Region

In terrigenous flysch strata of the Upper Kolyma Region in northeastern Russia, microaggregates of sulfides with spherical form are widespread. During dynamic metamorphism, spherical sulfide units were segregated into lenticular aggregates along the cleavage planes, were as seed, or were recrystallized into faceted metacrystals. Further stress on the rock sometimes led to a morphologically expressed particular dissolution of pyrite crystals along the cleavage directions, and to their depletion with admixture elements. A more substantial effect led to transformation of pyrite into pyrrotine with inclusions of chalcopyrite and Fe-Ni-Co-sulfoarsenides. Relict sulfides reflect, to a certain degree, the primary geochemical condition of the sedimentation period and its further evolution. When studying the numerous sulfidization zones, the composition of relict sulfides allows us to predict the geochemical specialization and the degree of inheritance of post-sedimentation mineralization.     

Spinel–sapphirine–quartz bearing composite inclusion within garnet from an ultrahigh-temperature pelitic granulite: Implications for metamorphic history and P–T path

We report here a multiphase mineral inclusion composed of quartz, plagioclase, K-feldspar, sapphirine, spinel, orthopyroxene, and biotite, in porphyroblastic garnet within a pelitic granulite from Rajapalaiyam in the Madurai Granulite Block, southern India. In this unique textural association, hitherto unreported in previous studies, sapphirine shows four occurrences: (1) as anhedral mineral between spinel and quartz (Spr-1), (2) subhedral to euhedral needles mantled by quartz (Spr-2), (3) subhedral to anhedral mineral in orthopyroxene, and (4) isolated inclusion with quartz (Spr-4). Spr-1, Spr-2, and Spr-4 show direct grain contact with quartz, providing evidence for ultrahigh-temperature (UHT) metamorphism at temperatures exceeding 1000 °C. Associated orthopyroxene shows high Mg/(Fe + Mg) ratio ( 0.75) and Al₂O₃ content (up to 9.6 wt.%), also suggesting T > 1050 °C and P > 10 kbar during peak metamorphism.

Coarse spinel (Spl-1) with irregular grain morphology and adjacent quartz grains are separated by thin films of Spr-1 and K-feldspar, suggesting that Spl-1 and quartz were in equilibrium before the stability of Spr-1 + quartz. This texture implies that the P–T conditions of the rock shifted from the stability field of spinel + quartz to sapphirine + quartz. Petrogenetic grid considerations based on available data from the FMAS system favour exhumation along a counterclockwise P–T trajectory. The irregular shape of the inclusion and chemistry of the inclusion minerals are markedly different from the matrix phases suggesting the possibility that the inclusion minerals could have equilibrated from cordierite-bearing silicate-melt pockets during the garnet growth at extreme UHT conditions.     

Pyrite tracks assimilation of crustal sulfur in Pyrenean peridotites

Cobalt-bearing pyrite (0.5?C2.0?wt.% Co) is abnormally abundant (up to 35?vol.% of the total volume of the sulfide phase) in some eastern Pyrenean peridotite massifs, compared to pieces of subcontinental mantle studied so far for sulfides. Pyrite occurs as vermicular intergrowths inside pentlandite and/or chalcopyrite or as coarser, blocky grains in the intergranular pores of host peridotites. Those different pyrites are characterized by different platinum-group element systematics (measured by laser ablation microprobe and ICP-MS). Vermicular pyrite intergrown with pentlandite displays Os-, Ir-, Ru- and Rh-enriched chondrite normalized PGE patterns of Monosulfide solid solution (Mss). In contrast, coarse-grained intergranular (??blocky??) pyrites, are PGE-poor. Chalcophile trace elements (i.e. Zn, Pb, Ag, Au) that are not usually concentrated in mantle-derived sulfides were commonly detected. By contrast, selenium contents are generally low, yielding thus pyrite with high S/Se ratio (>10⁵), consistent with a sedimentary sulfur source. Pyrite microtextures and chalcophile trace element contents support a process of assimilation of crustal sulfur from the metamorphosed sedimentary country rocks. These latter generated highly reactive CO₂-S fluids, which were injected into structural discontinuities of the lherzolitic bodies. Sulfur has reacted at T?=?300?C550°C with pre-existing, mantle-derived, metal-rich sulfide assemblages (pentlandite-chalcopyrite). Addition of crustal sulfur did produce Mss which, on cooling, exsolved the Os-rich pyrite in addition to pentlandite. The coarse-grained pyrite types have crystallized directly from S-rich fluids.     

U–Cr-rich high Mg-Al granulites from Karimnagar Granulite Belt, India: implications for Neoarchean-Paleoproterozoic events in southern India

High Mg-Al granulite occurs as enclave within granite gneisses at Karimnagar, southern India, and it contains coarse granoblastic aggregates of orthopyroxene and sapphirine with minor amount of cordierite, spinel and phlogopite. An important chemical characteristic of these minerals is their extremely high MgO content and the high Cr₂O₃ in sapphirine and spinel. Textural analysis shows sapphirine + orthopyroxene + cordierite as the peak-metamorphic assemblage that possibly evolved though the breakdown of a spinel-bearing assemblage. Cation exchange geothermometers involving orthopyroxene, sapphirine and spinel yield temperatures of 600–800 °C with a maximum of 860 °C implying an event of high temperature (HT) metamorphism. Pseudosection analysis in the FeO–MgO–Al₂O₃–SiO₂ chemical system shows the stability of the peak- assemblage below 6.2 kbar. Subsequently, the rock underwent hydration and cooling with the appearance of phlogopite in the assemblage. Chromium enrichment is possibly inherited from the protolith and its presence presumably stabilized sapphirine and spinel below their high-temperature stability field. The recorded Rb–Sr age of ca. 2,500 Ma in host granite gneiss marks the upper age limit of HT metamorphism. Presence of patchy, lobate grains as well as veinlets of uraninite and brannerite is also a characteristic feature of the rock. Uranium mineralization took place during the post peak metamorphic stage, sulfide mineralization represented by tiny grains and veinlets of pyrite, millerite and pentlandite coincided with, and outlasted the uranium mineralization. The U–Th–Pb chemical ages of uraninite grains suggest ca. 2,200?±?12 Ma for the age of uranium mineralization in the granulite. Based on the field relations, it is surmised that the granulite metamorphism in the study area is older than ca. 2,500 Ma and is comparable with an event in the other parts of Eastern Dharwar Craton. It can be conceived as a widespread event in southern India.     

Ore Mineralization in Ultramafic and Metasomatic Rocks of the Ospin–Kitoi Massif,Eastern Sayan

In the Ospin–Kitoi ultramafic massif of the Eastern Sayan, accessory and ore Cr-spinel are mainly represented by alumochromite and chromite. Copper–nickel mineralization hosted in serpentinized ultramafic rocks occurs as separate grains of pentlandite and pyrrhotite, as well as assemblages of (i) hexagonal pyrrhotite + pentlandite + chalcopyrite and (ii) monoclinal pyrrhotite + pentlandite + chalcopyrite. Copper mineralization in rodingite is presented by bornite, chalcopyrite, and covellite. Talc–breunnerite–quartz and muscovite–breunnerite–quartz listvenite contains abundant sulfide and sulfoarsenide mineralization: pyrite, gersdorffite, sphalerite, Ag–Bi and Bi-galena, millerite, and kuestelite. Noble metal mineralization is represented by Ru–Ir–Os alloy, sulfides, and sulfoarsenides of these metals, Au–Cu–Ag alloys in chromitite, laurite intergrowth, an unnamed mineral with a composition of Cu₃Pt, orcelite in carbonized serpentinite, and sperrylite and electrum in serpentinite. Sulfide mineralization formed at the late magmatic stage of the origination of intrusion and due to fluid–metamorphic and retrograde metasomatism of primary rocks.     

Sulfide composition and phase relations in the Fe-Ni-Cu ore deposits of the Ivrea-Verbano basic complex (western Alps,Italy)

The bulk composition, mineralogy and mineral chemistry of base-metal sulfides have been investigated in the Fe-Ni-(Cu) ore deposits of the Ivrea-Verbano basic complex.The sulfide ores mostly display textural evidence of having been primarily deposited as an immiscible melt. Bulk compositions of the ores indicate that considerably low Ni/Fe and Ni/Co ratios are found in deposits developed close to metasedimentary country rocks, possibly as a result of mixing with sedimentary sulfur.Phase relations of primary sulfides indicate that early crystallization of the ore was dominated by a monosulfide solid solution (Mss) with a pyrrhotite composition, from which pentlandite and chalcopyrite were formed through subsolidus exsolution. Pentlandite from contaminated ores is typically enriched in Co. Troilite and hexagonal intermediate pyrrhotite intergrowths frequently occur due to low-temperature equilibration of metal-rich pyrrhotites, suggesting a low S fugacity of the original sulfide melt.The sulfides may be locally mobilized and redeposited along shear zones within the same host rock, giving rise to fairly massive ores having a typical cemented-breccia texture. Bulk composition and assemblages suggest that mobilization occurred at various temperatures during the cooling history of the ore, when sulfides were still in the molten state or at a lower temperature under the influence of abundant deuteric fluids. In this last case, growth of pyrite is seen as being possibly due to sulfurization and/or oxidation.     

Very high-density carbonic fluid inclusions in sapphirine-bearing granulites from Tonagh Island in the Archean Napier Complex, East Antarctica: implications for CO2 infiltration during ultrahigh-temperature (T>1,100 °C) metamorphism

The ultrahigh-temperature (UHT) metamorphism of the Napier Complex is characterized by the presence of dry mineral assemblages, the stability of which requires anhydrous conditions. Typically, the presence of the index mineral orthopyroxene in more than one lithology indicates that H₂O activities were substantially low. In this study, we investigate a suite of UHT rocks comprising quartzo-feldspathic garnet gneiss, sapphirine granulite, garnet-orthopyroxene gneiss, and magnetite-quartz gneiss from Tonagh Island. High Al contents in orthopyroxene from sapphirine granulite, the presence of an equilibrium sapphirine-quartz assemblage, mesoperthite in quartzo-feldspathic garnet gneiss, and an inverted pigeonite-augite assemblage in magnetite-quartz gneiss indicate that the peak temperature conditions were higher than 1,000 °C. Petrology, mineral phase equilibria, and pressure-temperature computations presented in this study indicate that the Tonagh Island granulites experienced maximum P-T conditions of up to 9 kbar and 1,100 °C, which are comparable with previous P-T estimates for Tonagh and East Tonagh Islands. The textures and mineral reactions preserved by these UHT rocks are consistent with an isobaric cooling (IBC) history probably following an counterclockwise P-T path. We document the occurrence of very high-density CO₂-rich fluid inclusions in the UHT rocks from Tonagh Island and characterize their nature, composition, and density from systematic petrographic and microthermometric studies. Our study shows the common presence of carbonic fluid inclusions entrapped within sapphirine, quartz, garnet and orthopyroxene. Analysed fluid inclusions in sapphirine, and some in garnet and quartz, were trapped during mineral growth at UHT conditions as 'primary' inclusions. The melting temperatures of fluids in most cases lie in the range of -56.3 to -57.2 °C, close to the triple point for pure CO₂ (-56.6 °C). The only exceptions are fluid inclusions in magnetite-quartz gneiss, which show slight depression in their melting temperatures (-56.7 to -57.8 °C) suggesting traces of additional fluid species such as N₂ in the dominantly CO₂-rich fluid. Homogenization of pure CO₂ inclusions in the quartzo-feldspathic garnet gneiss, sapphirine granulite, and garnet-orthopyroxene gneiss occurs into the liquid phase at temperatures in the range of -34.9 to +4.2 °C. This translates into very high CO₂ densities in the range of 0.95-1.07 g/cm³. In the garnet-orthopyroxene gneiss, the composition and density of inclusions in the different minerals show systematic variation, with highest homogenization temperatures (lowest density) yielded by inclusions in garnet, as against inclusions with lowest homogenization (high density) in quartz. This could be a reflection of continued recrystallization of quartz with entrapment of late fluids along the IBC path. Very high-density CO₂ inclusions in sapphirine associated with quartz in the Tonagh Island rocks provide potential evidence for the involvement of CO₂-rich fluids during extreme crustal temperatures associated with UHT metamorphism. The estimated CO₂ isochores for sapphirine granulite intersect the counterclockwise P-T trajectory of Tonagh Island rocks at around 6-9 kbar at 1,100 °C, which corresponds to the peak metamorphic conditions of this terrane derived from mineral phase equilibria, and the stability field of sapphirine + quartz. Therefore, we infer that CO₂ was the dominant fluid species present during the peak metamorphism in Tonagh Island, and interpret that the fluid inclusions preserve traces of the synmetamorphic fluid from the UHT event. The stability of anhydrous minerals, such as orthopyroxene, in the study area might have been achieved by the lowering of H₂O activity through the influx of CO₂ at peak metamorphic conditions (>1,100 °C). Our microthermometric data support a counterclockwise P-T path for the Napier Complex.     

Geology and Mineral Chemistry of Gold Mineralization in Mirge‐Naqshineh Occurrence (Saqez,NW Iran): Implications for Transportation and Precipitation of Gold

The Mirge-Naqshineh gold district is situated at northwest of Iran with a NW-trending brittleductile shear zone. It is hosted by Precambrian meta-sedimentary and meta-volcanic units traversed by mineralized quartz veins. In terms of cross-cutting relationships and sulfide content three types of quartz veins are identified in the region. Among those, parallel to bedding quartz vein(type Ⅰ) is the main host for gold mineralization. Gold is found in three different forms: 1) submicrometer-size inclusions of gold in arsenian pyrite, 2) as electrum and 3) in the crystal lattice of sulfides(pyrite, galena and chalcopyrite). Six types of pyrite(Py1-Py6) were identified in this ore reserve. Py3 coexists with arsenopyrite and contains the greatest As-Au concentrations. There is a negative correlation between the As and S contents in Py2 and Py3, implying the substitution of sulfur by arsenic. Pyrites and mineralized quartz veins were formed via metamorphic-hydrothermal fluid and reflect the gold-transportation as Au(HS)_2~- under reducing and acidic conditions. The gold precipitation mainly controlled by crystallization of arsenian pyrite during fluid/rock interactions and variation of fO_2. The volcanic host rock has played an important role in gold concentration, as Py3 in this rock contains inclusion of gold particles, but gold is within the lattice of pyrite in phyllite or other units.     

四川拉拉铁氧化物铜金矿床硫同位素地球化学

硫的来源对于了解铁氧化物铜金矿床的形成过程和成因具有重要的意义。文中统计了拉拉铁氧化物铜金矿硫化物的 硫同位素数据,并结合地质特征和矿相学研究,分析和讨论了硫的同位素组成特征和硫的来源。结果表明,拉拉铜金矿硫 同位素组成变化较大(不考虑一个异常样品,δ34S 值极差达到 14.9‰),表明成矿硫来源的多样性;其中,黄铁矿 δ34S 值范 围为 -1.4‰ ~4.9‰(平均 1.8‰),黄铜矿的 δ34S 值范围为 -5.9‰ ~9‰(平均 1.5‰)。结合硫化物的生成机制分析,并与其 他典型矿床硫同位素数据对比,表明海水沉淀的蒸发岩是黄铁矿和黄铜矿的重要硫来源,但也不能排除岩浆硫的贡献。目 前没有证据支持变质作用减少拉拉矿区硫化物的硫同位素组成差异。     

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).     

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.     

Exsolution textures in orthopyroxene in aluminous granulites as indicators of UHT metamorphism: New evidence from the Eastern Ghats Belt, India

Highly aluminous orthopyroxene, coexisting with sapphirine, cordierite, sillimanite, quartz and garnet in various combinations, constitute granoblastic mosaic peak metamorphic assemblages in aluminous granulites from three localities in the Eastern Ghats Belt, India. Orthopyroxene contains four types of intergrowths: (a) involving sapphirine with or without cordierite, (b) involving spinel, but without sapphirine, (c) involving cordierite, but without sapphirine and spinel, and (d) involving garnet, without sapphirine, spinel or cordierite. On the basis of textural and compositional data, origin of the intergrowths is ascribed to breakdown of Mg-Tschermak component, locally also involving Fe- and Ti-Tschermak. An attempt is made to compute the “pre-breakdown” compositions of orthopyroxene by image analysis, which shows maximum Al₂O₃ content of 13.4 wt.% in the pristine orthopyroxene. Geothermometry, phase equilibria consideration and application of existing experimental data on alumina solubility in orthopyroxene coexisting with sapphirine and quartz, collectively indicate extreme thermal conditions of metamorphism (> 1000 °C) for the studied assemblages. This re-affirms the notion that Al₂O₃ solubility in orthopyroxene is the most powerful indicator of UHT metamorphism (Harley, S.L., 2004. Extending our understanding of ultrahigh temperature crustal metamorphism. J. Mineral. Petrol. Sci. 99, 140–158). The intergrowths are considered to have formed due to cooling from the thermal peak spanning a temperature range of approximately 150 °C. Appearance of diverse types of intergrowths is probably related to subtle differences in bulk composition, particularly Fe:Mg ratios.     

喀拉通克铜镍矿床硫同位素组成特征及其地质意义

硫同位素研究在喀拉通克岩体的地壳物质混染过程中有重要意义。通过对块状和浸染状矿石、斑点状和脉状矿石以及围岩中硫化物进行硫同位素测试,分析了黄铜矿、黄铁矿、磁黄铁矿的硫同位素在硫化物中的富集状态,探讨了喀拉通克铜镍矿床硫同位素组成特征及其地质意义。结果表明：块状矿石的同位素测定值与标准值之间的千分偏差δ（34S）为（-1.30～1.84）×10-3,浸染状矿石的δ（34S）为（-2.50～0.85）×10-3,脉状矿石的δ（34S）为（-1.54～3.00）×10-3,围岩中黄铁矿的δ（34S）为（-7.8～-3.3）×10-3;硫同位素在硫化物中的富集从大到小依次为黄铁矿、磁黄铁矿、黄铜矿,说明硫化物之间基本达到了硫同位素平衡;喀拉通克铜镍矿床的硫主要来自于地幔,只在岩浆熔离作用形成的浸染状矿石和岩浆后期热液阶段形成的脉状矿石以及晚期黄铁矿中有少量或局部地壳硫混染的痕迹;地壳硫的加入没有在岩浆源区发生,可能发生在岩浆上升并发生硫化物就地熔离的局部过程中,几乎不对硫饱和及硫化物的熔离产生影响;岩浆在地壳深部发生的橄榄石、铬铁矿等矿物的分离结晶作用,有可能是促使硫饱和与硫化物熔离的主要因素。