PGM in chromite ore of the Sopcheozero deposit, Kola Peninsula

The Sopcheozero chromite deposit is hosted in dunite of the Monchegorsk layered intrusion as a sheetlike body of disseminated ore with a chromite grade varying from 20 to 60%. The total PGM content in the ore attains 0.5–0.8 g/t. The composition of host rocks varies from plagioclase peridotite to dunite, but PGM were found only in chromite-bearing dunite. PGM inclusions were detected in the interstices of chromite and olivine grains and within grains themselves. The data obtained confirm the known tendency toward variation in PGM composition with increasing sulfur and light PGE contents in the residual magmatic melt. The first particles of refractory Ir, Os, and Ru intermetallides appeared at the final stage of olivine crystallization, whereas laurite (Ru,Os,Ir)S₂ and pentlandite (Fe,Ni)₉S₈ were formed at the final stage of chromite crystallization, when the sulfur concentration in the residual melt became sufficient.     

Transformation of PGM in supra subduction zones:Geochemical and mineralogical constraints from the Veria(Greece) podiform chromitites

Extremely abundant PGE-minerals(PGM)hosted in chromitites from the Veria ophiolite complex in Macedonia(N.Greece)may be unique among ophiolite complexes.This study focuses on differences between the low-and high-PGE chromitites.New textural,mineralogical and geochemical constraints from those ores are presented,aiming to define factors controlling the PGE enrichment in a supra subduction environment,in the light of postmagmatic processes.The whole ore analyses for mmajor and trace elements indicated an unusually high-IPGE content(up to 25 ppm)and higher Fe,Ca,Mn,Zn and V contents in high-PGE compared to low-PGE in massive chromitites.The wide compositional variation of chromite,even in the same polished section,the occurrence of very fine PGM(less than 20μm)as inclusions within chromite and extremely large(>1000μm),angular or fine-grained PGM aggregates ones within a matrix of highly fragmented chromite-Cr-garnet matrix,may indicate crystallization/recrystallization of chromite from more than one precursor phases.Laurite(RuS2)is very limited,occurring as remnants surrounding by Ru–Os–Ir oxides/hydroxides,of a wide compositional variation.Irarsite occurs as euhedral crystals up to 200μm,surrounding by chromite,as anhedral exsolutions 1–200μm within laurite,or creating segregates with platarsite and relics of(Ru,Pt,Rh,Os)sulfarsenides.Platinum–Ru–Rh–Pd-minerals occur commonly as relatively fine-grained assemblages,up to 50μm,along with irarsite and other relics of(Ru,Pt,Rh,Os)sulfarsenides.Pt-alloys show a variation ranging from tetraferroplatinum to Pt–Ir–Fe–Ni alloys.The presence of laurite relics in large IPGM,awaruite,heazlewoodite,and carbon-bearing material reflecting a super-reducing environment,and the transformation of primary PGM into Os–Ir–Ru-alloys and oxides/hydroxides in association with Fe-chromite and Fe3t-bearing garnet(andradite-uvarovite solidsolution series)may reflect changes of the redox conditions from reducing to oxidizing.The relatively high Na content in hydrous mineral inclusions within high-PGE chromitites suggest a hydrous mantle source and provide the possibility for estimation of the P(average 3.0 kbar)and T(average 874C),indicating formation at a shallow mantle environment.     

Re–Os isotopic constraints on the source of platinum-group minerals (PGMs) from the Vestřev pyrope-rich garnet placer deposit,Bohemian Massif

Mineralogical studies of the heavy fraction from a Holocene pyrope-rich garnet placer deposit at Vestřev (Krkonoše Piedmont Basin, Bohemian Massif) have identified the presence of very rare grains of platinum group minerals (PGM). Pt–Fe alloy grains are accompanied by Os–Ir–Ru minerals (native osmium, iridium, and ruthenium) with inclusions of Pt–Fe alloy and hongshiite (PtCu). This mineral assemblage is typical for several mantle settings including ophiolites. The chemistry of the Os–Ir–Ru minerals shows an enrichment of the PGM in Ru, which is typical of ophiolites. The grain morphology of PGM and pyrope-rich garnet (mostly rounded with numerous euhedral/subhedral grains) does not exclude a common source. In-situ laser-ablation MC-ICP-MS was used to measure the Re–Os isotopic compositions of single Os-rich grains, which show heterogeneous subchondritic Os isotopic compositions (¹⁸⁷Os/¹⁸⁸Os = 0.12082–0.12505 ± 0.00003). This precludes their low-temperature origin and indicates derivation of platinum-group elements (PGEs) essentially from mantle-derived rocks without a significant contribution of crustal Os. The mantle model age (T_MA) and Re-depletion model age (T_RD) model ages range from ~ 0.4 to ~ 1.0 Ga and most likely reflect a long history of melt depletion that affected the mantle sources of PGM.     

Composition and evolution of PGE mineralization in chromite ores from the Il’chir ophiolite complex (Ospa–Kitoi and Khara-Nur areas,East Sayan)

Data are presented on chromitites from the northern and southern sheets of the Il’chir ophiolite complex (Ospa–Kitoi and Khara-Nur (Kharanur) massifs). The new and published data are used to consider similarities and differences between ore chrome-spinel from the chromitites of the northern and southern ophiolite sheets as well as the species diversity of PGE minerals and the evolution of PGE mineralization. Previously unknown PGE minerals have been found in the studied chromitites.Ore chrome-spinel in the chromitites from the northern sheet occurs in medium- and low-alumina forms, whereas the chromitites from the southern sheet contain only medium-alumina chrome-spinel. The PGE minerals in the chromitites from the southern sheet are Os–Ir–Ru solid solutions as well as sulfides and sulfoarsenides of these metals. The chromitites from the northern sheet contain the same PGE minerals and diverse Rh–Pt–Pd mineralization: Pt–Ir–Ru–Os and isoferroplatinum with Ir and Os–Ir–Ru lamellae. Areas of altered chromitites contain a wide variety of low-temperature secondary PGE minerals: Pt–Cu, Pt–Pd–Cu, PdHg, Rh2SnCu, RhNiAs, PtAs2, and PtSb2. The speciation of the PGE minerals is described along with multiphase intergrowths. The relations of Os–Ir–Ru solid solutions with laurite and irarsite are considered along with the microstructure of irarsite–osarsite–ruarsite solid solutions. Zoned Os–Ir–Ru crystals have been found. Zone Os82–99 in these crystals contains Ni3S2 inclusions, which mark off crystal growth zones. Different sources of PGE mineralization are presumed for the chromitites from the northern and southern sheets.The stages of PGE mineralization have been defined for the chromitites from the Il’chir ophiolite belt. The Pt–Ir–Ru–Os and (Os, Ru)S2 inclusions in Os–Ir–Ru solid solutions might be relics of primitive-mantle PGE minerals. During the partial melting of the upper mantle, Os–Ir–Ru and Pt–Fe solid solutions formed syngenetically with the chromitites. During the late-magmatic stage, Os–Ir–Ru solid solutions were replaced by sulfides and sulfarsenides of these metals. Mantle metasomatism under the effect of reduced mantle fluids was accompanied by PGE remobilization and redeposition with the formation of the following assemblage: garutiite (Ni,Fe,Ir), zaccariniite (RhNiAs), (Ir,Ni,Cu)S3, Pt–Cu, Pt–Cu–Fe–Ni, Cu–Pt–Pd, and Rh–Cu–Sn–Sb. The zoned Os–Ir–Ru crystals in the chromitites from the northern sheet suggest dissolution and redeposition of Os–Ir–Ru primary-mantle solid solutions by bisulfide complexes. Most likely, the PGE remobilization took place during early serpentinization at 450–600 ºC and 13–16 kbar.During the crustal metamorphic stage, tectonic movements (obduction) and a change from reducing to oxidizing conditions were accompanied by the successive transformation of chrome-spinel into ferrichromite–chrome-magnetite with the active participation of a metamorphic fluid enriched in crustal components. The orcelite–maucherite–ferrichromite–sperrylite assemblage formed in epidote-amphibolitic facies settings during this stage.The PGE mineral assemblage reflects different stages in the formation of the chromitites and dunite-harzburgite host rocks and their transformation from primitive mantle to crustal metamorphic processes.     

Palaeoproterozoic Chibaisong mafic intrusion and mineralization (Northeast China), the oldest Cu–Ni sulphide deposit in China: evidence from Re–Os dating of pyrrhotite

The Chibaisong magmatic Cu–Ni sulphide deposit is located in Tonghua City, Jilin Province, in the eastern part of the northern margin of the North China Craton. The geological characteristics of the deposit have been investigated, and pyrrhotite Re–Os isotope dating has been utilized to constrain the age. Five pyrrhotite samples separated from the Chibaisong Cu–Ni sulphide deposit yielded a Re–Os isotopic isochron age of 2237 ± 62 Ma (mean squared weighted deviation = 1.13, n = 5), indicating that the only Palaeoproterozoic magmatic Cu–Ni sulphide deposit in China is the Chibaisong Cu–Ni sulphide deposit. The geodynamic setting during ore formation was related to the Liaoning–Jilin Palaeoproterozoic rift split. The Re–Os isotope analyses showed an initial ¹⁸⁷Os/¹⁸⁸Os ratio of 0.778 ± 0.033, and (¹⁸⁷Os/¹⁸⁸Os)_i and γOs(t) values ranged from 0.7531 to 0.8013 (average 0.7734) and from 574 to 617 (average 592), respectively, indicating that abundant crustal material (5–10%) was mixed with the Cu–Ni sulphide ore system during magma ascent and ore formation.     

Platinum group element mineralization of the Svetly Bor and Veresovy Bor clinopyroxenite–dunite massifs,Middle Urals,Russia

The new data for the geology and mineralogy of the platinum group element (PGE) mineralization related to the chromite–platinum ore zones within the dunite of the Svetly Bor and Veresovy Bor massifs in the Middle Urals are discussed. The geological setting of the chromite–platinum ore zones, their platinum content, compositional and morphological features of the platinum group minerals (PGM) are compared to those within the Nizhny Tagil massif, the world standard of the zonal complexes in the Platinum Ural belt. The chromite–platinum orebodies are spatially related to the contacts between differently granular dunites. Majority of PGM are formed by Pt–Fe alloys that are close in terms of stoichiometry to isoferroplatinum (Pt₃Fe), and associated with Os–Ir alloys, Ru–Os and Ir–Rh sulfides, and Ir–Rh thiospinels of the cuproiridsite–cuprorhodsite–ferrorhodsite solid solution. The tetraferroplatinum (PtFe)–tulameenite (PtFe_0.5Cu_0.5) solid solution and Pt–Cu alloys belong to the later PGM assemblage. The established features of the chromite–platinum ore zones testify to the highly probable identification of the PGE mineralization within the dunite of the Svetly Bor and Vesesovy Bor massifs and could be used in prospecting and exploration for platinum.     

Platinum-group Mineral (PGM) and Base-metal Sulphide (BMS) Inclusions in Chromitites of the Zedang Ophiolite, Southern Tibet, China and their Petrogenetic Significance

Voluminous platinum-group mineral(PGM) inclusions including erlichmanite(Os,Ru)S_2, laurite(Ru,Os)S_2, and irarsite(Ir,Os,Ru,Rh)As S, as well as native osmium Os(Ir) and inclusions of base metal sulphides(BMS), including millerite(NiS), heazlewoodite(Ni_3S_2), covellite(CuS) and digenite(Cu_3S_2), accompanied by native iron, have been identified in chromitites of the Zedang ophiolite, Tibet. The PGMs occur as both inclusions in magnesiochromite grains and as small interstitial granules between them; most are less than 10 μm in size and vary in shape from euhedral to anhedral. They occur either as single or composite(biphase or polyphase) grains composed solely of PGM, or PGM associated with silicate grains. Os-, Ir-, and Ru-rich PGMs are the common species and Pt-, Pd-, and Rh-rich varieties have not been identified. Sulfur fugacity and temperature appear to be the main factors that controlled the PGE mineralogy during crystallization of the host chromitite in the upper mantle. If the activity of chalcogenides(such as S, and As) is low, PGE clusters will remain suspended in the silicate melt until they can coalesce to form alloys. Under appropriate conditions of ?S_2 and ?O_2, PGE alloys might react with the melt to form sulfides-sulfarsenides. Thus, we suggest that the Os, Ir and Ru metallic clusters and alloys in the Zedang chromitites crystallized first under high temperature and low ?S_2, followed by crystallization of sulphides of the laurite-erlichmanite, solid-solution series as the magma cooled and ?S_2 increased. The abundance of primary BMS in the chromitites suggests that ?S_2 reached relatively high values during the final stages of magnesiochromite crystallization. The diversity of the PGE minerals, in combination with differences in the petrological characteristics of the magnesiochromites, suggest different degrees of partial melting, perhaps at different depths in the mantle. The estimated parental magma composition suggests formation in a suprasubduction zone environment, perhaps in a forearc.     

Chemical evolution of metal in refractory inclusions in CV3 chondrites

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to measure distributions of the siderophile elements V, Fe, Co, Ni, Mo, Ru, Rh, Pd, W, Re, Os, Ir, Pt, and Au in Fremdlinge with a spatial resolution of 15 to 25 μm. A sulfide vein in a refractory inclusion in Allende (CV3-oxidized) is enriched in Rh, Ru, and Os with no detectable Pd, Re, Ir, or Pt, indicating that Rh, Ru, and Os were redistributed by sulfidation of the inclusion, causing fractionation of Re/Os and other siderophile element ratios in Allende CAIs. Fremdlinge in compact Type-A inclusions from Efremovka (CV3-reduced) exhibit subsolidus exsolution into kamacite and taenite and minimal secondary formation of V-magnetite and schreibersite. Siderophile element partitioning between taenite and kamacite is similar to that observed previously in iron meteorites, while preferential incorporation of the light PGEs (Ru, Rh, Pd) relative to Re, Os, Ir, and Pt by schreibersite was observed. Fremdling EM2 (CAI Ef2) has an outer rim of P-free metal that preserves the PGE signature of schreibersite, indicating that EM2 originally had a phosphide rim and lost P to the surrounding inclusion during secondary processing. Most Fremdlinge have chondrite-normalized refractory PGE patterns that are unfractionated, with PGE abundances derived from a small range of condensation temperatures, ∼1480 to 1468 K at P_tot = 10⁻³ bar. Some Fremdlinge from the same CAI exhibit sloping PGE abundance patterns and Re/Os ratios up to 2 × CI that likely represent mixing of grains that condensed at various temperatures.     

Re–Os and U–Pb Geochronology of the Dawan Mo–Zn–Fe Deposit in Northern Taihang Mountains,China

The Dawan Mo–Zn–Fe deposit located in the Northern Taihang Mountains in the middle of the North China Craton (NCC) contains large Mo‐dominant deposits. The mineralization of the Dawan Mo–Zn–Fe deposit is associated with the Mesozoic Wanganzhen granitoid complex and is mainly hosted within Archean metamorphic rocks and Proterozoic–Paleozoic dolomites. Rhyolite porphyry and quartz monzonite both occur in the ore field and potassic alteration, strong silicic–phyllic alteration, and propylitic alteration occur from the center of the rhyolite porphyry outward. The Mo mineralization is spacially related to silicic and potassic alteration. The Fe orebody is mainly found in serpentinized skarn in the external contact zone between the quartz monzonite and dolomite. Six samples of molybdenite were collected for Re–Os dating. Results show that the Re–Os model ages range from 136.2 Ma to 138.1 Ma with an isochron age of 138 ± 2 Ma (MSWD = 1.2). U–Pb zircon ages determined by laser ablation inductively coupled plasma mass spectrometry yield crystallization ages of 141.2 ± 0.7 (MSWD = 0.38) and 130.7 ± 0.6 Ma (MSWD = 0.73) for the rhyolite porphyry and quartz monzonite, respectively. The ore‐bearing rhyolite porphyry shows higher K₂O/Na₂O ratios, ranging from 58.0 to 68.7 (wt%), than those of quartz monzonite. All of the rock samples are classified in the shoshonitic series and characterized by enrichment in large ion lithophile elements; depletion in Mg, Fe, Ta, Ni, P, and Y; enrichment in light rare earth elements with high (La/Yb)_n ratios. Geochronology results indicate that skarn‐type Fe mineralization associated with quartz monzonite (130.7 ± 0.6 Ma) formed eight million years later than Mo and Zn mineralization (138 ± 2 Ma) in the Dawan deposit. From Re concentrations in molybdenite and previously presented Pb and S isotope data, we conclude that the ore‐forming material of the deposit was derived from a crust‐mantle mixed source. The porphyry‐skarn type Cu–Mo–Zn mineralization around the Wanganzhen complex is related to the primary magmatic activity, and the skarn‐type Fe mineralization is formed at the late period magmatism. The Dawan Mo–Zn–Fe porphyry‐skarn ores are related to the magmatism that was associated with lithospheric thinning in the NCC.     

Depositional Age of a Fossil Whale Bone from São Paulo Ridge,South Atlantic Ocean,Based on Os Isotope Stratigraphy of a Ferromanganese Crust

Whale carcasses (whale falls) deposited on the deep seafloor are associated with a distinctive biotic community. A fossil whale bone recovered from São Paulo Ridge, South Atlantic Ocean, during cruise YK13–04 Leg 1 of R/V Yokosuka was covered by a ferromanganese (Fe–Mn) crust approximately 9 mm thick. Here, we report an age constraint for this fossil bone on the basis of Os isotopic stratigraphy (¹⁸⁷Os/¹⁸⁸Os ratio) of the Fe–Mn crust. Major‐ and trace‐element compositions of the crust are similar to those of Fe–Mn crusts of predominantly hydrogenous origin. Rare earth element concentrations in samples of the crust, normalized with respect to Post‐Archean average Australian Shale, exhibit flat patterns with positive Ce and negative Y anomalies. These results indicate that the Fe–Mn crust consists predominantly of hydrogenous components and that it preserves the Os isotope composition of seawater at the time of its deposition. ¹⁸⁷Os/¹⁸⁸Os ratios of three Fe–Mn crust samples increased from 0.904 to 1.068 in ascending stratigraphic order. The value of 1.068 from the surface slice (0–3 mm depth in the crust) was identical to that of present‐day seawater within error (~1.06). The value of 0.904 from the basal slice (6–9 mm) equaled seawater values from ca. 4–5 Ma. Because it is unknown how long the bone lay on the seafloor before the Fe–Mn crust was deposited, the Os stratigraphic age of ca. 5 Ma is a minimum age of the fossil. This is the first application, to our knowledge, of marine Os isotope stratigraphy for determining the age of a fossil whale bone. Such data may offer valuable insights into the evolution of the whale‐fall biotic community.     

Yarlongite: A New Metallic Carbide Mineral

Yarlongite occurs in ophiolitic chromitite at the Luobusha mine (29°5′N 92°5′E, about 200 km ESE of Lhasa), Qusum County, Shannan Prefecture, Tibet Autonomous Region, People’s Republic of China. Associated minerals are: diamond, moissanite, wüstite, iridium (“osmiridium”), osmium (“iridosmine”), periclase, chromite, native iron, native nickel, native chromium, forsterite, Cr-rich diopside, intermetallic compounds Ni-Fe-Cr, Ni-Cr, Cr-C, etc. Yarlongite and its associated minerals were handpicked from a large heavy mineral sample of chromitite. The metallic carbides associated with yarlongite are cohenite, tongbaite, khamrabaevite and qusongite (IMA2007-034). Yarlongite occurs as irregular grains, with a size between 0.02 and 0.06 mm, steel-grey colour, H Mohs: 5?-6. Tenacity: brittle. Cleavage: {0 0 1} perfect. Fracture: conchoidal. Chemical formula: (Cr4Fe4Ni)Σ9C4, or (Cr,Fe,Ni)Σ9C4, Crystal system: Hexagonal, Space Group: P63/mc, a = 18.839(2) ?, c = 4.4960 (9) ?, V = 745.7(2) ?3, Z = 6, Density (calc.) = 7.19 g/cm3 (with simplified formula). Yarlongite has been approved as a new mineral by the CNMNC (IMA2007-035). Holotype material is deposited at the Geological Museum of China (No. M11650).     

Enrichment of Rh,Ru, Ir and Os in Cr spinels from oxidized magmas: Evidence from the Ambae volcano,Vanuatu

Experimental studies, performed under oxidized conditions (fO₂ > QFM + 2, where QFM is quartz–fayalite–magnetite oxygen buffer), have shown that Rh, Ru, Ir and Os are strongly compatible with Cr spinel, whereas empirical studies of Cr spinels from ultramafic–mafic rocks suggest that the experimental results may overestimate the partition coefficients. We report laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analyses of platinum-group elements (PGE), Au and Re abundances in Cr spinels from the Ambae volcano, Vanuatu (fO₂ = QFM + 2.5), the Jimberlana layered intrusion, western Australia, and the Bushveld complex, South Africa (fO₂ ～ QFM). The results show that Rh and IPGEs (Iridium-group PGE; Ru, Ir, Os) partition strongly into the Cr spinels that crystallized from the oxidized Ambae lavas whereas most of the Cr spinels from the more reduced Jimberlana layered intrusion and the Bushveld complex contain no detectable PGE, Au or Re, with exception of ～10 ppb of Ir in some Jimberlana Cr spinels. In the Ambae Cr spinels, Rh, Ru and, to lesser extent Os, are positively correlated with Fe³⁺, Ni and V. The homogeneous distribution of Rh and IPGEs in LA-ICP-MS time-resolved spectra indicates that these elements are in solid solution in Cr spinels. Pt–Fe alloys occur as inclusions within the Ambae Cr spinels, which indicate that the Ambae melt was saturated with Pt.Our results show that partitioning of Rh, Ru and Ir into Cr spinels increases with increasing oxygen fugacity, which suggests that the high concentrations of these elements in the Ambae Cr spinels are due to the high oxygen fugacity of the host magma. Therefore, Cr spinels may play an important role in controlling the concentrations of Rh and IPGEs during fractional crystallization of oxidized ultramafic–mafic magmas and during partial melting of oxidized arc mantle.     

A Comprehensive Method for Precise Determination of Re,Os, Ir,Ru, Pt,Pd Concentrations and Os Isotopic Compositions in Geological Samples

A comprehensive method for the precise determination of Re, Os, Ir, Ru, Pt and Pd concentrations as well as Os isotopic compositions in geological samples is presented. Samples were digested by the Carius tube method, and the Os was extracted by conventional CCl₄ method. The Re, Ir, Ru, Pt and Pd were first subgroup separated from the matrix elements into Re‐Ru, Ir‐Pt and Pd by a 2‐ml anion exchange column. Subsequently, the Re‐Ru was further purified by a secondary 0.25 ml anion exchange column or by microdistillation of Ru using CrO₃‐H₂SO₄ as an oxidant followed by a secondary 0.25 ml anion exchange separation of Re. The Pd and Ir‐Pt were further successively purified by an Eichrom‐LN column to completely remove Zr and Hf, respectively. Rhenium, Ir, Ru, Pt and Pd were individually measured by multi‐collector inductively coupled plasma‐mass spectrometry (MC‐ICP‐MS), except for Ru after microdistillation purification was analysed by negative‐thermal ionisation mass spectrometry (N‐TIMS). The analytical results for peridotite reference material WPR‐1 agree well with the previously published data. Finally, several mafic rock reference materials including TDB‐1, WGB‐1, BHVO‐2, BCR‐2, BIR‐1a and DNC‐1a were analysed for Re‐Os isotopes and platinum‐group element concentrations to test their suitability for certification.     

First Reliable Re–Os Ages of Pyrite and Stable Isotope Compositions of Fe(‐Cu) Deposits in the Hami Region,Eastern Tianshan Orogenic Belt,NW China

The Eastern Tianshan Orogenic Belt (ETOB) in NW China is composed of the Dananhu–Tousuquan arc belt, the Kanggurtag belt, the Aqishan–Yamansu belt and the Central Tianshan belt from north to south. These tectonic belts have formed through arc–continent or arc–arc collisions during the Paleozoic. A number of Fe(‐Cu) deposits in the Aqishan–Yamansu belt, including the Heifengshan, Shuangfengshan and Shaquanzi Fe(‐Cu) deposits, are associated with Carboniferous–Early Permian volcanic rocks and are composed of vein‐type magnetite ores. Metallic minerals are dominated by magnetite and pyrite, with minor chalcopyrite. Calcite, chlorite, and epidote are the dominant gangue minerals. Pyrite separates of ores from those three deposits have relatively high and variable Re contents ranging from 3.7 to 184 ppb. All pyrite separates have very low common Os, allowing us calculation of single mineral model ages for each sample. Pyrite separates from the Heifengshan Fe deposit have an ¹⁸⁷Re–¹⁸⁷Os isochron age of 310 ± 23 Ma (MSWD = 0.04) and a weighted mean model age of 302 ± 5 Ma (MSWD = 0.17). Those from the Shuangfengshan Fe deposit have an isochron age of 295 ± 7 Ma (MSWD = 0.28) and a weighted mean model age of 292 ± 5 Ma (MSWD = 0.33). The Shaquanzi Fe‐Cu deposit has pyrite with an isochron age of 295 ± 7 Ma (MSWD = 0.26) and a weighted mean model age of 295 ± 6 Ma (MSWD = 0.23). Pyrite separates from these Fe(‐Cu) deposits have δ³⁴S_CDT ranging from ?0.41‰ to 4.7‰ except for two outliers. Calcite from the Heifengshan Fe deposit and Shaquanzi Fe‐Cu deposit have similar C and O isotope compositions with δ¹³C_PDB and δ¹⁸O_SMOW ranging from ?5.5‰ to ?1.0‰ and from 10‰ to 12.7‰, respectively. These stable isotopic data suggest that S, C, and O are magmatic‐hydrothermal in origin. The association of low‐Ti magnetite and Fe/Cu‐sulfides resembles those of Iron–Oxide–Copper–Gold (IOCG) deposits elsewhere. Our reliable Re–Os ages of pyrite suggest that the Fe(‐Cu) deposits in the Aqishan–Yamansu belt formed at ～296 Ma, probably in a back‐arc extensional environment.     

High-grade iron ore at Windarling, Yilgarn Craton: a product of syn-orogenic deformation, hypogene hydrothermal alteration and supergene modification in an Archean BIF-basalt lithostratigraphy

Banded iron formation (BIF)-hosted iron ore deposits in the Windarling Range are located in the lower greenstone succession of the Marda–Diemals greenstone belt, Southern Cross domain, Yilgarn Craton and constitute a total hematite–martite–goethite ore resource of minimum 52 Mt at 60 wt.% Fe (0.07 P). Banded iron formation is interlayered with high-Mg basalts at Windarling and precipitated during episodes of volcanic quiescence. Trace element content and the rare earth element (REE) ratios Y/Ho (42 to 45), Sm/Yb (1.5), together with positive La and Gd anomalies in ‘least-altered’ hematite–magnetite–metachert–BIF indicate the precipitation from Archean seawater that was fertilised by hydrothermal vent fluids with a basaltic HREE-Y signature. Hypogene iron ore in sub-greenschist facies metamorphosed BIF formed during three distinct stages: ore stage 1 was a syn- to post-metamorphic, syn-D₁, Fe–Ca–Mg–Ni–Co–P–REE metasomatism that produced local Ni–REE-rich Fe–dolomite–magnetite alteration in BIF. Hydrothermal alteration was induced by hot fluid flow controlled by brittle–ductile reactivation of BIF-basalt margins and crosscutting D₁ faults. The Ni–Co-rich content of dolomite and a shift in REE ratios in carbonate-altered BIF towards Archean mafic rock signature (Y/Ho to 31 to 40, Sm/Yb to 1 to 2 and Gd/Gd* to 1.2 to 1.4) suggest that high-Mg basalts in the Windarling Range were the primary source of introduced metals. During ore stage 2, a syn-deformational and likely acidic and oxidised fluid flow along BIF-basalt margins and within D₁ faults leached carbonate and precipitated lepidoblastic and anhedral/granoblastic hematite. High-grade magnetite–hematite ore is formed during this stage. Ore stage 3 hydrothermal specular hematite (spcH)–Fe–dolomite–quartz alteration was controlled by a late-orogenic, brittle, compressional/transpressional stage (D₄; the regional-scale shear-zone-related D₃ is not preserved in Windarling). This minor event remobilised iron oxides, carbonate and quartz to form veins and breccia but did not generate significant volumes of iron ore. Ore stage 4 involved Mesozoic(?) to recent supergene oxidation and hydration in a weathering environment reaching down to depths of ～100 to maximum 200 m below surface. Supergene ore formation involved goethite replacement of dolomite and quartz as well as martitisation. Important ‘ground preparation’ for supergene modification and upgrade were mainly the formation of steep D₁ to D₄ structures, steep BIF/basalt margins and particularly the syn-D₁ to syn-D₂ carbonate alteration of BIF that is most susceptible to supergene dissolution. The Windarling deposits are structurally controlled, supergene-modified hydrothermal iron ore systems that share comparable physical, chemical and ore-forming characteristics to other iron ore deposits in the Yilgarn Craton (e.g. Koolyanobbing, Beebyn in the Weld Range, Mt. Gibson). However, the remarkable variety in pre-, syn- and post-deformational ore textures (relative to D₁ and D₂) has not been described elsewhere in the Yilgarn and are similar to the ore deposits in high-strain zones, such as of Brazil (Quadrilátero Ferrífero or Iron Quadrangle) and Nigeria. The overall similarity of alteration stages, i.e. the sequence of hydrothermal carbonate introduction and hypogene leaching, with other greenstone belt-hosted iron ore deposits supports the interpretation that syn-orogenic BIF alteration and upgrade was crucial in the formation of hypogene–supergene iron ore deposits in the Yilgarn Craton and possibly in other Archean/Paleoproterozoic greenstone belt settings worldwide.     

Constitutive mass balance relations between chemical composition,volume, density,porosity, and strain in metasomatic hydrochemical systems: Results on weathering and pedogenesis

Relations characterizing the chemical, physical, and mechanical changes resulting from metasomatic hydrochemical processes are developed using mass balance models which formally link chemical composition to bulk density, mineral density, volumetric properties, porosity, and amount of deformation (strain). Rigorous analysis of aqueous solute transport effects is then made possible in a variety of porous media flow environments including chemical weathering, pedogenesis (soil formation), diagenesis, ore deposition and enrichment, and metamorphism. Application of these linear constitutive relations to chemical weathering profiles shows that immobile and locally mobile chemical elements, with masses conserved on the scale of soil profiles, can be accurately identified from analysis of appropriate data arrays and then used as natural geochemical tracers to infer the nature and extent of hydrochemical weathering processes and volume changes during pedogenesis. Assumptions commonly made in the past about the supposed immobility of certain elements, e.g., Ti and Zr, become unnecessary. Quantitative differentiation between the effects of residual and supergene fractionation is then easily made.These methods are applied to Ni-rich laterites developed by weathering of ultramafic rocks, showing that during ordinary residual enrichment, Ni is concentrated by as much as 4× protolith peridotite concentrations. This occurs simply by silicate mineral dissolution and removal of chemical elements other than Ni (e.g., Mg) with a corresponding reduction in saprolite density and increase in bulk porosity without significant deformation. In contrast, laterites with mineable concentrations of Ni which are similarly undeformed (such as the Nickel Mountain Mine in Riddle, Oregon) have experienced, in addition to residual enrichment, strong supergene enrichment by fractionation of ore elements between a leached zone from which Ni is extracted and a complementary enriched zone positioned farther along the direction of ground water flow.Soil-forming processes in podzol chronosequences developed on sandy beach terraces of the Mendocino Coast of California involved soil column collapse of 60 percent by dissolution of silicate minerals in the albic horizon of Al and Fe leaching, and 70 percent dilation (expansion) in the overlying organic-rich layer by root growth. The amount of erosion based upon paleosurface reconstructions using the excess mass of Fe, Al, Pb, Ga, and Cu in the zone of supergene enrichment (spodic horizon) below the ground water table indicates that subsurface erosion by dissolutional collapse is three times that of surficial erosion.Finally, using published chemical data for Ti, Zr, and Cr on major bauxite deposits in Australia where erosion rates are thought to be low, we infer that there may have been major amounts of dissolutional collapse to explain the upwards increase of detrital zircon and rutile in weathering profiles.     

Magma Mixing as a Trigger for Sulphide Saturation in the UG2 Chromitite (Bushveld): Evidence from the Silicate and Sulphide Melt Inclusions in Chromite

It is of great importance to understand the origin of UG2 chromitite reefs and reasons why some chromitite reefs contain relatively high contents of platinum group elements(PGEs: Os, Ir, Ru, Rh,Pt, Pd) or highly siderophile elements(HSEs: Au, Re, PGE). This paper documents sulphide-silicate assemblages enclosed in chromite grains from the UG2 chromitite. These are formed as a result of crystallisation of sulphide and silicate melts that are trapped during chromite crystallisation. The inclusions display negative crystal shapes ranging from several micrometres to 100 μm in size.Interstitial sulphide assemblages lack pyrrhotite and consist of chalcopyrite, pentlandite and some pyrite. The electron microprobe data of these sulphides show that the pentlandite grains present in some of the sulphide inclusions have a significantly higher iron(Fe) and lower nickel(Ni) content than the pentlandite in the rock matrix. Pyrite and chalcopyrite show no difference. The contrast in composition between inter-cumulus plagioclase(An_(68)) and plagioclase enclosed in chromite(An_(13)), as well as the presence of quartz, is consistent with the existence of a felsic melt at the time of chromite saturation.Detailed studies of HSE distribution in the sulphides and chromite were conducted by LA-ICP-MS(laser ablation-inductively coupled plasma-mass spectrometry), which showed the following.(Ⅰ) Chromite contained no detectable HSE in solid solution.(Ⅱ) HSE distribution in sulphide assemblages interstitial to chromite was variable. In general, Pd, Rh, Ru and Ir occurred dominantly in pentlandite, whereas Os,Pt and Au were detected only in matrix sulphide grains and were clearly associated with Bi and Te.(Ⅲ)In the sulphide inclusions,(a) pyrrhotite did not contain any significant amount of HSE,(b) chalcopyrite contained only some Rh compared to the other sulphides,(c) pentlandite was the main host for Pd,(d)pyrite contained most of the Ru, Os, Ir and Re,(e) Pt and Rh were closely associated with Bi forming a continuous rim between pyrite and pentlandite and(f) no Au was detected. These results show that the use of ArF excimer laser to produce high-resolution trace element maps provides information that cannot be obtained by conventional(spot) LA-ICP-MS analysis or trace element maps that use relatively large beam diameters.     

Use of Hydrofluoric Acid Desilicification in the Determination of Highly Siderophile Element Abundances and Re‐Pt‐Os Isotope Systematics in Mafic‐Ultramafic Rocks

Properly combining highly siderophile element (HSE: Re, Pd, Pt, Ru, Ir, Os) abundance data, obtained by isotope dilution, with corresponding ¹⁸⁷Os/¹⁸⁸Os and ¹⁸⁶Os/¹⁸⁸Os measurements of rocks requires efficient digestion of finely‐ground powders and complete spike‐sample equilibration. Yet, because of the nature of commonly used methods for separating Os from a rock matrix, hydrofluoric acid (HF) is typically not used in such digestions. Consequently, some silicates are not completely dissolved, and HSE residing within these silicates may not be fully accessed. Consistent with this, some recent studies of basaltic reference materials (RMs) have concluded that an HF‐desilicification procedure is required to fully access the HSE (Ishikawa et al. (2014) Chemical Geology, 384, 27–46; Li et al. (2015) Geostandards and Geoanalytical Research, 39, 17–30). Highly siderophile element abundance and Os isotope studies of intraplate basalts typically target samples with a range of MgO contents (< 8 to > 18% m/m, or as mass fractions, < 8 to > 18 g per 100 g), in contrast to the lower MgO mass fractions (< 10 g per 100 g) of basalt and diabase RMs (i.e., BIR‐1, BHVO‐2, TDB‐1). To investigate the effect of HF‐desilicification on intraplate basalts, experiments were performed on finely ground Azores basalts (8.1–17 g per 100 g MgO) using a ‘standard acid digestion’ (2:1 mixture of concentrated HNO₃ and HCl), and a standard acid digestion, followed by HF‐desilicification. No systematic trends in HSE abundances were observed between data obtained by standard acid digestion and HF‐desilicification. Desilicification procedures using HF do not improve liberation of the HSE from Azores basalts, or some RMs (e.g., WPR‐1). We conclude that HF‐desilicification procedures are useful for obtaining total HSE contents of some young lavas, but this type of procedure is not recommended for studies where Re‐Pt‐Os chronological information is desired. The collateral effect of a standard acid digestion to liberate Os, followed by HF‐desilicification to obtain Re and Pt abundances in samples, is that the measured Re/Os and Pt/Os may not correspond with measured ¹⁸⁷Os/¹⁸⁸Os or ¹⁸⁶Os/¹⁸⁸Os.     

Genetic Nature of Mineralization with Native and Intermetallic Compounds in the Bobruisk Ring Structure (Republic of Belarus)

The results of study of the Bobruisk ring structure (Republic of Belarus) containing ~80 rare rockforming and accessory minerals are reported. Among them are native (Fe, Cu, Sn, Zn, Pb, Ag, Mo, W, Al) and intermetallic (Fe, Cr, Ni, Mo, B, N, C, Si) compounds, natural alloys (Fe–Cr, Fe–Cr–Mo–W–B; brass (Cu–Zn–Pb); and bronze (Sn–Pb–Zn–Cu)). They are observed as segregations of various shapes and sizes, as well as their aggregates. The formation of mineralization is controlled by reduced mantle fluids enriched in H₂, CH₄, CO, Si, N, and O and stimulating accumulation of rare elements as native and intermetallic phases, alloys, rather than isomorphic impurities in minerals.     

Platinum-group mineral assemblage of the Prizhimny Creek (Koryak Highland)

In the alluvial deposits of the Prizhlimny Creek (southern part of the Koryak Highland), grains of platinum-group minerals are found along with gold. We have established that the grains are native platinum (Pt, Fe) containing Cu (up to 5 wt.%), Os (up to 8 wt.%), and Rh (up to 2 wt.%). Inclusions in the platinum are native osmium (the content of Ir impurity reaches 12 wt.%, the average content being 0.2–4 wt.%), an unnamed intermetallic compound of composition PtRh, sulfides and arsenides of PGE (cooperite, laurite, malanite, cuproiridsite, cuprorhodsite, sperrylite, hollingworthite, unnamed compounds PdS, (Ir,Ru)S₂, (Ir,Pt)S₂, Cu, and Fe (bornite, chalcopyrite), chromite, and Cr-magnetite. Replacement of native-osmium crystals by compound IrO₂ is described. It has been established that this compound formed during oxidation accompanied by the replacement of isoferroplatinum by native platinum. The data obtained agree with the results of study of platinum-group mineral assemblages from placers localized in weakly eroded Ural–Alaskan-type massifs whose apical parts formed under high oxygen activity conditions. Clinopyroxenites of the Prizhimny massif are considered to be the potential source of PGE.