Origin of primary PGM assemblage in сhromitite from a mantle tectonite at Harold’s Grave (Shetland Ophiolite Complex, Scotland)

In this paper we present textural and mineral chemistry data for a PGM inclusion assemblage and whole-rock platinum-group element (PGE) concentrations of chromitite from Harold’s Grave, which occurrs in a dunite pod in a mantle tectonite at Unst in the Shetland Ophiolite Complex (SOC), Scotland. The study utilized a number of analytical techniques, including acid digestion and isotope dilution (ID) ICP-MS, hydroseparation and electron microprobe analysis. The chromitite contains a pronounced enrichment of refractory PGE (IPGE: Os, Ir and Ru) over less refractory PGE (PPGE: Rh, Pt and Pd), typical of mantle hosted ‘ophiolitic’ chromitites. A ‘primary’ magmatic PGM assemblage is represented by euhedrally shaped (up to 60 μm in size) single and composite inclusions in chromite. Polyphase PGM grains are dominated by laurite and osmian iridium, with subordinate laurite + osmian iridium + iridian osmium and rare laurite + Ir-Rh alloy + Rh-rich sulphide (possibly prassoite). The compositional variability of associated laurite and Os-rich alloys at Harold’s Grave fit the predicted compositions of experiment W-1200-0.37 of Andrews and Brenan (Can Mineral 40: 1705–1716, 2002) providing unequivocal information on conditions of their genesis, with the upper thermal stability of laurite in equilibrium with Os-rich alloys estimated at 1200–1250 °C and f(S₂) of 10^?0.39–10^?0.07.     

铂族元素矿物共生组合(英文)

由于铂族元素能有效地降低汽车尾气的污染 ,其需求量日益增加 ,对铂族元素矿床的寻找已是当务之急。着重从矿物矿床学角度对铂族元素的矿物共生特点进行了探讨。铂族元素可呈独立矿床产出 ,主要产于基性超基性层状侵入体、蛇绿岩套及阿拉斯加式侵入体中。铂族元素也伴生于铜镍矿床中 ,该类铜镍矿床主要与苏长岩侵入体、溢流玄武岩及科马提岩有关。产于基性超基性层状侵入体中的铂族矿物有铂钯硫化物、铂铁合金、钌硫化物、铑硫化物、铂钯碲化物、钯砷化物及钯的合金。这些铂族矿物可与硫化物矿物共生 ,也可与硅酸盐矿物共生 ,还可与铬铁矿及其他氧化物矿物共生。产于蛇绿岩套中的铂族矿物主要是钌铱锇的矿物 ,而铂钯铑的矿物则较少出现 ,这些铂族矿物可呈合金、硫化物、硫砷化物以及砷化物 4种形式出现。产于阿拉斯加式侵入体中的铂族矿物主要有铂铁合金、锑铂矿、硫铂矿、砷铂矿、硫锇矿及马兰矿等少数几种 ,其中铂铁合金与铬铁矿及与其同时结晶的高温硅酸盐矿物共生 ,而其他的铂族矿物则与后来的变质作用及蛇纹岩化作用中形成的多金属硫化物及砷化物共生。产于铜镍矿床中的铂族矿物主要是铂和钯的矿物。产于基性超基性层状侵入体、蛇绿岩套及阿拉斯加式侵入体中的铂族矿物的共同特点是它们均与铬铁矿?     

Platinum–Group Minerals in Podiform Chromitite from the Kamuikotan Zone, Hokkaido, Northern Japan

Abstract: Ru–Os–Ir alloys have been found in two podiform chromitites located at the Chiroro and Bankei mines in the Sarugawa peridotite complex in the Kamuikotan zone, Hokkaido, Japan. This is the first report on the occurrence of PGM (= platinum-group minerals) from chromitites in Japan. The Ru–Os–Ir alloys most typically form polyhedra associated with other minerals (Ni–Fe alloys and heazlewoodite) in chromian spinel. The PGM are possibly pseudomorphs after some primary PGM such as laurite and are chemically highly inhomogeneous, indicating a low-temperature alteration origin. This is consistent with intense alteration (formation of serpentine, uvarovite and kämmererite) imposed on the Kamuikotan chromitites. High-temperature primary PGE (platinum–group elements)–bearing sulfides were possibly recrystallized at low temperatures into a new assemblage of PGM, Ni-Fe alloys and sulfides. Placer PGM around the peridotite complexes are chemically different from the PGM in dunite and chromitite possibly due to the, as yet, incomplete search for the rock-hosted PGM. The PGE content in chromitites is distinctly higher in those in the Kamuikotan zone than in those in the Sangun zone of Southwest Japan, consistent with the more refractory nature (Cr# of spinel, up to 0.8) of the former than the latter (Cr# of spinel, 0.5).     

Platinum-group-mineral inclusions in chromite from the bird river sill,Manitoba

Platinum-group minerals (PGM) have been identified as inclusions in chromite from the Bird River Sill, Manitoba. The inclusions are small (<20 microns) and are commonly euhedral. The PGM inclusions are (Ru, Os, Ir) S₂, laurite, and (Os, Ir, Ru alloy), rutheniridosmine: Laurites contain up to 2.99 wt. % palladium. Arsenic content is negligible and no platinum or rhodium has been detected. One platinum-group element alloy contains 0.96 wt. % rhodium but neither platinum nor palladium has been detected. Laurite inclusions in chromite from the ultramafic zone record two compositional trends; first increasing and then decreasing Ru/(Ru+Os+Ir) up section. PGM inclusions and other solid inclusions occur as discrete phases in chromite and are part of the chromite precipitation event. Increasing oxygen fugacity by wall rock assimilation or new magma injection initiates chromite precipitation, locally increasing the sulphur content of the magma to convert PGE alloys to sulphides.     

Palladium and gold mineralization in podiform chromitite at Kraubath, Austria

Summary ?We report, for the first time, the occurrence of five palladium-rich, one palladium bearing and two gold-silver minerals from podiform chromitites in the Eastern Alps. Minerals identified include braggite, keithconnite, stibiopalladinite, potarite, mertieite II, Pd-bearing Pt-Fe alloy, native gold and Ag-Au alloy. They occur in heavy mineral concentrates produced from two massive podiform chromitite samples (unaltered and highly altered) of the Kraubath ultramafic massif, Styria, Austria. Distribution patterns of platinum-group elements (PGE) in these chromitites show considerable differences in the behaviour of the less refractory PGE (PPGE-group: Rh, Pt, Pd) compared to the refractory PGE (IPGE-group: Os, Ir, Ru). PPGE are more enriched in chromitite showing pronounced alteration features. The unaltered chromitite displays a negatively sloped chondrite-normalised PGE pattern similar to typical ophiolitic-podiform chromitite. Except for the Pd- and Au-Ag minerals that are generally rare in ophiolites, about 20 other platinum-group minerals (PGM) have been discovered. They include PGE-sulphides (laurite, erlichmanite, kashinite, bowieite, cuproiridsite, cuprorhodsite, unnamed Ir-rich variety of ferrorhodsite, unnamed Ni-Fe-Cu-Rh- and Ni-Fe-Cu-Ir-Rh monosulphides), PGE alloys (Pt-Fe, Ir-Os, Os-Ir and Ru-Os-Ir), PGE-sulpharsenides (irarsite, hollingworthite, platarsite, ruarsite and a number of intermediate species), sperrylite and a Ru-rich oxide (?). Three PGM assemblages have been recognised and attributed to different processes ranging from magmatic to hydrothermal and weathering-related. Pd-rich minerals are characteristic of both chromitite types, although their chemistry and relative proportions vary considerably. Keithconnite, braggite and Pd-bearing ferroan platinum, together with a number of PGE-sulphides (mainly laurite-erlichmanite) and alloys, are typical only of the unaltered podiform chromitite (assemblage I). Euhedral mono- and polyphase PGM grains in the submicron to 100 μm range show features of primary magmatic assemblages. The diversity of PGM in these assemblages is unusual for ophiolitic environments. In assemblage II, laurite-erlichmanite is intergrown with and overgrown by PGE-sulpharsenides; other minerals of assemblage I are missing. Potarite, stibiopalladinite, mertieite II, native gold and Ag-Au alloys, as well as PGE-sulpharsenides, sperrylite and base metal arsenides and sulphides are characteristic for the highly altered chromitite (assemblage III). They occur either interstitial to chromite in association with metamorphic silicates, in chromite rims or along cracks, and are thus interpreted as having formed by remobilization of PGE by hydrothermal processes during polyphase regional metamorphism. Received August 3, 2000;/revised version accepted December 28, 2000     

Distribution and mineralogy of platinum-group elements in altered chromitites of the Campo Formoso layered intrusion (Bahia State, Brazil): control by magmatic and hydrothermal processes

Summary Polyphase, penetrative hydrothermal metasomatism in chromitites of the Campo Formoso layered intrusion produced spectacular chromite – ferrian chromite zoning and transformed the primary intercumulus silicates into a chlorite – serpentine – carbonate – talc assemblage. Alteration did not substantially modify the composition of chromite cores and the distribution of platinum-group elements (PGE) through the sequence of chromitite layers, which still are consistent with magmatic fractionation processes. Texture and composition of laurite and Os–Ir–Ru alloys included in chromite cores indicate that these PGM were not altered, and are probably magmaticin origin. In contrast, the PGM located in the intergranular chlorite matrix (laurite, Ir–Ru–Rh sulfarsenides and Pt–Pd compounds with Sb, Bi and Te) display evidence of hydrothermal reworking. These PGM are intimately intergrown with low-temperature Ni-sulfides. The paragenesis suggests that the Ni-sulfides-PGM assemblage formed at the expenses of unknown PGM precursors, which must have been originally present in the intercumulus silicate matrix. Mechanism of formation involves a sequence of dissolution-precipitation events controlled by variation of redox conditions during chromite alteration. The presence of a secondary ore mineral assemblage consisting of galena, bismuthinite, native antimony, and various Pb–Sb compounds suggests a possible contribution of fluids derived from the adjacent granite.     

Improved Platinum-Group Element Extraction by NiS Fire Assay from Chromitite Ore Samples Using a Flux Containing Sodium Metaphosphate

Many chromite-rich rocks contain relatively high concentrations of the platinum-group elements (PGE). In many cases, the phases carrying PGE occur as either platinum-group minerals (PGM) or as base metal sulfides in solid solution in sulfides. In some cases, such as the UG-2 unit of the Bushveld Complex, the PGM are occluded inside chromite grains. Chromites are notably difficult to dissolve in most fluxes and if the chromite contains some PGM the possibility exists that not all the PGE will be recovered during fusion. In this work, shortcomings in published methods of analysis based on the nickel sulfide fire assay procedure were investigated and a new procedure developed based on the addition of sodium metaphosphate to the fusion mixture. Optimum composition of the fusion mixture was found to be 10 g sodium metaphosphate and 9 g silica to 10 g sample, 15 g sodium carbonate, 30 g lithium tetraborate, 7.5 g nickel and 4.5 g sulfur to achieve complete dissolution of chromite grains. The new flux mixture was evaluated by the analysis of reference material CHR-Pt+ (which is known to contain PGM inside chromite grains) and no undissolved chromite grains were found in the glassy slag. Analysis of the nickel sulfide beads from this fire assay using neutron activation analysis showed similar results for Rh and Ru when compared with published conventional true (or accepted) values, while Au, Ir, Os, Pd and Pt values determined here were 10 to 30% higher than the corresponding published conventional true values. It was concluded that the addition of sodium metaphosphate improved chromite dissolution in the flux and appears to improve PGE recovery.     

Geochemistry and mineralogy of platinum-group elements(PGE) in chromites from CentralnoyeⅠ,Polar Urals,Russia

The Polar Urals region of northern Russia is well known for large chromium(Cr)-bearing massifs with major chromite orebodies,including the Centralnoye I deposit in the Ray-Iz ultramafic massif of the Ural ophiolite belt.New data on platinum(Pt)-group elements(PGE).geochemistry and mineralogy of the host dunite shows that the deposit has anomalous iridium(Ir) values.These values indicate the predominance of ruthenium-osmium-iridium(Ru-Os-Ir)-bearing phases among the platinum-group mineral (PGM) assemblage...     

The mineralogy and mineral associations of platinum group elements and gold in the Platreef at Zwartfontein, Akanani Project, Northern Bushveld Complex, South Africa

The mineralogy of the platinum-group elements (PGE), and gold, in the Platreef of the Bushveld Complex, was investigated using an FEI Mineral Liberation Analyser. Polished sections were prepared from 171 samples collected from two boreholes, for the in-situ examination of platinum group minerals (PGM). PGM and gold minerals encountered include maslovite (PtBiTe, 32 area% of total PGM), kotulskite (Pd(BiTe), 17?%), isoferroplatinum (Pt₃Fe, 15?%), sperrylite (PtAs₂, 11?%), cooperite (PtS, 5?%), moncheite (PtTe₂; 5?%), electrum (AuAg; 5?%), michenerite (PdBiTe; 3?%), Pd alloys (Pd, Sb, Sn; 3?%), hollingworthite ((Rh,Pt)AsS; 2?%), as well as minor (all <1 area% of total PGM) merenskyite (PdBiTe₂), laurite (RuS₂), rustenburgite (Pt_0.4Pd_0.4Sn_0.2), froodite (PdBi₂), atokite (Pd_0.5Pt_0.3Sn_0.2), stumpflite (PtSb), plumbopalladinite (Pd₃Pb₂), and zvyagintsevite (Pd₃Pb). An observed association of all PGM with base metal sulfides (BMS), and a pronounced association of PGE tellurides, arsenides and Pd&Pt alloys with secondary silicates, is consistent with the remobilisation and recrystallisation of some of the PGM’s during hydrothermal alteration and serpentinisation subsequent to their initial (primary) crystallisation from BMS (e.g. Godel et al. J Petrol 48:1569–1604, 2007; Hutchinson and McDonald Appl Earth Sci (Trans Inst Min Metall B) 114:B208–224, 2008).     

Alteration of Platinum-Group and Base-Metal Mineral Assemblages in Ophiolite Chromitites from the Dobromirtsi Massif,Rhodope Mountains (Bulgaria)

The Dobromirtsi Ultramafic Massif, located in the Rhodope Mountains (SE Bulgaria), is a portion of a Paleozoic sub-oceanic mantle affected by polyphase regional metamorphism. This massif contains several small, podiform chromitite bodies which underwent the same metamorphic evolution as their host peridotites. Like other ophiolite chromitites, those found in Dobromirtsi carry abundant platinum-group minerals (PGM) and base-metal minerals (BMM). The PGM consist mainly of Ru-, Os-, and Ir-based PGM (laurite RuS₂-erlichmanite OsS₂, Os-Ru-Ir alloys, irarsite [IrAsS], Ru-rich pentlandite, and an unknown Ir-sulfide) but minor Rh- and Pd-based PGM (hollingworthite [RhAsS] and a series of unidentified stannides and sulfantimonides) are also present. In contrast, the BMM are dominated by pentlandite (Ni,Fe)₉S₈, followed by heazlewoodite (Ni₃S₂), breithauptite (NiSb), maucherite (Ni₁₁As₈), godlevskite (Ni₇S₆), gersdorffite (NiAsS), millerite (NiS), undetermined minerals containing Ni, As and Sb, orcelite (Ni_5-XAs₂), awaruite (Ni₃Fe) and chalcopyrite (CuFeS₂). The detailed study of the textural relationships, morphology and composition of the PGM and BMM inclusions indicate the existence of two different PGM-BMM assemblages: (i) a primary or magmatic; and (ii) a secondary related with postmagmatic alteration. The PGM and BMM inclusions in unaltered zones of chromite crystals (mainly laurite-erlichmanite and pentlandite) are considered to be primary magmatic minerals formed under variable temperature (1200–1100°C) and sulfur fugacity (between −2 and −0.5 log fS₂). In contrast, PGM and BMM located along altered edges of chromite and serpentinised silicate matrix are considered to be secondary, formed from or re-equilibrated with altering fluids. Secondary PGM and BMM assemblages are considered as result of the combination of reducing and oxidising events related with regional metamorphism. Under low fO₂ states, fS₂ also drops giving place to the formation of S-poor Ni-rich sulfides and secondary Ru-alloys by desulfurisation of primary S-containing minerals. In contrast, predominance of platinum-group elements and/or base-metal arsenides and sulfarsenides associated with the altered edges of chromite (chromite strongly enriched in Fe₂O₃) is related with the fixing of remobilised PGE (mainly Ir, Rh and Pd) and base-metals (mainly Ni and Fe) when late oxidising fluids supplied As as well as Sb and Sn.     

Platinum-group minerals from the Jinbaoshan Pd–Pt deposit,SW China: evidence for magmatic origin and hydrothermal alteration

The Jinbaoshan Pt–Pd deposit in Yunnan, SW China, is hosted in a wehrlite body, which is a member of the Permian (∼260 Ma) Emeishan Large Igneous Province (ELIP). The deposit is reported to contain one million tonnes of Pt–Pd ore grading 0.21% Ni and 0.16% Cu with 3.0 g/t (Pd + Pt). Platinum-group minerals (PGM) mostly are ∼10 μm in diameter, and are commonly Te-, Sn- and As-bearing, including moncheite (PtTe₂), atokite (Pd₃Sn), kotulskite (PdTe), sperrylite (PtAs₂), irarsite (IrAsS), cooperite (PtS), sudburyite (PdSb), and Pt–Fe alloy. Primary rock-forming minerals are olivine and clinopyroxene, with clinopyroxene forming anhedral poikilitic crystals surrounding olivine. Primary chromite occurs either as euhedral grains enclosed within olivine or as an interstitial phase to the olivine. However, the intrusion has undergone extensive hydrothermal alteration. Most olivine grains have been altered to serpentine, and interstitial clinopyroxene is often altered to actinolite/tremolite and locally biotite. Interstitial chromite grains are either partially or totally replaced by secondary magnetite. Base-metal sulfides (BMS), such as pentlandite and chalcopyrite, are usually interstitial to the altered olivine. PGM are located with the BMS and are therefore also interstitial to the serpentinized olivine grains, occurring within altered interstitial clinopyroxene and chromite, or along the edges of these minerals, which predominantly altered to actinolite/tremolite, serpentine and magnetite. Hydrothermal fluids were responsible for the release of the platinum-group elements (PGE) from the BMS to precipitate the PGM at low temperature during pervasive alteration. A sequence of alteration of the PGM has been recognized. Initially moncheite and atokite have been corroded and recrystallized during the formation of actinolite/tremolite, and then, cooperite and moncheite were altered to Pt–Fe alloy where they are in contact with serpentine. Sudburyite occurs in veins indicating late Pd mobility. However, textural evidence shows that the PGM are still in close proximity to the BMS. They occur in PGE-rich layers located at specific igneous horizons in the intrusion, suggesting that PGE were originally magmatic concentrations that, within a PGE-rich horizon, crystallized with BMS late in the olivine/clinopyroxene crystallization sequence and have not been significantly transported during serpentinization and alteration.     

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.     

Chemical composition and osmium-isotope systematics of primary and secondary PGM assemblages from high-Mg chromitite of the Nurali lherzolite massif,the South Urals,Russia

The isotopic and geochemical characteristics of PGE mineralization in high-Mg chromitite from the banded dunite–wehrlite–clinopyroxenite complex of the Nurali lherzolite massif, the South Urals, Russia is characterized for the first time. Electron microprobe analysis and LA MC-ICP-MS mass spectrometry are used for studying Cr-spinel and platinum-group minerals (PGM). Two processes synchronously develop in high-Mg chromitite subject to metamorphism: (1) the replacement of Mg–Al-rich Cr-spinel, orthopyroxene, and diopside by chromite, Cr-amphibole, chlorite, and garnet; (2) the formation of a secondary mineral assemblage consisting of finely dispersed ruthenium or Ru-hexaferrum aggregate and silicate–oxide or silicate matter on the location of primary Ru–Os-sulfides of the laurite–erlichmanite solid solution series. Similar variations of Os-isotopic composition in both primary and secondary PGM assemblages are evidence for the high stability of the Os isotope system in PGM and for the possibility of using model ¹⁸⁷Os/¹⁸⁸Os ages in geodynamic reconstructions.     

Alteration of platinum-group minerals and dispersion of platinum-group elements during progressive weathering of the Aguablanca Ni–Cu deposit, SW Spain

The distribution, mineralogy and mobility of the platinum-group elements (PGE) in the surface environment are poorly understood. This study of the lower, less altered and upper, more altered gossan, overlying the Aguablanca Ni–Cu-(PGE) magmatic deposit (Spain), has shown that the platinum-group minerals (PGM) are progressively oxidised and dispersed into iron oxides that form the gossan. A combination of the characterization of PGE in host PGM, using a scanning electron microscope, and measurement of PGE at lower concentrations in host iron oxides, using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), has for the first time allowed the total distribution of the PGE within a gossan to be documented. This study has revealed a complete in situ alteration and dispersion sequence of the PGM including (1) breakdown of both the more stable Pt-arsenides, Pt/Pd-tellurides and the less stable bismuthotellurides, (2) formation of partially oxidised PGM, (3) development of a wide range of oxidised Pt- and Pd-bearing phases, (4) subsequent formation of Fe–PGE-oxides and PGE-hydroxides, (5) incorporation of PGE into ferruginous supergene products and lastly (6) concentration of PGE at the edges of veins and iron oxides. Dispersion of Pd is greater than for the other PGE with Pd being widely distributed throughout the iron oxides. This oxidising environment produced PGE-oxides rather than PGE-alloys, also commonly found in the surface environment, especially in placers. These results provide critical evidence for the stages of mineralogical change from PGE host mineralogy in magmatic ores to surface weathering producing PGE-oxides.     

Platinum-group mineral inclusions in chromitites of the Finero mafic-ultramafic complex (Ivrea-Zone,Italy)

Zusammenfassung Kleine Chromititkörper wurden in Phlogopit-reichen Peridotiten des Finero-Komplexes (Ivrea Zone, Italien) entdeckt. Chromit enthdlt winzige (< 20 m) Einschlüsse von Platingruppen-Mineralen (PGM), sowie von Buntmetalsulfïden (BMS) and -legierungen (BMA); these führen Platin gruppen-Elemente (PGE) in Form von solid solutions.Als PGM wurden Laurit, gedigen Ir und Ir-Cu-Rh-Sulfide unterschiedlicher Zusammensetzung bestimmt.Die PGE-führenden BMS sind rhodiumführender Pentlandit und Millerit, iridium-führender Digenit und unbekannte Ir-reiche Ni-Fe-Cu Sulfide mit einem Metall/Schwefelverhältnis von etwa 1. Die BMA bestehen aus: Cu-Rh-Fe, Cu-Pt-Ag, Cu-Pb-Rh und Pb-Rh.Im Vergleich mit anderen untersuchten Vorkommen, in denen Ru-Os-Ir Legierungen und Laurit dominieren, zeigt die PGE-Mineralogie der Finero-Chromitite eine höhere Schwefelfugazität bei der Bildung an. Außerdem sind Cu und Rh in dieser Mineralgesellschaft weit verbreitet und auch Mikrosondenuntersuchungen belegen das Verhandensein von Ag und Pb in vielen der PGE-führenden Phasen.Dies ist für Chromit-bildende Systeme ungewöhnlich und wird mit der Aktivität einer alkali-reichen fluiden Phase, die auch für die Kristallisation des weitverbreiteten Phlogopits im Finero-Komplex verantwortlich ist, in Zusammenhang gebracht.

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Platinum-group mineral inclusions in chromitites of the Finero mafic-ultramafic complex (Ivrea-Zone, Italy)

Summary Small scale chromitites have been recently discovered in the phlogopite-rich peridotite of the Finero complex (Ivrea Zone, Italy). The chromite contains minute (<20 um) inclusions of platinum-group minerals (PGM), and base-metal sulfides (BMS) and alloys (BMA) which frequently bear platinum-group elements (PGE) in solid solution. The PGM are laurite, native Ir and Ir-Cu-Rh sulfides with variable compositions. The PGE-bearing BMS are rhodian pentlandite, rhodian millerite, iridian digenite, and unknown Ir-rich Ni-Fe-Cu sulfides with Metal/Sulfur ratio close to 1. The BMA's consist of the associations: Cu-Rh-Fe, Cu-Pt-Ag, Cu-Pb-Rh and Pb-Rh.Compared with other investigated occurrences dominated by Ru-Os-Ir alloys and laurite, the PGE-mineralogy of the Finero chromitites indicates a higher sulfur fugacity of formation. In addition, there is an overall abundance of Cu and Rh in the assemblage, and microprobe analyses revealed the presence of appreciable amounts of Ag and Pb in many of the PGE-bearing phases. These features are unusual for the chromite-forming system and are ascribed to the activity of the alkali-rich fluid phase responsible for the crystallization of abundant phlogopite in the Finero body.

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With 7 Figures     

Closed-system behaviour of the Re–Os isotope system recorded in primary and secondary platinum-group mineral assemblages: Evidence from a mantle chromitite at Harold's Grave (Shetland Ophiolite Сomplex,Scotland)

This study evaluates in detail the mineral chemistry, whole-rock and mineral separate Os-isotope compositions of distinct platinum-group mineral (PGM) assemblages in an isolated chromitite pod at Harold's Grave which occurs in mantle tectonite in the Shetland Ophiolite Complex (SOC), Scotland. This was the first ophiolite sequence worldwide that was shown to contain ppm levels of all six platinum-group elements (PGE) in podiform chromitite, including the contrasting type localities found here and at Cliff. At Harold's Grave the primary PGM assemblage is composed mainly of laurite and/or Os-rich iridium and formed early together with chromite, whereas the secondary PGM assemblage dominated by laurite, Os-rich laurite, irarsite, native osmium and Ru-bearing pentlandite is likely to reflect processes including in-situ serpentinization, alteration during emplacement and regional greenschist metamorphism. The osmium isotope data define a restricted range of ‘unradiogenic’ ¹⁸⁷Os/¹⁸⁸Os values for coexisting laurite and Os-rich alloy pairs from ‘primary’ PGM assemblage (0.12473–0.12488) and similar ‘unradiogenic’ ¹⁸⁷Os/¹⁸⁸Os values for both ‘primary’ and ‘secondary’ PGM assemblages (0.1242 ± 0.0008 and 0.1245 ± 0.0006, respectively), which closely match the bulk ¹⁸⁷Os/¹⁸⁸Os value of their host chromitite (0.1240 ± 0.0006). The unprecedented isotopic similarity between primary or secondary PGM assemblages and chromitite we report suggests that the osmium isotope budget of chromitite is largely controlled by the contained laurite and Os-rich alloy. This demonstrates that closed system behaviour of the Re–Os isotope system is possible, even during complex postmagmatic hydrothermal and/or metamorphic events. The preserved mantle Os-isotope signatures provide further support for an Enstatite Chondrite Reservoir (ECR) model for the convective upper mantle and are consistent with origin of the complex as a Caledonian ophiolite formed in a supra-subduction zone setting shortly before obduction.     

A secondary precious and base metal mineralization in chromitites linked to the development of a Paleozoic accretionary complex in Central Chile

Platinum-group element (PGE) and gold inclusions are usually present in peridotites and chromitite deposits associated with ophiolites. Here, we present the first detailed study of the mineralogy of precious metals in ultramafic rocks hosted in the Paleozoic Coastal Accretionary Complex of Central Chile. In these ultramafic rocks the mineralization of precious metals is associated with small meter-size pods and veins of massive chromitite hosted in serpentinite-filled shear zones. Crystallographic orientation maps of single chromite grains, obtained using the Electron-Backscattered Secondary Diffraction technique, allow us to identify two types of chromite in the precious-metal bearing chromitites: (1) Type A chromite, characterized by an average misorientation per grain of ≤ 2° and chemically homogeneous cores surrounded by a porous rim with abundant inclusions of chlorite, and (2) Type B chromite, which exhibits higher degrees of misorientation (2–8°) and porosity, and abundant silicate inclusions, but a relatively homogeneous chemical composition. In situ analyses using EMPA and LA-ICP-MS for major, minor and trace elements indicate that composition of the magmatic chromite is only preserved in the cores of Type A chromite grains. Core to rim chemical trends in these Type A chromites are characterized by a progressive increase of the Cr# with a decrease of the Mg#, loss of Al and addition of Fe^2 + in the porous rim. The observed changes in the microstructure and chemistry of chromite are associated with the infiltration of external fluids through shear zones filled with antigorite (± talc) developed in partly serpentinized peridotites (i.e., olivine–lizardite dunites). Thermodynamic calculations using the phase equilibria relations in the system Cr₂O₃–MgO–FeO–Al₂O₃–SiO₂–H₂O (CrMFASH) indicate that Fe^2 +-rich porous chromite + chlorite replaced the original assemblage chromite + olivine in the chromitite while prograde antigorite was formed. According to our results this transformation occurred at ~ 510–560 °C when external fluids penetrated the ultramafic/chromitite bodies through shear zones. These temperatures are slightly higher than estimated for the metamorphic peak in the host metapelitic rocks (i.e., ~ 420 °C at 9.3 kbar), suggesting that a hotter ultramafic body was captured by the metasediments of the accretionary prism during their exhumation through subduction channel. Chlorite geothermometry yielded a wide range of lower temperature from 430 to 188 °C, for chlorite present in the porous chromite rims. These results are in agreement with the retrograde overprint under greenchist-facies metamorphism conditions recorded by metapelitic host rocks and minor volcanogenic massive sulphide deposits in the area (300–400 °C, ~ 3–4 kbar). We suggest that although initially decoupled, the chromitite-bearing ultramafic rocks and their metasedimentary host undergone a common metamorphic PT pathway of exhumation during the formation and evolution of the subduction-related accretionary complex.The chromitites contain appreciable amounts of the platinum-group elements (up to 347 ppb total) and gold (up to 24 ppb), present as inclusions of platinum-group minerals (PGM) and alloys as well as native gold. The PGM identified include native osmium, laurite (RuS₂), irarsite (IrAsS), osarsite (OsAsS), omeiite (OsAs₂), Pt–Fe alloy (possibly isoferroplatinum) and a suite of inadequately identified phases such as PtSb (possibly stumpflite), PdHg (possibly potarite), RhS, Ir–Ni and Ir–Ni–Ru compounds. Only a few grains of osmium and laurite were identified in unaltered cores of chromite and therefore considered as magmatic in origin formed during the high-T event of chomite crystallisation in the upper mantle. The other PGM were located in the porous chromite associated with chlorite or base-metal minerals (BMM) that often fill the pores of this altered chromite or are intergrowth with antigorite in the host serpentinized ultramafic rock. The assemblage of BMM identified in the studied rocks include sulphides [millerite (NiS), polydymite (Ni₃S₄), violarite (FeNi₂S₄), galena (PbS), sphalerite (ZnS), chalcocite (CuS)], arsenides [(orcelite (Ni_5 − xAs₂) and maucherite (Ni₁₁As₈)], the sulpharsenide gersdorfitte (NiAsS), and native bismuth. The irregular shape of several PGM grains observed in porous chromite suggest disequilibrium, whereas others exhibit perfectly developed crystal faces with the associated secondary silicate or base-metal mineral suggesting neoformation of PGMs in situ from metamorphic fluids. We suggest that the origin of these PGM inclusions is magmatic, but some grains were reworked in situ when metalloid (i.e., As, Sb, Pb, Zn and Hg)-rich fluids released from metasediments penetrated the ultramafic rocks through active shear zones, once the ultramafic bodies became tectonically mixed with the host metasedimentary host rocks. During this event, gold sourced from the (meta)sediments was also precipitated within chromitites and serpentinites.     

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.     

Ore petrology of chromite-PGE mineralization in the Kempirsai ophiolite complex

Summary The platinum group minerals (PGM) in chromite ores of the Kempirsai ophiolite massif, located south of the Ural Mountains, are extremely varied in composition and represented predominantly by alloys, sulfides, arsenides, and sulfosalts of the iridium-group PGE (IPGE). The earlier Ir-Os-Ru alloys prevail over the later Cu-Os-Ru, Cu-Ir, Ni-Ir, Ni-Os-Ir-Ru, and Ni-Ru-Os-Fe alloys rich in base metals (BM). The earlier Ru-Os disulfides crystallize coevally with Ir-Os-Ru alloys, whereas the later sulfides are represented by compounds with a variable stoichiometry and a wide miscibility of Ni, Cu, Ir, Rh, Os, and Fe. Phase relations of PGE alloys with PGE-BM alloys, sulfides and sulfoarsenides confirm that deposition of these minerals was defined by a general evolution of PGE fractionation in the mineral-forming system but not by a super-imposed process. The leading mechanism of PGM crystallization is thought to be their dendritic growth during gas-transport reactions from low-density gaseous fluid enriched in PGE. The representative technological sampling of 0.5 million tons of an ore showed that the average PGE content in chromite ore is 0.71 ppm which leads to an evaluation of the PGE resources to be no less than 250 tons. Hence, the Kempirsai deposit is not only a giant chromium deposit, but also a giant deposit of IPGE: Ir, Ru, and Os. The size parameters of PGM and their aggregates suggests that the PGE may be recoverable in separate concentrates. Author’s address: Vadim Vadimovich Distler, Institute of Geology of Ore Deposits, Mineralogy, Petrography and Geochemistry Russian Academy of Sciences (IGEM RAS), Staromonetny 35, 119017 Moscow, Russia     

PGE mineralization in the late Archaean iron-rich mafic-ultramafic Hanumalapur Complex, Karnataka, India

Summary An unusually thick sulfur-poor mineralized zone enriched in platinum-group elements (PGE) is described in the Hanumalapur Complex, Shimoga District, Karnataka State, India. This promising occurrence was discovered in the early 1990s and the best samples at the time of writing have yielded Pt+Pd concentrations in excess of six ppm. The western part of the area concerned belongs to the late Archaean Dharwar Super Group (3000–2500 Ma), while the eastern part is occupied predominantly by a granite-gneiss terrain ∼3000 Ma in age. Ten mafic-ultramafic complexes which host interesting vanadium-bearing titanomagnetite occurrences are encountered in the western part, one of which is the Hanumalapur Complex. The PGE mineralized zone in this complex may be divided into four mineralogically distinctive types, which are, in descending order of PGE content: 1) a silicate-hosted Pd type, 2) a silicate-hosted Pt type, 3) a base-metal sulfide-hosted Pd type, and 4) an oxide-hosted PGE type. The genesis of the mineralization is somewhat unclear at this point of investigation, especially because of complete re-crystallization, but the evidence gathered so far suggests something different than a traditional orthomagmatic model requiring magma mixing processes and resulting in sulfide immiscibility. This is backed-up by the general lack of base metal sulfides in favor of chromite, although pure chlorite-amphibole and chlorite-albite-epidote-amphibole rocks may contain significant PGE concentrations regardless of the amount of chromite. The PGM textures show little evidence of hydrothermal alteration and remobilization, but the PGE mineralogy itself displays some characteristics of fluid action, as it seems that there are some OH-bearing Pt and Pd minerals present. The first author was Deceased Author’s address: R. J. Kaukonen, Department of Geosciences, University of Oulu, Oulu, P.O. Box 3000, FIN-90014 Finland