The activation energy values estimated by the Arrhenius equation as a controlling factor of platinum-group mineral formation

In ophiolite complexes and Ural/Alaskan-type intrusions the platinum-group element minerals (PGM) occur as laurite (RuS₂), erlichmanite (OsS₂), irarsite (IrAsS) and alloys (Os-Ir-Ru and Pt-Fe). They are commonly found as small inclusions (normally less than 10 μm, occasionally up to 100 μm) in chromite. The origin of coarse-grained PGM, in the form of 0.5-10 mm nuggets, in placer deposits related with mafic/ultramafic complexes remains still unclear. Literature data on grain size (r) of platinum-group minerals (PGM) and their formation temperature (range of temperatures between 700 and 1100 °C), revealed an Arrhenius temperature dependence. Correlation of the rate of crystal formation that depends on temperature (T) with the size (r) of the grain results in a linear relationship between ln(r) and 1/T. From the slope of the line n × ln(r) = −const. + E_act/RT the activation energy for the formation of IPGM (Ir-platinum-group minerals) was estimated, for the first time in the present study, to be approximately 450 ± 45 kJ mol⁻¹. Applying the Arrhenius equation, the corresponding formation temperature for extremely large IPGM grains (up to 1.3 mm) in chromite ores related to ophiolites was found to be approximately 740 °C. It seems to be consistent with a lower formation temperature than with the typical formation temperature of small PGM grains associated with ophiolitic chromitites. This suggests that coarse-grained PGM in mafic/ultramafic complexes, along the permeable shear zones, may have been re-crystallized during plastic deformation at relatively lower temperatures (700-800 °C), under appropriate pressure, temperature, redox conditions and an increased H₂O content. Thus, applying the plot of ln(r) versus 1/T on large Os-Ir-Ru-minerals (sulfides or alloys), characterized by an r value falling into the linear part of the graph and having evidence supporting their formation at relatively high temperatures, then the corresponding formation temperature of those IPGM can be found.     

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.     

Climatic control on clay mineral formation: Evidence from weathering profiles developed on either side of the Western Ghats

Many physico-chemical variables like rock-type, climate, topography and exposure age affect weathering environments. In the present study, an attempt is made to understand how the nature of clay minerals formed due to weathering differs in tropical regions receiving high and low rainfall. Clay mineralogy of weathering profiles in west coast of India, which receives about 3 m rainfall through two monsoons and those from the inland rain-shadow zones (<200 cm rainfall) are studied using X-ray diffraction technique. In the west coast, 1:1 clays (kaolinite) and Fe—Al oxides (gibbsite/goethite) are dominant clay minerals in the weathering profiles while 2:1 clay minerals are absent or found only in trace amounts. Weathering profiles in the rain shadow region have more complex clay mineralogy and are dominated by 2:1 clays and kaolinite. Fe—Al oxides are either less or absent in clay fraction. The kaolinite—smectite interstratified mineral in Banasandra profiles are formed due to transformation of smectites to kaolinite, which is indicative of a humid paleoclimate. In tropical regions receiving high rainfall the clay mineral assemblage remains the same irrespective of the parent rock type. Rainfall and availability of water apart from temperature, are the most important factors that determine kinetics of chemical weathering. Mineral alteration reactions proceed through different pathways in water rich and water poor environments.     

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     

Processes of the development of the molecular world at early stages of its formation: Evidence from the investigation of the behavior of the vibrational entropy of molecules

We analyzed the possibility of explaining empirical relations in the evolution of the molecular world on the basis of fundamental physical laws and theories of the behavior of the entropy of a system. Quantitative expressions were evaluated describing the entropy of internal motion of atoms in a molecular ensemble (vibrational entropy), which is a term of total entropy with a clear physical meaning. It was shown that vibrational entropy is controlled primarily by the structure of the compound rather than the number and identity of atoms in the molecule. During the early stages of evolution, the appearance of acyclic structures is more advantageous than that of cyclic structures. An increase in the complexity of the molecular world inevitably leads to the appearance of molecules with a complex skeleton formed mainly by bonds of the same elasticity as C–C. The necessity of helical structures, whose spatial elasticity is provided by hydrogen bonds, was explained.     

Diamond formation and source carbonation: mineral associations in diamonds from Namibia

Mineral inclusions in diamonds from Namibia document a range of mantle sources, including eclogitic, websteritic and peridotitic parageneses. Based on unusual textural features a group of inclusions showing websteritic, peridotitic and transitional chemical features is assigned to an 'undetermined suite' (12% of the studied diamonds). The mutual characteristic of this group is the occurrence of lamellar intergrowths of clinopyroxene and orthopyroxene. In addition, the 'undetermined suite' is associated with a number of uncommon phases: in one diamond MgCO₃ is enclosed by clinopyroxene. Other minerals that form touching inclusions with the pyroxene lamellae are (1) a SiO₂ phase observed in three diamonds, together with CaCO₃ in one of them, (2) phlogopite and a Cr-rich 'titanate' (probably lindsleyite). The inclusions document a metamorphic path of decreasing pressures and temperatures after entrapment in diamond. First, homogeneous low-Ca clinopyroxenes were entrapped at high temperatures. They subsequently exsolved orthopyroxene and probably also SiO₂ (coesite) on cooling along a P,T trajectory that did not allow garnet to be exsolved as well. Phlogopite, carbonates and LIMA phases are the result of overprint of a peridotitic source rock by a carbon-rich agent. The resulting unusual, olivine-free mineral association and the host diamonds are interpreted as products of extensive carbonation of the peridotite.     

Platinum-group element contents of chromites from mafic–ultramafic layered flows, Abitibi greenstone belt, Ontario: implications for geochemical fractionation and mineral exploration

Summary ?The PGE contents of chromite separated from peridotite layers of Archaean mafic–ultramafic flows, Abitibi belt (Canada), indicate enrichment in Os–Ir–Ru (600 ppb) relative to Pd–Au (<5 ppb). Evidently, chromite was a sink for Ir–Os–Ru during melt-chromite fractionation in each of the flows. However, an additional phase, probably olivine, is required to explain the bulk Ir content of the sulphide-poor peridotites. In contrast, the chromite Pt contents range from <10 ppb to 400 ppb, with large variation in Pt/Ru (0.02–2.76) and Pt/Pd (5–400) ratios. The Pt enrichment may be related to the presence of Pt spinel structure compounds in oxidised melt, reflecting Fe–Ti spinel-related mineralisation in higher pyroxenite-gabbro layers. Received December 5, 2002; revised version accepted January 7, 2003     

Manganese hydroxides in alluvium as an example of aquagene mineral formation

We found and studied the phosphate and ferromanganese mineralization in the Holocene alluvium at upper reaches of the Severnaya Dvina River. Possible sources and accumulation mechanisms of manganese during the aquagene-fluvial hydroxide formation are first discussed. The report at the XIII Geological Congress of the Komi Republic, January 26, 1999.     

Physicochemical formation parameters of hydrothermal mineral deposits: Evidence from fluid inclusions. II. Gold,silver, lead,and zink deposits

Information from a database, which was compiled and continuously updated by the authors of this paper and now includes information from 19500 publication on fluid and melt inclusions in minerals, is used to summarize results on the physicochemical formation parameters of hydrothermal Au, Ag, Pb, and Zn deposits. The database provides information on fluid inclusions in minerals from 970 Pb-Zn, 220 Au-Ag-Pb-Zn, and 825 Au-Ag deposits in various settings worldwide. Histograms for the homogenization temperatures of fluid inclusion are presented for the most typical minerals of the deposits. In sphalerite, most homogenization temperatures (1327 measurements) of fluid inclusions lie within the range of 50–200°C with a maximum at 100–200°C for this mineral from Pb-Zn deposits and within the range of 100–350°C (802 measurements) with a maximum at 200–300°C for this mineral from Au deposits. Data are presented on fluid pressures at Au (1495 measurements) and Pb-Zn (180 measurements) deposits. The pressure during the preore, ore-forming, and postore stages at these deposits ranged from 4–10 to 6000 bar. The reason for the high pressures during preore stages at the deposits is the relations of the fluids to acid magmatic and metamorphic processes. More than 70% of the fluid pressures values measured at Pb-Zn deposits lie within the range of 1–1500 bar. Au-Ag deposits are characterized by higher fluid pressures of 500–2000 bar (61% of the measurements). The overall ranges of the salinity and temperature of the mineral-forming fluid at Au-Ag (6778 measurements) and Pb-Zn (3395 measurements) deposits are 0.1–80 wt % equiv. NaCl and 20–800°C. Most measurements (～64%) for Au-Ag deposits yield fluid salinity <10 wt % equiv. NaCl and temperatures of 200–400°C (63%). Fluids at Pb-Zn deposits are typically more saline (10–25 wt % equiv. NaCl, 51% measurements) and lower temperature (100–300°C, 74% measurements). Several measurements of the fluid density fall within the range of 0.8–1.2 g/cm³. The average composition of volatile components of the fluids was evaluated by various techniques. The average composition of volatile components of fluid inclusions in minerals is calculated for hydrothermal W, Au, Ag, Sn, and Pb-Zn deposits, metamorphic rocks, and all geological objects. The Au, Ag, Pb, and Zn concentrations in magmatic melts and mineral-forming fluids is evaluated based on analyses of individual inclusions.     

Supra-subduction affinity in the Neoproterozoic serpentinites in the Eastern Desert, Egypt: Evidence from mineral composition

Serpentinites in the Eastern Desert (ED) of Egypt represent integral components of the ophiolites. Metamorphic textures of the serpentinites preserve the complex mineralogical evolution from primary peridotite through metamorphism, and late-stage hydrothermal alteration. Two textural types are distinguished in the olivines of the present serpentinized peridotites, namely (a) highly-strained olivine grains with kink bands, as in the deformed mantle tectonites from ophiolites, and (b) non-strained grains. The latter may represent recrystallized crystals during later thermal metamorphic events due to the intrusion of granite. On the basis of X-ray diffraction analysis, antigorite is the main serpentine minerals with lesser chrysotile and lizardite which indicates that serpentinites were formed under prograde metamorphism. Relict primary minerals of the serpentinites are Cr-spinel, olivine and pyroxene. Chrome spinel relicts have high Cr# (0.60–0.80), whereas primary olivines are Mg-rich nature (Fo = 89–96). Geochemical compositions of serpentinites indicate that they formed not at mid-ocean ridges but at spreading centers associated with subduction zones and this could have happened in a supra-subduction zone either in the fore-arc or back-arc environments. Mineral compositions of primary chrome spinels and olivines are similar to those of modern fore-arcs. High Cr# in the relict chrome spinels and Fo in the primary olivines of serpentinites indicate that they are residual after extensive partial melting and originated by sea-floor spreading during subduction initiation.     

阿尔金断裂剪切过程中定向生长锆石的发现及其意义—来自于显微构造和锆石内部矿物包裹体的证据

阿尔金断裂带中段出露一套走滑过程中形成的花岗质和角闪质糜棱岩。从糜棱岩中分选出3种类型的锆石:岩浆成因的长柱状锆石、柱状锆石和变质成因的次浑圆状锆石。这3种锆石的显微结构和构造特征以及它们内部的矿物包裹体均有所区别。其中长柱状锆石在岩石中定向排列,晶体长轴方向与拉伸线理方向一致,并且内部的所有矿物包裹体的长轴方向均与锆石的长轴方向平行,即与拉伸线理方向平行;拉曼研究表明包裹体矿物具熔融相特征;阴极发光图像中反映出这种锆石具有相对均一的内部结构。因此,该长柱状锆石是在韧性剪切过程中部分熔融环境下快速定向生长的,不仅代表了走滑剪切过程中的剪切应变方向,而且其生长年龄代表了走滑剪切的时代。     

Platinum-group element geochemistry of mafic rocks from the Dongchuan area,southwestern China

Mafic intrusions and dykes are well preserved in the Yinmin and Lanniping districts, located within the western margin of the Yangtze Block, SW China. Although these mafic rocks from the two areas formed during different periods, they share similar ranges of PGE concentration. Most of the Yinmin gabbroic dykes contain relatively high PGE concentrations (PGEs = 13.9–87.0 ppb) and low S contents (0.003 %–0.020 %), higher than the maximum PGE concentrations of mafic magmas melting from the mantle. Two exceptional Yinmin samples are characterized by relatively low PGE (PGEs = 0.31–0.37 ppb) and high S (0.114 %–0.257 %) contents. In contrast, most samples from the Lanniping gabbroic intrusion have low PGE concentrations (PGEs = 0.12–1.02 ppb) and high S contents (0.130 %–0.360 %), except that the three samples exhibit relatively high PGE (PGEs = 16.3–34.8 ppb) and low S concentrations (0.014 %–0.070 %). All the Yinmin and Lanniping samples are characterized by the enrichment of PPGE relative to IPGE in the primitive-mantle normalized diagrams, and the high-PGE samples exhibit obvious Ru anomalies. This study suggests that during the ascent of the parental magma, removal of Os–Ir–Ru alloys and/or chromite/spinel leads to high Pd/Ir ratios and Ru anomalies for the Yinmin high-PGE samples and relatively lower Pd/Ir ratios and Ru anomalies for the Lanniping low-PGE samples. We propose that the magmas parental to the Yinmin gabbroic dykes are initially S-unsaturated, and subsequently, minor evolved magma reached sulfur saturation and led to sulfide segregation. Although the Lanniping parental magmas are originally not saturated in S, the high Cu/Pd ratios (3.8 × 10⁴ to 3.2 × 10⁶) for most of the Lanniping samples indicate the S-saturated state and sulfide segregation. A calculation shows that the PGE-poor magmas might have experienced 0.01 %–0.1 % sulfide segregation in the magma chamber. Therefore, our study provides a possible opportunity to discover PGE-enriched sulfide mineralization somewhere near or within the Lanniping mafic intrusion.     

Boundaries of intergrowths between mineral individuals: A zone of secondary mineral formation in aggregates

Intergrowth boundaries between mineral individuals in dunite of the Gal’moenan massif in Koryakia was studied in terms of crystal morphology, crystal optics, and ontogenesis. The results obtained allowed us to trace the staged formation of olivine and chromite and four generations of these minerals. Micro-and nanotopography of boundary surfaces between intergrown mineral individuals of different generations was examined with optic, electron, and atomic force microscopes. The boundaries between mineral individuals of different generations are distinguished by their microsculpture for both olivine and chromite grains. Both minerals demonstrate a compositional trend toward refinement from older to younger generations. The decrease in the iron mole fraction in olivine and chromite is accompanied by the crystallization of magnetite along weakened zones in olivine of the first generation and as outer rims around the chromite grains of the second generation observable under optic and electronic microscopes. The subsequent refinement of chromite results in the release of PGE from its lattice, as established by atomic power microscopy. The newly formed PGM are localized at the boundaries between mineral individuals and, thus, mark a special stage in the ontogenetic evolution of mineral aggregates. Further recrystallization is expressed in the spatial redistribution of grain boundaries and the formation of monomineralic intergrowth boundaries, i.e., the glomerogranular structure of rock and substructures of PGM, chromite, and olivine grains as intermediate types of organization of the granular assemblies in the form of reticulate, chain, and cellular structures and substructures of aggregates.     

Parental media of natural diamonds and primary mineral inclusions in them: Evidence from physicochemical experiment

A generalized diagram was constructed for the compositions of multicomponent heterogeneous parental media for diamonds of kimberlite deposits on the basis of the mantle carbonatite concept of diamond genesis. The boundary compositions on the diagram of the parental medium are defined by the components of minerals of the peridotite and eclogite parageneses, mantle carbonatites, carbon, and the components of volatile compounds of the C-O-H system and accessory phases, both soluble (chlorides, phosphates, and others) and insoluble (sulfides and others) in carbonate-silicate melts. This corresponds to the compositions of minerals, melts, and volatile components from primary inclusions in natural diamonds, as well as experimental estimations of their phase relations. Growth media for most natural diamonds are dominated by completely miscible carbonate-silicate melts with dissolved elemental carbon. The boundary compositions for diamond formation (concentration barriers of diamond nucleation) in the cases of peridotite-carbonate and eclogite-carbonate melts correspond to 30 wt % peridotite and 35 wt % eclogite; i.e., they lie in the carbonatite concentration range. Phase relations were experimentally investigated at 7 GPa for the melting of the multicomponent heterogeneous system eclogite-carbonatite-sulfide-diamond with a composition close to the parental medium under the conditions of the eclogite paragenesis. As a result, “the diagram of syngenesis” was constructed for diamond, as well as paragenetic and xenogenic mineral phases. Curves of diamond solubility in completely miscible carbonate-silicate and sulfide melts and their relationships with the boundaries of the fields of carbonate-silicate and sulfide phases were determined. This allowed us to establish the physicochemical mechanism of natural diamond formation and the P-T conditions of formation of paragenetic silicate and carbonate minerals and coexistence of xenogenic sulfide minerals and melts. Physicochemical conditions of the capture of paragenetic and xenogenic phases by growing diamonds were revealed. Based on the mantle carbonatite concept of diamond genesis and experimental data, a genetic classification of primary inclusions in natural diamond was proposed. The phase diagrams of syngenesis of diamond, paragenetic, and xenogenic phases provide a basis for the analysis of the physicochemical history of diamond formation in carbonatite magma chambers and allow us to approach the formation of such chambers in the mantle material of the Earth.     

Platinum-group element alloy inclusions in chromites from Archaean mafic-ultramafic units: evidence from the Abitibi and the Agnew-Wiluna Greenstone Belts

Summary The paper investigates the role of primary magmatic phases in the fractionation and concentration of PGE in Archaean mafic and ultramafic systems. The composition of chromites and olivines in sulphur-poor (S<0.6wt%) komatiites from the Agnew-Wiluna Belt (Western Australia), and of chromite concentrated from komatiitic basalt, ferropicritic basalt and tholeiitic basalt from the Abitibi Belt (Canada) were analysed. The results of laser ablation ICP-MS analyses show that PGE-bearing alloys are not stable in crystallising komatiite and that ruthenium is soluble in chromite during crystallisation. Conversely, analyses of chromites separated from Theos Flow tholeiitic basalt indicate that Ir–Os–(±Pt) enrichments (>200ppb) reflect the presence of PGM. Chromites from Freds Flow komatiitic basalt contain Ir-rich clusters, whereas Pt enrichments (>370ppb) in Boston Creek ferropicritic basalt reflect the presence of Pt-rich compounds. The presence of PGE-bearing alloys in Theos Flow and Freds Flow is due to late S-supersaturation, whereas the presence of Pt-rich compounds in Boston Creek Flow reflects high state of melt oxidisation. The lack of PGE-bearing alloys in the olivines and chromites of komatiites can be explained by thermal instability of PGM, depletion in PGE at the mantle source, early S-supersaturation, the oxidisation conditions of the melt, or a combination of these factors.