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 the chromitites from the Great Serpentinite Belt,NSW, Australia

Summary Occurrences of platinum-group minerals (PGM) from chromitites of the Great Serpentinite Belt of New South Wales are reported for the first time in this study. On the basis of their major components, these minerals are classified into various groups, including sulphides, sulpharsenides, arsenides, antimonides, amalgams, and alloys of Os-Ir-Ru-(Fe Ni), Pd Cu Sn, Ni-Fe-Pt-Pd, Pd-Pb-Cu, and Rh-Sn-Cu. They are present: (i) as inclusions within chromite, (ii) in interstitial silicates, (iii) in ferritchromite and (iv) along fractures in chromite. Ir-subgroup (Ir, Os, Ru) minerals (IPGM) dominate podiform chromitites hosted by upper mantle serpentinised harzburgite, whereas Pdsubgroup (Pd, Pt, Rh) minerals (PPGM) characterise banded chromitites in cumulates of the overlying magmatic series. A highly brecciated podiform chromitite, however, is distinguished by abundant disseminated PPGM containing Sb ± Cu. Primary magmatic PGM in podiform chromitite comprise IPGM sulphides, sulpharsenides, and alloys, whereas hydrothermal PGM are characterised by PPGM alloys with Hg, Sb, and Cu. Dominantly hydrothermal PGM in the banded chromitites formed by remobilisation of primary magmatic PGM during serpentinisation. The contrast in PGM association is related to the crystallisation of the host chromitites; IPGM crystallised early from the parental magma along with podiform chromitite, but PPGM formed later at lower temperatures during crystallisation of banded chromitite.[

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Platingruppen-Minerale in den Chromititen aus dem Great Serpentinite Belt, NSW, Australien

Zusammenfassung In dieser Studie wird zum ersten Mal über das Vorkommen von PlatingruppenMineralen (PGM) in Chromititen der Great Serpentinite Belt berichtet. Die auftretenden Mineralphasen umfassen Sulfide, Sulfarsenide, Arsenide, Antimonide, Amalgam und Legierungen von Os-Ir-(Fe-Ni), Pd-Cu-Sn, Ni-Fe-Pt-Pd, Pd-Pb-Cu and Rh-Sn-Cu. Sie treten als i) Einschlüsse im Chromit, ii) in Silikaten der Grundmasse, iii) Im Ferritchromit und iv) in Frakturen des Chromit auf. Mineralphasen der Ir-Untergruppe (IPGM = Ir, Os, Ru) dominieren in podiformen Chromititen, die in serpentinisierten Harzburgiten des oberen Mantels auftreten. Minerale der Pd-Untergruppe (PPGM = Pd, Pt, Rh) charakterisieren gebänderte Chromitite, die innerhalb der über der Mantelsequenz liegenden Kumulatabfolge vorkommen. Ein deutlich brekzierter podiformer Chromitit unterscheidet sich von den übrigen podiformen Chromititen durch häufiges Auftreten von disseminierten PPGM, die auch Sb ± Cu führen. Primär magmatisch gebildete PGM in podiformen Chromititen umfassen IPGM in Form von Sulfide, Sulfarsenide und Legierungen, während PPGM als Legierungen mit Hg, Sb und Cu hydrothermale Phasen darstellen. Die hydrothermalen PGM in den gebänderten Chromititen wurden überwiegend durch Remobilisation aus primär magmatischen PGM während der Serpentinisierung gebildet. Der markante Unterschied in den während der Serpentinisierung gebildet. Der markante nterschied in den PGM-Assoziationen steht mit der Kristallisation des jeweiligen Chromitit in Verbindung: Während IPGM früh aus dem Magma zusammen mit den podiformen Chromititen kristallisierten, wurden PPGM später unter niedrigeren Temperaturen während der Kristallisation der gebänderten Chromitite gebildet.[

     

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 mineral formation: Evidence of an interchange process from the entropy of activation values

Small grains of Ru–Os–Ir sulfides or alloys that formed in the early stages of the crystallization of basaltic magmas occur as inclusions in chromitites from many ophiolite complexes, Ural/Alaskan-type and layered intrusions. The nature of platinum-group elements is debated, i.e., whether they originally occurred in a metallic state or bonded with sulfur or other ligands. The application of kinetics and suggestions regarding the mechanisms of PGE formation may contribute to a better understanding of the genetic processes for platinum-group mineral (PGM) formation. The aim of the present study is to investigate the type of mechanism (associative, dissociative or interchange) and the possibility of direct formation of PGM from the reaction of free metals with sulfur, defining also the structure of possible intermediate species.The literature on the grain sizes (r) of platinum-group minerals (PGM) and their formation temperatures (range between 700 and 1100 °C) reveals an Arrhenius temperature dependence. The activation energy was estimated to be 450 ± 45 kJ mol⁻¹. Applying the Eyring equation to the same data, a linear relationship between 2.5ln(r) + ln(T) versus 1/T was obtained, leading to an estimation of the free energy of activation, ΔG^≠ = 440 ± 43 kJ mol⁻¹. The thermodynamic relation ΔG^≠ = ΔH^≠ − TΔS^≠, used together with the relation ΔΗ^≠ = E_act − RT leads to the calculation of ΔS^≠ at various temperatures. The estimated entropy of activation at various temperatures being almost zero, we suggest an interchange mechanism for PGM formation.The possibility of PGM formation from the direct reaction of free metals with sulfur would be inconsistent with the estimated entropy of activation values (ΔS^≠  0) at various temperatures. In the cases of PGMs of known r, the formation temperatures can be estimated, and then the free energy of activation obtained, applying 2.5ln(r) + ln(T) versus 1/T (straight line). From that value, the entropy of activation can be calculated [ΔS^≠ = −R + (E_act − ΔG^≠)/T], and an interchange mechanism is proposed. Furthermore, applying the relation of 2.5ln(r) + ln(T) versus 1/T on PGM grains of known r and T, an interchange mechanism for their formation can be suggested if they fit the above line.     

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.     

Geodynamic implications of ophiolitic chromitites in the La Cabaña ultramafic bodies,Central Chile

Chromitites (>80% volume chromite) hosted in two ultramafic bodies (Lavanderos and Centinela Bajo) from the Palaeozoic metamorphic basement of the Chilean Coastal Cordillera were studied in terms of their chromite composition, platinum-group element (PGE) abundances, and Re-Os isotopic systematics. Primary chromite (Cr# = 0.64–0.66; Mg# = 48.71–51.81) is only preserved in some massive chromitites from the Centinela Bajo ultramafic body. This chemical fingerprint is similar to other high-Cr chromitites from ophiolite complexes, suggesting that they crystallized from arc-type melt similar to high-Mg island-arc tholeiites (IAT) and boninites in supra-subduction mantle. The chromitites display enrichment in IPGE (Os, Ir, Ru) over PPGE (Rh, Pt, Pd), with PGE concentrations between 180 and 347 ppb, as is typical of chromitites hosted in the mantle of supra-subduction zone (SSZ) ophiolites. Laurite (RuS₂)-erlichmanite (OsS₂) phases are the most abundant inclusions of platinum-group minerals (PGM) in chromite, indicating crystallization from S-undersaturated melts in the sub-arc mantle. The metamorphism associated with the emplacement of the ultramafic bodies in the La Cabaña has been determined to be ca. 300 Ma, based on K-Ar dating of fuchsite. Initial ¹⁸⁷Os/¹⁸⁸Os ratios for four chromitite samples, calculated for this age, range from 0.1248 to 0.1271. These isotopic compositions are well within the range of chromitites hosted in the mantle section of other Phanaerozoic ophiolites. Collectively, these mineralogical and geochemical features are interpreted in terms of chromite crystallization in dunite channels beneath a spreading centre that opened a marginal basin above a supra-subduction zone. This implies that chromitite-bearing serpentinites in the metamorphic basement of the Coastal Cordillera are of oceanic-mantle origin and not oceanic crust as previously suggested. We suggest that old subcontinental mantle underlying the hypothetical Chilenia micro-continent was unroofed and later altered during the opening of the marginal basin. This defined the compositional and structural framework in which the protoliths of the meta-igneous and meta-sedimentary rocks of the Eastern and Western Series of the Chilean Coastal Cordillera basement were formed.     

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.     

Laser depth profiling studies of helium diffusion in Durango fluorapatite

Ultraviolet lasers coupled with sensitive mass spectrometers provide a useful way to measure laboratory-induced noble gas diffusion profiles in minerals, thus enabling the calculation of diffusion parameters. We illustrate this laser ablation depth profiling (LADP) technique for a previously well-studied mineral-isotopic system: ⁴He in Durango fluorapatite. LADP studies were conducted on oriented, polished slabs from a single crystal that were heated under vacuum to a variety of temperatures between 300 and 450 °C for variable times. The resolved ⁴He profiles exhibited error-function loss as predicted by previous bulk ⁴He diffusion studies. All of the slabs, regardless of crystallographic orientation, yielded modeled diffusivities that are statistically co-linear on an Arrhenius diagram, suggesting no diffusional anisotropy of ⁴He in this material. The data indicate an activation energy of 142.2 ± 5.0 (2σ) kJ/mol and diffusivity at infinite temperature - reported as ln(D₀) - of −4.71 ± 0.94 (2σ) m²/s. These values imply a bulk closure temperature for ⁴He in Durango fluorapatite of 74 °C for a 50 μm radius grain, infinite cylinder geometry, and a cooling rate of 10 °C/Myr.     

The first occurrence of platinum group minerals (PGM) in a chromite deposit in the Eastern Desert, Egypt

 The platinum-group mineralogy (PGM) of the chromitite from Gebel Lawi, in the southeastern desert has been investigated. The most abundant base metal sulfides (BMS) associated with the Lawi chromite are pentlandite, millerite and heazlewoodite. The major platinum-group minerals identified were as follows: laurite (IrOsRu)S2, osmian iridium (OsIr), hollingworthite (RhAsS), tellurian arsenopalladinite (PdTeSbAs), potarite (PdHg) besides cuprian palladian gold (CuPdAu), a Pd-Sb-Hg and HgTe phases. Laurite and osmian iridium occur preferentially in chromite. Os-Ir commonly forms composite PGM with laurite. Hollingworthite and tellurian arsenopalladinite are included within serpentine and, close to the base-metal sulfides, the cuprian palladian gold shares boundaries with chromite. Potarite together with the Pd-Sb-Hg and HgTe phases are embedded in serpentine. Palladium is the most abundant PGE in the Gebel Lawi chromite. A paragenetic sequence of PGM formation is described. Textural evidence indicates that Os-, Ir- and Ru-bearing PGM formed early and were followed by Rh- and Pd-bearing PGM. The concentration of all five PGE could be magmatic, but much of the PGE mineralogy except for laurite and osmian iridium in the center of chromite grains, has been modified by subsequent processes. At later stages, the environment became Te-, Sb-, As- and Hg-rich, which finally led to the formation of low-temperature alteration minerals. Received: 24 April 1995 / Accepted: 28 March 1996     

Dissolution kinetics of diopside as a function of solution saturation state: Macroscopic measurements and implications for modeling of geological storage of CO2

Measurements of the dissolution rate of diopside (r) were carried out as a function of the Gibbs free energy of the dissolution reaction (ΔG_r) in a continuously stirred flow-through reactor at 90 °C and pH_90 °C = 5.05. The overall relation between r and ΔG_r was determined over a free energy range of −130.9 < ΔG_r < −47.0 kJ mo1⁻¹. The data define a highly non-linear, sigmoidal relation between r and ΔG_r. At far-from-equilibrium conditions (ΔG_r ? −76.2 kJ mo1⁻¹), a rate plateau is observed. In this free energy range, the rates of dissolution are constant, independent of [Ca], [Mg] and [Si] concentrations, and independent of ΔG_r. A sharp decrease of the dissolution rate (∼1 order of magnitude) occurs in the transition ΔG_r region defined by −76.2 < ΔG_r ? −61.5 kJ mo1⁻¹. Dissolution closer to equilibrium (ΔG_r > −61.5 kJ mo1⁻¹) is characterised by a much weaker inverse dependence of the rates on ΔG_r. Modeling the experimental r-ΔG_r data with a simple classical transition state theory (TST) law as implemented in most available geochemical codes is found inappropriate. An evaluation of the consequences of the use of geochemical codes where the r-ΔG_r relation is based on basic TST was carried out and applied to carbonation reactions of diopside, which, among other reactions with Ca- and Mg-bearing minerals, are considered as a promising process for the solid state sequestration of CO₂ over long time spans. In order to take into account the actual experimental r-ΔG_r relation in the geochemical code that we used, a new module has been developed. It reveals a dramatic overestimation of the carbonation rate when using a TST-based geochemical code. This points out that simulations of water-rock-CO₂ interactions performed with classical geochemical codes should be evaluated with great caution.     

Seawater temperature proxies based on DSr, DMg, and DU from culture experiments using the branching coral Porites cylindrica

In order to investigate the incorporation of Sr, Mg, and U into coral skeletons and its temperature dependency, we performed a culture experiment in which specimens of the branching coral (Porites cylindrica) were grown for 1 month at three seawater temperatures (22, 26, and 30 °C). The results of this study showed that the linear extension rate of P. cylindrica has little effect on the skeletal Sr/Ca, Mg/Ca, and U/Ca ratios. The following temperature equations were derived: Sr/Ca (mmol/mol) = 10.214(±0.229) − 0.0642(±0.00897) × T (°C) (r² = 0.59, p < 0.05); Mg/Ca (mmol/mol) = 1.973(±0.302) + 0.1002(±0.0118) × T (°C) (r² = 0.67, p < 0.05); and U/Ca (μmol/mol) = 1.488(±0.0484) − 0.0212(±0.00189) × T (°C) (r² = 0.78, p < 0.05). We calculated the distribution coefficient (D) of Sr, Mg, and U relative to seawater temperature and compared the results with previous data from massive Porites corals. The seawater temperature proxies based on D calibrations of P. cylindrica established in this study are generally similar to those for massive Porites corals, despite a difference in the slope of D_U calibration. The calibration sensitivity of D_Sr, D_Mg, and D_U to seawater temperature change during the experiment was 0.64%/°C, 1.93%/°C, and 1.97%/°C, respectively. These results suggest that the skeletal Sr/Ca ratio (and possibly the Mg/Ca and/or U/Ca ratio) of the branching coral P. cylindrica can be used as a potential paleothermometer.     

Platinum and palladium mobility in supergene environment: The residual origin of the Pirogues River mineralization, New Caledonia

Eluvial concentration of platinum-group minerals (PGM) has developed in the south of New Caledonia, from the weathering of a mafic and ultramafic cumulate. The platinum/palladium (Pt/Pd) ratio evolution from the bottom to the top of the weathering profile indicates a chemical mobilization of Pd in supergene environment. The examination by scanning electron microscopy of the residual PGM collected in the weathering profile and their chemical characterization by electronic microprobe show a preservation of the structure and chemical signature (in the core of the grains) of the fresh PGM. This clearly demonstrates that the PGM studied here are residual and are affected by dissolution process.     

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.     

A greenstone belt in southeast Tibet: An accreted middle–late Permian oceanic plateau

Studies of accreted oceanic plateau sections provide crucial information on their structures, compositions, and origins. We investigate the petrogenesis of ultramafic–mafic rocks in the Tangjia–Sumdo greenstone belt of southeast Tibet using petrography, whole-rock geochemistry, and U-Pb zircon geochronology. These rocks are divided into four groups based on geochemical characteristics that include depleted and tholeiitic mafic rocks, transitional mafic rocks, enriched and alkaline mafic rocks, and picritic ultramafic rocks. Depleted and tholeiitic mafic rocks have the oldest crystallization ages (～272 Ma), followed by picritic ultramafic rocks (～270 Ma), transitional mafic rocks (267–254 Ma), and enriched and alkaline mafic rocks (252–250 Ma). Hafnium and neodymium isotope ratios of depleted and tholeiitic mafic rocks (ε_Hf(t) = +13.1–+16.9; ε_Nd(t) = +6.9–+7.1), transitional mafic rocks (ε_Hf(t) = +1.8–+16.9; ε_Nd(t) = +0.8–+5.5), enriched and alkaline mafic rocks (ε_Hf(t) = +0.5–+5.4; ε_Nd(t) = ?1.5 to +1.9) and picritic ultramafic rocks (ε_Hf(t) = +14.9–+17.2; ε_Nd(t) = +7.8–+9.0) are similar to those of N-MORB, E-MORB, OIB and depleted-type picritic mafic rocks in other oceanic plateaus, respectively. The geochemical characteristics of the depleted and tholeiitic mafic rocks suggest that they formed by partial melting of depleted spinel lherzolite in a mid-ocean ridge setting, whereas the picritic ultramafic rocks suggest a high degree of partial melting of depleted lherzolite in a hot mantle plume head. The transitional mafic rocks formed by partial melting of moderately enriched garnet lherzolite. The youngest rocks (enriched and alkaline mafic rocks) formed by partial melting of a more enriched garnet lherzolite (compared to transitional mafic rocks) at relatively low temperatures. We propose that the depleted and tholeiitic mafic rocks represent normal oceanic crust of the Sumdo Paleo-Tethys Ocean and the transitional mafic rocks, enriched and alkaline mafic rocks and picritic ultramafic rocks are the fragments of the oceanic plateau, which were related to middle–late Permian mantle plume activity in the Sumdo Paleo-Tethys Ocean. We further suggest that the majority of the Tangjia–Sumdo greenstone belt represents a middle–late Permian oceanic plateau that reflects a previously unrecognized middle–late Permian mantle plume.     

Diffusion of Ar in muscovite

Hydrothermal treatment of closely sized muscovite aggregates in a piston-cylinder apparatus induced ⁴⁰Ar^∗ loss that is revealed in ⁴⁰Ar/³⁹Ar step heating spectra. Age spectra and Arrhenius data, however, differ from that expected from a single diffusion length scale. A numerical model of episodic loss assuming the presence of multiple diffusion domains yields excellent fits between synthetic and actual degassing spectra. We used this model to isolate ⁴⁰Ar^∗ loss from the grains that remained intact during hydrothermal treatment at 10 kbar permitting calculation of diffusion coefficients in the temperature range 730-600 °C. Diffusion data generated in this manner yield an activation energy (E) of 63 ± 7 kcal/mol and frequency factor (D_o) of 2.3  cm²/s. Experiments at 20 kbar yield diffusivities lower by about an order of magnitude and correspond to an activation volume of ∼14 cm³/mol. Together, these parameters predict substantially greater retentivity of Ar in muscovite than previously assumed and correspond to a closure temperature (T_c) of 425 °C for a 100 μm radius grain cooling at 10 °C/Ma at 10 kbar (T_c = 405 °C at 5 kbar. Age and log (r/r_o) spectra for the run products show strong correlations indicating that muscovites can retain Ar diffusion boundaries and mechanisms that define their natural retentivity during vacuum step heating. This may permit the application of high resolution, continuous ⁴⁰Ar/³⁹Ar thermochronology to low grade, regionally metamorphosed terranes.     

Solubility of cyclooctasulfur in pure water and sea water at different temperatures

The solubility of cyclooctasulfur in water and sea water at various temperatures in the range between 4 and 80 °C was determined. Cyclooctasulfur in equilibrium with rhombic sulfur reacted with hot acidic aqueous potassium cyanide to form thiocyanate anion which was measured by anion chromatography. Sulfur solubility in pure water was found to increase with temperature by more than 78 times: from 6.1 nM S₈ at 4 °C to 478 nM S₈ at 80 °C. The following thermodynamic values for solubilisation of S₈ in water were calculated from the experimental data: K° = 3.01 ± 1.04 × 10⁻⁸, ΔG_r° = 42.93 ± 0.73 kJ mol⁻¹, ΔH_r° = 47.4 ± 3.6 kJmol⁻¹, ΔS_r° = 15.0 ± 11.7 J mol⁻¹ K⁻¹). Solubility of cyclooctasulfur in sea water was found to be 61 ± 13% of the solubility in pure water regardless of the temperature.     

Chemical composition of platinum-group minerals from the Bor-Uryakh massif (Maimecha-Kotui Province,Russia)

This contribution firstly presents particularities of mineral chemistry of platinum-group elements (PGE) mineralization from placer deposits linked to the Bor-Uryakh massif of the Maimecha-Kotui Province, northern part of the Siberian Craton. The chemical composition of PGE mineralization has been studied by electron microprobe analysis. At Bor-Uryakh, main platinum-group minerals (PGM) comprise Os-Ir and Pt-Fe alloys represented by individual crystals, and polyphase PGM assemblages. The majority (e.g., 12 out of 19) of the Os-rich nuggets are iridian osmium, with subordinate amounts of native osmium (Os) and chengdeite (Ir₃Fe). Pt-Fe alloys have a stoichiometric composition close to Pt₂Fe. According to the nomen-clature by L. Cabri and C. Feather [1975] these minerals correspond to ferroan platinum. Based on geological position and geochemical features of investigated PGE mineralization the particular rock sources have been established. This study has demonstrated the similarity of chemical characteristics of Os-Ir and Pt-Fe alloys of the Bor-Uryakh massif to those of PGM from the Guli massif (Maimecha-Kotui Province), platiniferous zoned-type ultramafic massifs (e.g., Kondyor, Inagli and Chad) of the Aldan Province and Platinum belt of the Urals (Nizhny Tagil, Kytlym, etc.).     

The influence of artificial radiation damage and thermal annealing on helium diffusion kinetics in apatite

Recent work [Shuster D. L., Flowers R. M. and Farley K. A. (2006) The influence of natural radiation damage on helium diffusion kinetics in apatite. Earth Planet. Sci. Lett.249(3-4), 148-161] revealing a correlation between radiogenic ⁴He concentration and He diffusivity in natural apatites suggests that helium migration is retarded by radiation-induced damage to the crystal structure. If so, the He diffusion kinetics of an apatite is an evolving function of time and the effective uranium concentration in a cooling sample, a fact which must be considered when interpreting apatite (U-Th)/He ages. Here we report the results of experiments designed to investigate and quantify this phenomenon by determining He diffusivities in apatites after systematically adding or removing radiation damage.Radiation damage was added to a suite of synthetic and natural apatites by exposure to between 1 and 100 h of neutron irradiation in a nuclear reactor. The samples were then irradiated with a 220 MeV proton beam and the resulting spallogenic ³He used as a diffusant in step-heating diffusion experiments. In every sample, irradiation increased the activation energy (E_a) and the frequency factor (D_o/a²) of diffusion and yielded a higher He closure temperature (T_c) than the starting material. For example, 100 h in the reactor caused the He closure temperature to increase by as much as 36 °C. For a given neutron fluence the magnitude of increase in closure temperature scales negatively with the initial closure temperature. This is consistent with a logarithmic response in which the neutron damage is additive to the initial damage present. In detail, the irradiations introduce correlated increases in E_a and ln(D_o/a²) that lie on the same array as found in natural apatites. This strongly suggests that neutron-induced damage mimics the damage produced by U and Th decay in natural apatites.To investigate the potential consequences of annealing of radiation damage, samples of Durango apatite were heated in vacuum to temperatures up to 550 °C for between 1 and 350 h. After this treatment the samples were step-heated using the remaining natural ⁴He as the diffusant. At temperatures above 290 °C a systematic change in T_c was observed, with values becoming lower with increasing temperature and time. For example, reduction of T_c from the starting value of 71 to ∼52 °C occurred in 1 h at 375 °C or 10 h at 330 °C. The observed variations in T_c are strongly correlated with the fission track length reduction predicted from the initial holding time and temperature. Furthermore, like the neutron irradiated apatites, these samples plot on the same E_a − ln(D_o/a²) array as natural samples, suggesting that damage annealing is simply undoing the consequences of damage accumulation in terms of He diffusivity.Taken together these data provide unequivocal evidence that at these levels, radiation damage acts to retard He diffusion in apatite, and that thermal annealing reverses the process. The data provide support for the previously described radiation damage trapping kinetic model of Shuster et al. (2006) and can be used to define a model which fully accommodates damage production and annealing.     

Ruthenium in komatiitic chromite

The distinction between Ru in solid solution and Ru-bearing inclusions is essential for the predictive modeling of platinum-group element (PGE) geochemistry in applications such as the lithogeochemical exploration for magmatic sulfide deposits in komatiites. This study investigates the role of chromite in the fractionation of Ru in ultramafic melts by analyzing chromite grains from sulfide-undersaturated komatiites and a komatiitic basalt from the Yilgarn Craton in Western Australia. In situ analysis using laser ablation ICP-MS yields uniform Ru concentrations in chromites both within-grain and on a sample scale, with concentrations between 220 and 540 ppb. All other platinum-group elements are below the detection limit of the laser ablation ICP-MS analysis. Carius tube digestion isotope dilution ICP-MS analysis of chromite concentrates confirms the accuracy of the in-situ method. Time resolved laser ablation ICP-MS analyses have identified the presence of sub-micron Ir-bearing inclusions in some chromite grains from the komatiitic basalt. However, Ru-bearing inclusions have not been recognized in the analyzed chromites and this combined with the in situ data suggests that Ru exists in solid solution in the crystal lattice of chromite. These results show that chromite can control the fractionation and concentration of Ru in ultramafic systems.     

Argon diffusion in plagioclase and implications for thermochronometry: A case study from the Bushveld Complex, South Africa

Plagioclase is not only the most abundant mineral in the Earth’s crust, but is present in almost all terrestrial tectonic settings and is widespread in most extraterrestrial material. Applying the K-Ar system to this common mineral would provide a powerful tool for quantifying thermal histories in a wide variety of settings. Nonetheless, plagioclase has rarely been used for thermochronometry, largely due to difficulties in simultaneously acquiring precise geochronologic data and quantifying argon diffusion kinetics from a mineral with low-K concentration. Here we describe an analytical technique that generates high-precision ⁴⁰Ar/³⁹Ar data and quantifies Ar diffusion kinetics of low-K minerals. We present results of five diffusion experiments conducted on single crystals of plagioclase from the Bushveld Complex, South Africa. The observed diffusion kinetics yield internally consistent thermochronological constraints, indicating that plagioclase is a reliable thermochronometer. Individual grains have activation energies of 155-178 kJ/mol and ln(D₀/a²) varies between 3.5 and 6.5. These diffusion parameters correspond to closure temperatures of 225-300 °C, for a 10 °C/Ma cooling rate. Age spectra generally conform to single-domain diffusive loss profiles, suggesting that grain-scale diffusion dominates argon transport in this fairly simple plagioclase. Conjointly examining several single-grain analyses enables us to distinguish episodic reheating from slow cooling and indicates that the Bushveld Complex cooled rapidly and monotonically from magmatic temperature to <300 °C over 3 Ma, followed by protracted cooling to ambient crustal temperatures of 150-200 °C over ∼600 Ma.