The effect of Cl on Pt solubility in haplobasaltic melt: Implications for micronugget formation and evidence for fluid transport of PGEs

Platinum solubility was determined in a haplobasaltic, diopside-anorthite melt at 1523 K and 0.2 GPa as a function of oxygen fugacity and chlorine content. Synthetic glass powder of an An₄₂Di₅₈ composition was sealed in a platinum or platinum-iridium alloy capsule and equilibrated with a solid CaCl₂ and MgCl₂ chlorine source, water and the noble-metal capsule. All experiments were run in an internally-heated pressure-vessel equipped with a rapid-quench device with oxygen fugacity controlled by the water content and intrinsic hydrogen fugacity of the autoclave (MnO-Mn₃O₄). Resultant glasses were analyzed by isotope dilution ICP-MS and LA-ICP-MS to determine the solubility and distribution of Pt and assess potential Cl-complexation of Pt in the melt.Experiments with run durations longer than 96 h show Pt solubilities consistent with solubilities determined for the equivalent Cl-free diopside-anorthite system, under the same P-T conditions. These results indicate that chlorine has no discernable effect on Pt solubility and there is no evidence of Pt-Cl complexing in the silicate melt from 0.6 to 2.75 wt% Cl (saturation).However, products from short run duration experiments (<96 h) contain Pt concentrations which are orders of magnitude higher than those of the Pt-free starting glass and of the experimental products of the longer run duration experiments. These anomalously high levels are most pronounced in the shortest experiments and Pt concentration decreases with increasing run duration. It is suggested that this excess platinum is dissolved within the Cl-bearing fluid during the heating stages of the experiment and is left behind as the fluid dissolves into the melt leaving small amounts of Pt as “micronuggets”, increasing the bulk Pt concentration. With increasing run duration the platinum appears to migrate out of the melt, back to the capsule walls, decreasing the amount of Pt contained within the glass. This behavior offers compelling evidence that Cl-bearing fluids have the capacity to transport significant amounts of Pt under magmatic conditions.Mass balance calculations on the excess amount of Pt in the glass (above inherent solubility) in short duration experiments lead to an estimation of Pt concentration in the Cl-bearing fluid ranging from tens to a few hundred ppm, versus ppb levels in the melt. The correspondingly high estimated apparent partition coefficients of 10³-10⁴ suggest that Cl-bearing fluids can be highly efficient at enriching and transporting platinum in mafic magmatic-hydrothermal ore-forming systems. These values strongly contrast with recent experimental results in felsic systems, highlighting the potential importance of melt composition on partitioning, the need for composition specific partitioning experiments, as well as a detailed understanding of Pt distribution in experimental products.     

Oxygen fugacity control in piston-cylinder experiments

The main goal of this study was to develop and test a capsule assembly for use in piston-cylinder experiments where oxygen fugacity could be controlled in the vicinity of the QFM buffer without H₂O loss or carbon contamination of the sample material. The assembly consists of an outer Pt-capsule containing a solid buffer (Ni–NiO or Co–CoO) plus H₂O and an inner AuPd-capsule, containing the sample, H₂O and a Pt-wire. No H₂O loss is observed from the sample, even after 48 h, but a slight increase in H₂O content is found in longer runs due to oxygen and hydrogen diffusion into the AuPd-capsule. Oxygen fugacity of runs in equilibrium with the Ni–NiO (NNO) and Co–CoO (CoCO) buffers was measured by analyzing Fe dissolved in the Pt-wire and in the AuPd-capsule. The second method gives values that are in good agreement with established buffer values, whereas results from the first method are one half to one log units higher than the established values.     

Experimental study of platinum solubility in silicate melt to 14 GPa and 2273 K: Implications for accretion and core formation in Earth

We determined the solubility limit of Pt in molten haplo-basalt (1 atm anorthite-diopside eutectic composition) in piston-cylinder and multi-anvil experiments at pressures between 0.5 and 14 GPa and temperatures from 1698 to 2223 K. Experiments were internally buffered at ∼IW + 1. Pt concentrations in quenched-glass samples were measured by laser-ablation inductively coupled-plasma mass spectrometry (LA-ICPMS). This technique allows detection of small-scale heterogeneities in the run products while supplying three-dimensional information about the distribution of Pt in the glass samples. Analytical variations in ¹⁹⁵Pt indicate that all experiments contain Pt nanonuggets after quenching. Averages of multiple, time-integrated spot analyses (corresponding to bulk analyses) typically have large standard deviations, and calculated Pt solubilities in silicate melt exhibit no statistically significant covariance with temperature or pressure. In contrast, averages of minimum ¹⁹⁵Pt signal levels show less inter-spot variation, and solubility shows significant covariance with pressure and temperature. We interpret these results to mean that nanonuggets are not quench particles, that is, they were not dissolved in the silicate melt, but were part of the equilibrium metal assemblage at run conditions. We assume that the average of minimum measured Pt abundances in multiple probe spots is representative of the actual solubility. The metal/silicate partition coefficients (D^met/sil) is the inverse of solubility, and we parameterize D^met/sil in the data set by multivariate regression. The statistically robust regression shows that increasing both pressure and temperature causes D^met/silto decrease, that is, Pt becomes more soluble in silicate melt. D^met/sil decreases by less than an order of magnitude at constant temperature from 1 to 14 GPa, whereas isobaric increase in temperature produces a more dramatic effect, with D^met/sil decreasing by more than one order of magnitude between 1623 and 2223 K. The Pt abundance in the Earth’s mantle requires that D^met/sil is ∼1000 assuming core-mantle equilibration. Geochemical models for core formation in Earth based on moderately and slightly siderophile elements are generally consistent with equilibrium metal segregation at conditions generally in the range of 20-60 GPa and 2000-4000 K. Model extrapolations to these conditions show that the Pt abundance of the mantle can only be matched if oxygen fugacity is high (∼IW) and if Pt mixes ideally in molten iron, both very unlikely conditions. For more realistic values of oxygen fugacity (∼IW − 2) and experimentally-based constraints on non-ideal mixing, models show that D^met/sil would be several orders of magnitude too high even at the most favorable conditions of pressure and temperature. These results suggest that the mantle Pt budget, and by implication other highly siderophile elements, was added by late addition of a ‘late veneer’ phase to the accreting proto-Earth.     

Crystal chemistry of ferric iron in (Mg,Fe)(Si,Al)O<Subscript>3</Subscript> majorite with implications for the transition zone

Fifteen samples of (Mg,Fe)SiO₃ majorite with varying Fe/Mg composition and one sample of (Mg,Fe)(Si,Al)O₃ majorite were synthesized at high pressure and temperature under different conditions of oxygen fugacity using a multianvil press, and examined ex situ using X-ray diffraction and Mössbauer and optical absorption spectroscopy. The relative concentration of Fe³⁺ increases both with total iron content and increasing oxygen fugacity, but not with Al concentration. Optical absorption spectra indicate the presence of Fe²⁺–Fe³⁺ charge transfer, where band intensity increases with increasing Fe³⁺ concentration. Mössbauer data were used in conjunction with electron microprobe analyses to determine the site distribution of all cations. Both Al and Fe³⁺ substitute on the octahedral site, and charge balance occurs through the removal of Si. The degree of Mg/Si ordering on the octahedral sites in (Mg,Fe)SiO₃ majorite, which affects both the c/a ratio and the unit cell volume, is influenced by the thermal history of the sample. The Fe³⁺ concentration of (Mg,Fe)(Si,Al)O₃ majorite in the mantle will reflect prevailing redox conditions, which are believed to be relatively reducing in the transition zone. Exchange of material across the transition boundary to (Mg,Fe) (Si,Al)O₃ perovskite would then require a mechanism to oxidize sufficient iron to satisfy crystal-chemical requirements of the lower-mantle perovskite phase.     

云南因民铁铜矿区辉长岩类中黑云母-金红石化特征及其指示意义

对云南因民铁铜矿区深部辉长岩类中金红石、黑云母、碳酸盐和绿泥石的矿物地球化学特征进行研究,以探讨赋存于辉长岩类中的铁氧化物铜金型矿(化)体的成岩成矿环境。金红石由岩浆结晶和多期蚀变作用形成,其结晶温度为820~1 082 ℃,多期蚀变温度为444~730 ℃,金红石与黑云母密切共生;黑云母可划分为原生高钛镁质黑云母、热液蚀变镁质黑云母和铁质黑云母,形成温度分别为653~750 ℃、525~619 ℃和551~577 ℃,氧逸度均位于Ni NiO缓冲剂附近,表明黑云母形成于高温强氧化环境,有利于金红石化;铁白云石-菱铁矿化揭示了强还原环境,交代蚀变金红石;绿泥石多由铁镁矿物蚀变形成,形成于中低温(174~243 ℃)、低氧逸度(-4468~-5142)和高硫逸度(-1442~-1976)的强还原环境,有利于金属硫化物形成。本区岩浆结晶演化和黑云母-金红石化蚀变具有高温强氧化地球化学岩相学特征,有利于钛、铁矿化,后期叠加中低温强还原地球化学岩相,为IOCG矿床成矿的有利地球化学岩相学类型。     

Partitioning of Cu, Ni, Au, and platinum-group elements between monosulfide solid solution and sulfide melt under controlled oxygen and sulfur fugacities

We have performed six experiments in which we equilibrated monosulfide solid solution (mss) with sulfide melt in evacuated silica capsules containing solid buffers to fix oxygen and sulfur fugacity, at temperatures of 950°C, 1000°C and 1050°C at bulk concentrations of ∼50 ppm for each of the PGE and Au, 5% Ni, and 7% Cu. Concentrations of O, S, Fe, Ni and Cu were determined by electron microprobe, whereas precious metal concentrations were determined by laser-ablation inductively-coupled mass spectrometry. Partition coefficients of all elements studied show minimal dependences on oxygen fugacity from the IW to the QFM buffers when sulfur fugacity is fixed at the Pt-PtS buffer. Cu, Pt, Pd and Au are strongly incompatible and Ru remains moderately to strongly compatible under all conditions studied. At all oxygen fugacities, at the Pt-PtS sulfur buffer, Ir and Rh remain highly compatible in mss. In the single run at both low oxygen and low sulfur fugacity Ir and Rh were found to be strongly incompatible in mss. At QFM and Pt-PtS the partition coefficient for Ni shows weak temperature dependence, ranging from 0.66 at 1050°C to 0.94 at 950°C. At lower oxygen and sulfur fugacity Ni showed much more incompatible behavior. Comparison with the compositions of sulfide ores from the Lindsley deposit of Sudbury suggests that the sulfide magma evolved under conditions close to the QFM and Pt-PtS buffers. The compatible behavior observed for Ni, Ir and Rh at Lindsley and most other magmatic sulfide deposits hosted by mafic rocks requires equilibration of mss and sulfide liquid at moderately high sulfur fugacity and low temperatures near to the solidus of the sulfide magma. We argue that this constraint requires that the sulfide magma must have evolved by equilibrium crystallization, rather than fractional segregation of mss as is commonly supposed.     

Solubility of platinum and palladium in silicate melts under high water pressure as a function of redox conditions

The solubility of platinum and palladium in a silicate melt of the composition Di ₅₅ An ₃₅ Ab ₁₀ was determined at 1200°C and 2 kbar pressure in the presence of H₂O-H₂ fluid at an oxygen fugacity ranging from the HM to WI buffer equilibria. The influence of sulfur on the solubility of platinum in fluid-bearing silicate melt was investigated at a sulfur fugacity controlled by the Pt-PtS equilibrium at 1200°C and a pressure defined in such a way that the \(f_{H_2 O} \) and \(f_{O_2 } \) values were identical to those of the experiments without sulfur. The experiments were conducted in a high pressure gas vessel with controlled hydrogen content in the fluid. Oxygen fugacity values above the NNO buffer were controlled by solid-phase buffer mixtures using the two-capsule technique. Under more reducing conditions, the contents of H₂O and H₂ were directly controlled by the argon to hydrogen ratio in a special chamber. The hydrogen fugacity varied from 5.2 × 10^?2 bar (HM buffer) to 1230 bar (\(X_{H_2 } \) = 0.5). Pt and Pd contents were measured in quenched glass samples by neutron activation analysis. The results of these investigations showed that the solubility of Pt and Pd increases significantly in the presence of water compared with experiments in dry systems. The content of Pd within the whole range of redox conditions and that of Pt at an oxygen fugacity between the HM to MW buffer reactions are weakly dependent on \(f_{O_2 } \) and controlled mainly by water fugacity. This suggests that, in addition to oxide Pt and Pd species soluble at the ppb level in haplobasaltic melts, much more soluble (ppm level) hydroxide complexes of these metals are formed under fluid-excess conditions. Despite a decrease in water fugacity under reducing conditions, Pt solubility increases sharply near the MW buffer. It was shown by electron paramagnetic resonance spectrometry that, in contrast to dry melts, fluid-saturated silicate melts do not contain a pure metal phase (micronuggets). Therefore, the increase in Pt solubility under reducing conditions can be explained by the formation of Pt hydride complexes or Pt-fluid-silicate clusters. At a sulfur fugacity controlled by the Pt-PtS equilibrium, the solubility of Pt in iron-free silicate melts as a function of redox conditions is almost identical to that obtained in the experiments without sulfur at the same water and oxygen fugacity values. These observations also support Pt dissolution in iron-free silicate melts as hydroxide species.     

Crystal chemistry of Fe-containing sphalerites

 Cell dimensions and solvus properties of Fe-containing sphalerites, depending on temperature and sulfur fugacity, were investigated using equilibrated powdered materials synthesized from elements and binary sulfides under vacuum. The Fe solvus in sphalerite, determined by optical microscopy and microprobe analysis, are directly correlated with increasing temperature and decreasing sulfur fugacity controlled by solid-state buffers. The increase of lattice parameters with Fe correlates with an increase of FeS independent of sulfur fugacity up to 10 mol% FeS within ZnS. Above about 10 mol% the lattice parameters are strongly depending on the sulfur fugacity controlled Fe³⁺/Fe²⁺ ratios. The Fe³⁺/Fe²⁺ ratios determined by Moessbauer spectroscopy and involving metal vacancies depend on the sulfur fugacity. The critical Fe²⁺ content determined by experimental simulations as well as the minimal Fe³⁺/ Fe²⁺ ratios agree with the required minimal Fe content for CuFeS₂-DIS in sphalerite. The critical Fe²⁺ content also agrees with the change of Moessbauer signal from a singlet to a doublet for Fe²⁺ containing sphalerite. Pyrrhotite exsolutions in sphalerite caused by higher sulfur fugacity show orientationally intergrown with the sphalerite matrix. Density data calculated from lattice parameters and composition are compared with experimental density measurements. Received: 25 April 2001 / Accepted: 14 February 2003     

辽宁宽甸地幔矿物三价铁的穆斯堡尔谱测定及意义

摘　要　利用穆斯堡尔谱仪对辽宁宽甸地幔岩包体中的矿物进行了三价铁的测定‚测试结果 与国内外已发表的数据接近。Fe 3＋ ／∑Fe 比值分别为：斜方辉石0∙066～0∙196‚单斜辉石 0∙216～0∙344‚尖晶石0∙283～0∙299‚石榴石0∙057～0∙223。依据电价平衡原理计算的 Fe 3＋ 含量受 Si 4＋ 、Al 3＋ 和 Cr 3＋ 的电子探针分析误差影响很大。根据地幔矿物的电子探针分析结果 计算平衡温度、压力和氧逸度时‚二辉石 En、Ca 转移反应温度计和石榴石 斜方辉石 Al 压力 计的计算结果不超过温压计的一般误差范围‚而石榴石 单斜辉石 Fe 2＋ Mg 交换反应温度计 在忽略 Fe 3＋ 时计算的温度值可偏高100℃以上;采用橄榄石／斜方辉石／尖晶石组合氧压力计 计算的氧逸度值‚误差一般约在±0∙7个对数单位。     

Reaction Between Ultramafic Rock and Fractionating Basaltic Magma II. Experimental Investigation of Reaction Between Olivine Tholeiite and Harzburgite at 1150-1050?C and 5 kb

We present results of experiments on mixtures of olivine tholeiiteand mantle harzburgite, at 5 kb and 1050–1150?C, underconditions of controlled hydrogen fugacity. The basalt end-memberwas Kilauea 1921 olivine tholeiite+3 wt.% H₂O, and the harzburgiteend-member was a mixture of olivine and orthopyroxene mineralseparates made from a mantle-derived lherzolite xenolith. Theexperiments on mixtures of basalt and harzburgite difl not reachequilibrium in runs ranging from 12 to 200 h duration. Relativelylarge concentration gradients persisted in both liquid and solidphases in mixed samples, whereas ‘control’ samplescontaining only basalt were reasonably homogeneous and wereprobably close to equilibrium. Compositions of solid phases produced, measured by electronmicroprobe, show a regular increase in Mg/(Mg+Fe) with increasingproportion of harzburgite at constant temperature, but olivineand clinopyroxene in mixed samples were not in Fe-Mg exchangeequilibrium. Modes measured for each sample show that the fractionof liquid relative to the amount of basalt in the sample wasconstant at constant temperature, and independent of bulk composition:reaction between 1921 basalt and harzburgite does not changethe mass of liquid in the system. Average experimental liquidcompositions for each sample were obtained by mass balance.Using Kds defined by the ‘control’ sample for eachtemperature, and mass balance constraints, phase assemblages(solid- and liquid-phase compositions and proportions) werecalculated for all mixtures. Whether samples included harzburgite or not, all average experimentalliquid compositions, and all predicted liquid compositions,for samples run at 1050?C, are high-alumina basalts by the definitionof Kuno (1960). By the criteria of Irvine & Baragar (1971),all but two average experimental liquid compositions in basalt-harzburgitemixtures, and all predicted liquid compositions in basalt-harzburgitemixtures, are calc-alkaline basalts and basaltic andesites,whereas liquids in samples containing only basalt are tholeiiticbasalts. Combined crystallization and reaction with harzburgitein the upper mantle will produce calc-alkaline derivative liquidsfrom an olivine tholeiite liquid under conditions of temperature,pressure, water and oxygen fugacity, and initial bulk compositionwhich would produce a tholeiitic liquid line of descent by crystallizationin a closed system. ^*Present address: Woods Hole Oceanographic Institution, Woods Hole, Massachusetts 02543Present address: Grant Institute of Geology, University of Edinburgh, West Mains Road, Edinburgh EH9 3JW, UK     

Distribution of noble metals in ore mineral assemblages of the Volkovsky gabbroic pluton, central Urals

Relationships between noble-metal and oxide-sulfide mineralization during the origin of the Volkovsky gabbroic pluton are discussed on the basis of geochemical data and thermodynamic calculations. The basaltic magma initially enriched in noble metals (NM) relative to their average contents in mafic rocks, except for Pt, is considered to be a source of Pd, Pt, Au, and Ag in the gabbroic rocks of the Volkovsky pluton. The ores were formed with a progressive gain of NM in the minerals during the fractionation of the basaltic magma. The active segregation of NM in the form of individual minerals (palladium tellurides and native gold) hosted in titanomagnetite and copper sulfide ore occurred during the final stage of gabbro crystallization, when the residual fluid-bearing melt acquired high concentrations of Cu, Fe, Ti, and V, along with volatile P and S. Copper sulfides—bornite and chalcopyrite—are the major minerals concentrating NM; they contain as much as 22.65–25.20 ppm Pd and 0.74–1.56 ppm Pt; 4.39–8.0 ppm Au, and 127.2–142.6 ppm Ag, respectively. The copper ore and associated NM mineralization were formed at a relatively low sulfur fugacity, which was a few orders of magnitude (attaining 5 log units) lower than that of the pyrite-pyrrhotite equilibrium. The low sulfur fugacity and the close chemical affinity of Pd and Pt to Te precluded the formation of pyrrhotite, pyrite, and PGE disulfides. The major ore minerals and NM mineralization were formed within a wide temperature range (800–570°C), under nearly equilibrium conditions. Foreign elements (Ni, Co, and Fe) affected the thermodynamic stability of Pd and Pt compounds owing to the difference in their affinity to Te and to elements of the sulfur group (S, Se, and As). The replacement of Pd with Ni and Co and, to a lesser extent, with Pt and the replacement of Te with S, As, and Se diminish the stability field of palladium telluride. Comparison of Pd tellurides from copper sulfide ores at the Volkovsky and Baronsky deposits showed the enrichment of the former in Au, Sb, and Bi, while the latter are enriched in Pt, Ni, and Ag. The enrichment of Pd tellurides at the Baronsky deposit in Ni is correlated with the analogous enrichment of the host gabbroic rocks.     

The dependence of the partitioning of iron and europium between plagioclase and hydrous tonalitic melt on oxygen fugacity

The dependence of iron and europium partitioning between plagioclase and melt on oxygen fugacity was studied in the system SiO₂(Qz)—NaAlSi₃O₈(Ab)—CaAl₂Si₂O₈(An)—H₂O. Experiments were performed at 500 MPa and 850 °C/750 °C under water saturated conditions. The oxygen fugacity was varied in the log f _O2-range from −7.27 to −15.78. To work at the most reducing conditions the classical double-capsule technique was modified. The sample and a C—O—H bearing sensor capsule were placed next to each other within a BN jacket to minimise loss of hydrogen to the vessel atmosphere. By this setup redox conditions slightly more reducing than the FeO—Fe₃O₄ buffer could be maintained even in 96 h runs. Raman spectra showed that the BN was modified by reaction with hydrogen resulting in a low hydrogen permeability. The partition coefficients determined for Eu at 850 °C and 500 MPa vary from 0.095 at conditions of the Cu—Cu₂O buffer to 1.81 at the most reducing conditions (C—O—H sensor). In the same f _O2 interval the partition coefficient for Fe varies from 0.55 at oxidising conditions to 0.08 at the most reducing conditions. The partitioning of Sm, which was added as a reference for a trivalent REE, does not vary with the oxygen fugacity, yielding an average value for D = 0.07. Lowering the temperature to 750 °C for a given f _O2 decreases the partition coefficient of Eu and increases that of Fe. Comparison with published data at 1 atm and at higher temperatures shows that both temperature and composition of the melt have strong effects on the partitioning behaviour. As the change of the partition coefficients in the geologically relevant f _O2 range is quite strong, element partitioning of Eu and Fe might be used to estimate redox conditions for the genesis of igneous rocks. Furthermore, by modelling the partitioning data it is possible to extract information about the redox state of the melt. Resulting ferric-ferrous ratios show significant differences from those predicted by empirical models. Received: 14 October 1998 / Received: 5 March 1999     

榴辉岩部分熔融过程中钒分配系数的实验测定

钒(V)是常见的变价元素,其在矿物-熔体间的分配行为主要受氧逸度控制。近年来, V的分配行为与氧逸度之间的关系常被用于揭示地幔的氧化还原状态。板块俯冲过程中, V能否迁移是理解俯冲带V地球化学行为的关键环节,也是探讨俯冲带地幔楔氧逸度的重要前提。本文使用活塞圆筒装置模拟含水榴辉岩部分熔融过程,测定石榴子石、单斜辉石和金红石与熔体之间V的分配系数。实验压力为2.5GPa、温度介于900～1125℃之间,实验产物计算的氧逸度ΔFMQ介于-5.24～+0.74之间,实验结果表明V在石榴子石、单斜辉石和金红石中为相容元素(矿物/熔体分配系数D>1.0),并且DV(金红石)>DV(单斜辉石)>DV(石榴子石); V的分配系数也是氧逸度、温度和熔体聚合度的函数,随氧逸度和温度的增加,石榴子石、单斜辉石和金红石的V分配系数都减小,而随着熔体聚合程度的增加, V分配系数增大。模拟结果表明在榴辉岩部分熔融过程中熔体将显著亏损V,因此, V在榴辉岩(俯冲带洋中脊玄武岩)部分熔融过程中是不运移的;而板块俯冲过程中,榴辉岩部分熔融产生的熔体交代地幔楔不能明显改变地幔的V含量, V在地幔矿物和...     

Separation of Platinum from Palladium and Iridium in Iron Meteorites and Accurate High‐Precision Determination of Platinum Isotopes by Multi‐Collector ICP‐MS

This study presents a new measurement procedure for the isolation of Pt from iron meteorite samples. The method also allows for the separation of Pd from the same sample aliquot. The separation entails a two‐stage anion‐exchange procedure. In the first stage, Pt and Pd are separated from each other and from major matrix constituents including Fe and Ni. In the second stage, Ir is reduced with ascorbic acid and eluted from the column before Pt collection. Platinum yields for the total procedure were typically 50–70%. After purification, high‐precision Pt isotope determinations were performed by multi‐collector ICP‐MS. The precision of the new method was assessed using the IIAB iron meteorite North Chile. Replicate analyses of multiple digestions of this material yielded an intermediate precision for the measurement results of 0.73 for ε¹⁹²Pt, 0.15 for ε¹⁹⁴Pt and 0.09 for ε¹⁹⁶Pt (2 standard deviations). The NIST SRM 3140 Pt solution reference material was passed through the measurement procedure and yielded an isotopic composition that is identical to the unprocessed Pt reference material. This indicates that the new technique is unbiased within the limit of the estimated uncertainties. Data for three iron meteorites support that Pt isotope variations in these samples are due to exposure to galactic cosmic rays in space.     

Cations in olivine,Part 2: Diffusion in olivine xenocrysts,with applications to petrology and mineral physics

Diffusivities for calcium, iron, magnesium, manganese and aluminum have been measured for St. John's olivine undergoing cation exchange with synthetic basaltic melts. The variety of temperature, pressure and fO₂ conditions under which the diffusivities were measured complement the equilibrium-partitioning study of calcium in olivine-bearing basalts by Jurewicz and Watson, 1988. Olivine was found to be anisotropic with respect to the diffusion of calcium, iron, magnesium and manganese. This anisotropy is a weak function of temperature, but strongly dependent upon oxygen fugacity.Because diffusion is independent of olivine composition over the small range of compositions used in this study, it could be shown that the absolute values of the diffusion coefficients were also functions of temperature and fO₂. At near-atmospheric total pressure and an oxygen fugacity of 10^–8atm, D _Fe>D _Mn>D _Ca and D _MgD _Mn for a range of geologically reasonable temperatures. These relative diffusivities were shown to change with oxygen fugacity. The power-law dependence of diffusion on oxygen partial-pressure was determined for each cation and the results are consistent with the range of values given by Stocker (1978) and by other workers.For Ca and Fe, the effect of hydrostatic pressure on diffusion appears to be weak, at least for transport parallel to the c crystallographic direction. Unfortunately, no true activation volumes (or other pressure-related parameters) could be computed because the oxygen fugacity was not held constant over changes in pressure, and because accurate post-experiment reconstruction of sample orientation was not possible. Al was found to enter high-pressure olivines at concentrations of up to 0.14 weight percent, thus allowing aluminum diffusion to be characterized. The diffusivity of aluminum is, within error, the same as iron at 20 kb at 1430° C at the ambient fO₂ of our piston-cylinder cells. This correspondence suggests that diffusion of Al may depend on transport of either Fe or of Fe ⁺³ defects. While the results of these experiments are generally consistent with results published elsewhere, there are important inconsistencies. Tracer diffusion and interdiffusion in pure, ordered, olivine endmembers (e.g., tephroite and forsterite) showed significantly higher activation energies. This discrepancy could reflect the role of Fe⁺³ defects in diffusion; however, it may also suggest that order-disorder phenomena may be significant factors influencing diffusion in analog systems.The results of this study are applied to four petrologic problems: (1) calculation of rates of equilibration for olivine xenocrysts; (2) calculation of closure temperatures for the CaO/MgO olivine/basalt geothermometer (Jurewicz and Watson 1988); (3) delineation of an intrinsic-/O₂ geobarometer; and (4) investigation of the dependence of olivine dissolution upon crystallographic orientation. In addition, it is demonstrated that diffusion-exchange experiments are useful for studying the dominant point-defect mechanisms for cation diffusion.Currently, a visiting scientist with Air Force Wright Aeronautical Laboratories Materials Laboratory (MLLM), Wright-Patterson AFB, OH 45433     

Effect of oxygen fugacity and water on phase equilibria of a hydrous tholeiitic basalt

The influence of oxygen fugacity and water on phase equilibria and the link between redox conditions and water activity were investigated experimentally using a primitive tholeiitic basalt composition relevant to the ocean crust. The crystallization experiments were performed in internally heated pressure vessels at 200 MPa in the temperature range 940–1,220°C. The oxygen fugacity was measured using the H₂-membrane technique. To study the effect of oxygen fugacity, three sets of experiments with different hydrogen fugacities were performed, showing systematic effects on the phase relations and compositions. In each experimental series, the water content of the system was varied from nominally dry to water-saturated conditions, causing a range of oxygen fugacities varying by ~3 log units per series. The range in oxygen fugacity investigated spans ~7 log units. Systematic effects of oxygen fugacity on the stability and composition of the mafic silicate phases, Cr–spinel and Fe–Ti oxides, under varying water contents were recorded. The Mg# of the melt, and therefore also the Mg# of olivine and clinopyroxene, changed systematically as a function of oxygen fugacity. An example of the link between oxygen fugacity and water activity under hydrogen-buffered conditions is the change in the crystallization sequence (olivine and Cr–spinel) due to a change in the oxygen fugacity caused by an increase in the water activity. The stability of magnetite is restricted to highly oxidizing conditions. The absence of magnetite in most of the experiments allows the determination of differentiation trends as a function of oxygen fugacity and water content, demonstrating that in an oxide-free crystallization sequence, water systematically affects the differentiation trend, while oxygen fugacity seems to have a negligible effect.     

广西新元古代BIF的铁同位素特征及其地质意义

通过分析广西三江地区新元古代条带状含铁建造的Fe同位素和主量元素组成,对海水的氧化还原状态提供了制约,为富禄期的地球处于间冰期提供了证据。相对于标准物质IRMM-014,新元古代含铁建造不同条带全岩样品的δ57Fe值变化范围1.60‰～2.20‰,平均值为1.85‰,表明BIF样品富集铁的重同位素。条带状含铁建造主要由Fe2O3和SiO2组成,但却具有较高的Al2O3含量。这表明条带状含铁建造样品不是纯净的化学沉积物,而是具有一定的碎屑物质输入。碎屑输入量的不同引起深色和浅色条带之间铁同位素组成存在着0.4‰的差别。剔除碎屑的影响,新元古代BIF从海水中沉淀的赤铁矿δ57Fe的平均值在2‰左右,略高于太古代条带状铁建造的Fe同位素组成,这表明当时海水的氧逸度可能比太古代还低。这说明在富禄期绝大部分海洋仍旧被冰盖覆盖,只在局部出现融化。因此,富禄期的地球可能出于冰期的相对温暖阶段,而不是间冰期。     

Interaction of Fe and Fe<Subscript>3</Subscript>C with hydrogen and nitrogen at 6–20 GPa: a study by in situ X-ray diffraction

A method of in situ X-ray diffraction at Spring-8 (Japan) was used to analyze simultaneously the hydrogen incorporation into Fe and Fe₃C, as well as to measure the relative stability of carbides, nitrides, sulfides, and hydrides of iron at pressures of 6–20 GPa and temperatures up to 1600 K. The following stability sequence of individual iron compounds was established in the studied pressure and temperature interval: FeS > FeN > FeC > FeH > Fe. A change in the unit-cell volume as compared to the known equations of state was used to estimate the hydrogen contents in carbide Fe₃C and hydride FeH_x. Data on hydride correspond to stoichiometry with x ≈ 1. Unlike iron sulfides and silicides, the solubility of hydrogen in Fe₃C seemed to be negligibly low—within measurement error. Extrapolating obtained data to pressures of the Earth’s core indicates that carbon and hydrogen are mutually incpompatible in the iron–nickel core, while nitrogen easily substitutes carbon and may be an important component of the inner core in the light of the recent models assuming the predominance of iron carbide in its composition.     

西南三江金厂河矽卡岩型多金属矿床铁同位素分馏机制及其对成矿物质来源的制约SCIEI北大核心CSCD

金厂河矿床是西南三江成矿省保山地块最具代表性的远端矽卡岩型多金属矿床之一,查明其成矿金属来源对理解该类矿床成因以及区域成矿规律具有重要意义。本文通过分析不同成矿阶段代表性含铁矿物的铁同位素组成,探讨其在成矿过程中的分馏机制,从而示踪成矿金属的源区特征。金厂河矽卡岩型矿床中成矿前阶段未蚀变的石榴子石和氧化物成矿阶段的磁铁矿均相对富集铁的重同位素,其δ;Fe值分别为0.05‰~0.16‰和0.07‰~0.18‰,而硫化物成矿阶段的黄铁矿和黄铜矿则相对富集铁的轻同位素,其δ;Fe值分别为-0.12‰~0.17‰和-0.54‰~-0.38‰,整体显示出从高氧逸度的成矿前阶段向低氧逸度的硫化物成矿阶段演化过程中矿物δ;Fe值逐渐降低的趋势,指示Fe;富集铁的重同位素,Fe;富集铁的轻同位素。同时,金厂河矿床各阶段矿物的δ;Fe值均显著低于碳酸盐围岩,而接近全球花岗岩的δ;Fe值,表明成矿的铁不是由围岩贡献,而是来自于隐伏的中酸性岩体。     

新疆玉海-三岔口铜矿黑云母矿物化学特征及成岩成矿意义

黑云母的化学成分对于揭示结晶条件、岩石成因、成矿演化以及含矿性评价等具有重要的指示意义.利用电子探针（EPMA）对新疆玉海和三岔口铜矿中的黑云母进行成分分析,结果表明与成矿相关岩体的黑云母具有富镁贫铁的特征,而无矿化岩体中的黑云母则呈现富铁贫镁的特征.分析结果显示矿化岩体中黑云母为再平衡镁质黑云母,而无矿化岩体中黑云母为原生铁质黑云母;它们的寄主岩石均属于I型花岗岩,形成于与俯冲相关的构造背景,但是与矿化相关岩体的岩浆源区为壳幔混合来源,而无矿岩体的源区为地壳来源,形成过程中有新生地壳组分的混染;两类黑云母的结晶温度为529~677 ℃,寄主岩体的固结压力为1.1~2.8 kbar,均形成于高氧逸度条件;此外,黑云母的Mg/Fe和Fe2+/（Fe2++Mg2+）还可以区分斑岩型铜矿的含矿性.