Platinum-group element distribution in base-metal sulfides of the Merensky Reef from the eastern and western Bushveld Complex, South Africa

Base-metal sulfides in magmatic Ni-Cu-PGE deposits are important carriers of platinum-group elements (PGE). The distribution and concentrations of PGE in pentlandite, pyrrhotite, chalcopyrite, and pyrite were determined in samples from the mineralized portion of four Merensky Reef intersections from the eastern and western Bushveld Complex. Electron microprobe analysis was used for major elements, and in situ laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) for trace elements (PGE, Ag, and Au). Whole rock trace element analyses were performed on representative samples to obtain mineralogical balances. In Merensky Reef samples from the western Bushveld, both Pt and Pd are mainly concentrated in the upper chromitite stringer and its immediate vicinity. Samples from the eastern Bushveld reveal more complex distribution patterns. In situ LA-ICP-MS analyses of PGE in sulfides reveal that pentlandite carries distinctly elevated PGE contents, whereas pyrrhotite and chalcopyrite only contain very low PGE concentrations. Pentlandite is the principal host of Pd and Rh in the ores. Palladium and Rh concentrations in pentlandite reach up to 700 and 130 ppm, respectively, in the samples from the eastern Bushveld, and up to 1,750 ppm Pd and up to 1,000 ppm Rh in samples from the western Bushveld. Only traces of Pt are present in the base-metal sulfides (BMS). Pyrrhotite contains significant though generally low amounts of Ru, Os, and Ir, but hardly any Pd or Rh. Chalcopyrite contains most of the Ag but carries only extremely low PGE concentrations. Mass balance calculations performed on the Merensky Reef samples reveal that in general, pentlandite in the feldspathic pyroxenite and the pegmatoidal feldspathic pyroxenite hosts up to 100 % of the Pd and Rh and smaller amounts (10–40 %) of the Os, Ir, and Ru. Chalcopyrite and pyrrhotite usually contain less than 10 % of the whole rock PGE. The remaining PGE concentrations, and especially most of the Pt (up to 100 %), are present in the form of discrete platinum-group minerals such as cooperite/braggite, sperrylite, moncheite, and isoferroplatinum. Distribution patterns of whole rock Cu, Ni, and S versus whole rock Pd and Pt show commonly distinct offsets. The general sequence of “offset patterns” of PGE and BMS maxima, in the order from bottom to top, is Pd in pentlandite?→?Pd in whole rock?→?(Cu, Ni, and S). The relationship is not that straightforward in general; some of the reef sequences studied only partially show similar trends or are more complex. In general, however, the highest Pd concentrations in pentlandite appear to be related to the earliest, volumetrically rather small sulfide liquids at the base of the Merensky Reef sequence. A possible explanation for the offset patterns may be Rayleigh fractionation.     

Platinum-group elements in Cu-sulphide ores at Carolusberg and East Okiep, Namaqualand, South Africa

Cu-sulphide ores at Carolusberg and East Okiep have Cu/Ni ratios of up to 80, an order of magnitude higher than most magmatic sulphide ores elsewhere. In contrast, Se/S ratios (500–1700 × 10⁻⁶) and PGE tenors (up to 5 ppm) of the sulphides are in the range of more typical magmatic sulphide ores. The observed metal patterns may be explained by a process of monosulphide solid solution (mss) fractionation of a magmatic sulphide melt at depth, but this model is currently considered unlikely, due to the paucity of refractory ores in the district. Assimilation of Cu-rich country rocks during ascent of the Koperberg magmas proved difficult to test with the available data, but this provides no explanation for the common high-grade metamorphic setting of similar ores elsewhere. A restitic origin of the pyroxenites appears to explain many of the observed ore features and is presently favoured here. Desulphidization of a primary magmatic sulphide ore could not have yielded the observed metal patterns and is therefore considered to be of relatively minor importance in ore genesis. Received: 12 April 1999 / Accepted: 27 November 1999     

Platinum-group elements in alpine-type ultramafic rocks and related chromite ores of the main ophiolite belt of the Urals

On the basis of a representative collection of ultramafic rocks and chromite ores and a series of technological samples from the largest (Central and Western) deposits in the Rai-Iz massif of the Polar Urals and the Almaz-Zhemchuzhina and Poiskovy deposits in the Kempirsai massif of the southern Urals, the distribution and speciation of platinum-group elements (PGE) in various type sections of mafic-ultramafic massifs of the Main ophiolite belt of the Urals have been studied. Spectral-chemical and spectrophotometric analyses were carried out to estimate PGE in 700 samples of ultramafic rocks and chromite ores; 400 analyses of minerals from rocks, ores, and concentrates and 100 analyses of PGE minerals (PGM) in chromite ores and concentrates were performed using an electron microprobe. Near-chondritic and nonchondritic PGE patterns in chromitebearing sections have been identified. PGE mineralization has been established to occur in chromite ore from all parts of the mafic-ultramafic massifs in the Main ophiolite belt of the Urals. The PGE deposits and occurrences discovered therein are attributed to four types (Kraka, Kempirsai, Nurali-Upper Neiva, and Shandasha), which are different in mode of geological occurrence, geochemical specialization, and placer-forming capability. Fluid-bearing minerals of the pargasite-edenite series have been identified for the first time in the matrix of chromite ore of the Kempirsai massif (the Almaz-Zhemchuzhina deposit) and Voikar-Syn’ya massif (the Kershor deposit). The PGE grade in various types of chromite ore ranges from 0.1–0.2 to 1–2 g/t or higher. According to technological sampling, the average PGE grade in the largest deposits of the southeastern ore field of the Kempirsai massif is 0.5–0.7 g/t. Due to the occurrence of most PGE as PGM 10–100 mm in size and the proved feasibility of their recovery into nickel alloys, chromites of the Kempirsai massif can be considered a complex ore with elevated and locally high Os, Ir, and Ru contents. The Nurali-Upper Neiva type of ore is characterized by small-sized primary deposits, which nevertheless are the main source of large Os-Ir placers in the Miass and Nev’yansk districts of the southern and central Urals, respectively.     

Magmatic metasomatism and formation of the Merensky reef,Bushveld Complex

The rare earth element (REE) contents of pyroxenes and other minerals from the Merensky reef and stratigraphically adjacent rocks of the Atok section, Bushveld Complex, have been determined with the ion microprobe. Merensky reef clinopyroxene and orthopyroxene contain much higher and more variable concentrations of the REE than their cumulus counterparts in rocks several meters below the reef. Chondrite-normalized Merensky clinopyroxene Ce contents vary from 10 to 90 for Ce and from 4 to 17 for Yb. They also possess deep, negative Eu anomalies, the Eu anomalics being deeper for crystals having high REE contents and relatively shallow for pyroxenes with low REE contents. Similar compositional characteristics are displayed by Cl-rich apatite, which is an accessory phase in the rocks. Interstitial pyroxene in cumulates above and below the reef also tends to have elevated REE contents and in general is not in equilibrium with coexisting cumulus minerals. The melt from which the cumulus minerals crystallized falls within the compositional range of continental basalts; that from which Merensky and postcumulus pyroxenes crystallized is inferred to be much more highly enriched in REE than any normal tholeiitic or alkalic basalt. Despite their highly evolved nature in terms of the REE, the Merensky reef pyroxenes are not evolved in terms of major elements. The decoupling of incompatible trace and major elements is best explained by a metasomatic process. It is speculated that metasomatism involved upward percolation of hydrated silicate melt through and its reaction with the crystalline cumulate pile. The fact that the rocks enriched in the platinum group elements are also those that show evidence for metasomatism suggests that these elements were also metasomatically redistributed.     

Geochemistry of the Merensky reef, Rustenburg Section, Bushveld Complex: controls on the silicate framework and distribution of trace elements

This whole rock and silicate mineral study focuses on the genesis of the Merensky reef sequence, as well as the footwall and hanging wall norites at an area of Rustenburg Platinum Mines in a demonstrably normal (undisturbed) environment. Continuous sampling provides major and trace element variations and mineral compositions and allows an evaluation of the post- liquidus processes which affected the sequence. Following the formation of liquidus phases three stages are envisaged to have modified the rocks. These are (a) migration of fluid during early compaction of cumulates, (b) circulation of fluids within the crystal mush, and (c) reaction and solidification of trapped liquid. Liquidus compositions are nowhere preserved in the sequence. A strong link is demonstrated between orthopyroxene compositions (e.g. Mg# and TiO₂) and the incompatible trace element content of the whole rocks. The final amount of trapped liquid is shown to have been variable but never exceeded 10%. Calculated liquidus (pre-equilibration) orthopyroxene compositions show an up- sequence progression of evolving compositions from the footwall norite to the hanging wall norite. Initial Sr isotopic values do not support a simple magma mixing model by which radiogenic Main Zone magma mixes with that of the Critical Zone at the level of the Merensky reef. There is evidence that the hanging wall norite formed from a much more evolved magma. These conclusions have implications for the distribution and origin of the PGE-enriched Merensky reef package. Received: 7 October 1998 / Accepted: 5 March 1999     

Platinum group elements in gold-sulfide and base-metal ores of the Sayan-Baikal Fold Region and possible platinum and palladium speciation in sulfides

The concentration levels and distribution features of the platinum group elements (PGE) in quartz-sulfide and base-metal ores in deposits of the Sayan-Baikal Fold Region (SBFR) are discussed. Microfire assay neutron activation analysis (MF-NAA), which enables one to work on a nondestructive basis and allows one to avoid inaccuracies related to chemical sample preparation, was used as the main analytical technique. Three types of hydrothermal mineralization with elevated grades of PGE (especially Pt, Pd, and Ru) have been identified: (1) pyrite-pyrrhotite (massive sulfide) mineralization hosted in black shales of the Il’chir Sequence; (2) gold-sulfide ores of the Zun-Kholba, Tainsky, Kamenny, and some other gold deposits; and (3) silver-basemetal ores of the Dzhida-Vitim Zone. The PGE contents significantly vary, from global average values to tens of grams per ton. An absence of PGE minerals implies that these elements are finely dispersed in sulfide minerals and native gold. Taking into account difficulties in conversion of PGE into analytical forms, their nonuniform distribution in sulfide minerals, their high affinity to coordination compounds, and experimental results, cluster species of Pt and Pd in major minerals are suggested for the gold-sulfide and silver-base-metal ores in deposits, which are related to suprasubduction ophiolites and island-arc and intraplate settings in the SBFR.     

Platinum-group elements (PGE) and rhenium in marine sediments across the Cretaceous-Tertiary boundary: constraints on Re-PGE transport in the marine environment

The nature of Re-platinum-group element (PGE; Pt, Pd, Ir, Os, Ru) transport in the marine environment was investigated by means of marine sediments at and across the Cretaceous-Tertiary boundary (KTB) at two hemipelagic sites in Europe and two pelagic sites in the North and South Pacific. A traverse across the KTB in the South Pacific pelagic clay core found elevated levels of Re, Pt, Ir, Os, and Ru, each of which is approximately symmetrically distributed over a distance of ∼1.8 m across the KTB. The Re-PGE abundance patterns are fractionated from chondritic relative abundances: Ru, Pt, Pd, and Re contents are slightly subchondritic relative to Ir, and Os is depleted by ∼95% relative to chondritic Ir proportions. A similar depletion in Os (∼90%) was found in a sample of the pelagic KTB in the North Pacific, but it is enriched in Ru, Pt, Pd, and Re relative to Ir. The two hemipelagic KTB clays have near-chondritic abundance patterns. The ∼1.8-m-wide Re-PGE peak in the pelagic South Pacific section cannot be reconciled with the fallout of a single impactor, indicating that postdepositional redistribution has occurred. The elemental profiles appear to fit diffusion profiles, although bioturbation could have also played a role. If diffusion had occurred over ∼65 Ma, the effective diffusivities are ∼10⁻¹³ cm²/s, much smaller than that of soluble cations in pore waters (∼10⁻⁶ cm²/s). The coupling of Re and the PGEs during redistribution indicates that postdepositional processes did not significantly fractionate their relative abundances. If redistribution was caused by diffusion, then the effective diffusivities are the same. Fractionation of Os from Ir during the KTB interval must therefore have occurred during aqueous transport in the marine environment. Distinctly subchondritic Os/Ir ratios throughout the Cenozoic in the South Pacific core further suggest that fractionation of Os from Ir in the marine environment is a general process throughout geologic time because most of the inputs of Os and Ir into the ocean have Os/Ir ratios ≥1. Mass balance calculations show that Os and Re burial fluxes in pelagic sediments account for only a small fraction of the riverine Os (<10%) and Re (<0.1%) inputs into the oceans. In contrast, burial of Ir in pelagic sediments is similar to the riverine Ir input, indicating that pelagic sediments are a much larger repository for Ir than for Os and Re. If all of the missing Os and Re is assumed to reside in anoxic sediments in oceanic margins, the calculated burial fluxes in anoxic sediments are similar to observed burial fluxes. However, putting all of the missing Os and Re into estuarine sediments would require high concentrations to balance the riverine input and would also fail to explain the depletion of Os at pelagic KTB sites, where at most ∼25% of the K-T impactor’s Os could have passed through estuaries. If Os is preferentially sequestered in anoxic marine environments, it follows that the Os/Ir ratio of pelagic sediments should be sensitive to changes in the rates of anoxic sediment deposition. There is thus a clear fractionation of Os and Re from Ir in precipitation out of sea water in pelagic sections. Accordingly, it is inferred here that Re and Os are removed from sea water in anoxic marine depositional regimes.     

Trace elements in the Merensky Reef and adjacent norites Bushveld Complex South Africa

Trace elements were analysed in rocks and minerals from three sections across the Merensky Reef in the Rustenburg Platinum Mine in the Bushveld Complex of South Africa. Whole rocks and separated minerals were analysed by inductively coupled plasma-mass-spectrometer (ICP-MS) and in situ analyses were carried out by ion microprobe and by laser-source ICP-MS. Merensky Reef pyroxenites contain extremely high concentrations of a wide range of trace elements. These include elements incompatible with normal silicate minerals as well as siderophile and chalcophile elements. For major elements and compatible trace elements, the measured concentrations in cumulus phases and the bulk rock compositions are similar. For highly incompatible elements, however, concentrations in bulk rocks are far higher than those measured in the cumulus phases. In situ analyses of plagioclase have far lower concentrations of Th, Zr and rare earth elements than ICP-MS analyses of bulk separates of plagioclase, a difference that is attributed to the presence of trace-element-rich accessory phases in the bulk mineral separates. We used these data to calculate the trace-element composition of the magmas parental to the Merensky Unit and adjacent norites. We argue that there is no reason to assume that the amount of trapped liquid in the Merensky orthopyroxenite was far greater than in the norites and we found that the pyroxenite formed from a liquid with higher concentrations of incompatible trace elements than the liquid that formed the norites. We propose that the Bushveld Complex was fed by magma from a deeper magma chamber that had been progressively assimilating its crustal wall rocks. The magma that gave rise to the Merensky Unit was the more contaminated and unusually rich in incompatible trace elements, and when it entered the main Bushveld chamber it precipitated the unusual phases that characterize the Merensky Reef. The hybrid magma segregated sulphides or platinum-group-element-rich phases during the course of the contamination in the lower chamber. These phases accumulated following irruption into the main Bushveld chamber to form the Merensky ore deposits.     

Low temperature alteration of magmatic Ni-Cu-PGE sulfides as a source for hydrothermal Ni and PGE ores: A quantitative approach using automated mineralogy

Magmatic Ni-Cu-PGE sulfide assemblages are almost ubiquitously comprised of pyrrhotite-pentlandite-chalcopyrite(-pyrite). Sulfide alteration is common during syn- or post-magmatic fluid interaction, usually replacing sulfides with amphiboles or serpentine. However, some are altered to a low temperature (<200 °C) hydrothermal assemblage of pyrite-millerite-chalcopyrite (PMC). An example is the Ni-Cu-PGE mineralisation in the Grasvally-Norite-Pyroxenite-Anorthosite (GNPA) Member, northern Bushveld Complex, which displays a continuum of mineralogical styles formed through progressive alteration: Style 1 primary pyrrhotite-pentlandite-chalcopyrite; which is altered to Style 2 pyrrhotite-pyrite-pentlandite-chalcopyrite; Style 3 pyrite-pentlandite-chalcopyrite; Style 4 pyrite-pentlandite-millerite-chalcopyrite; and Style 5 pyrite-millerite-chalcopyrite-cubanite. Modelling using CHILLER confirms this mineralogical sequence is thermodynamically possible at ∼200 °C. Quantitative characterisation using automated Energy-Dispersive X-ray spectroscopy mapping alongside in situ laser ablation analyses determined mineral proportions, major and trace element concentrations and deportments in each style. The early loss of pyrrhotite removes over half of the bulk Fe and S during the initial stages of PMC alteration, increasing Cu, Ni and PGE tenors of the remaining sulfides significantly. As water–rock interaction progresses, pyrrhotite is replaced by pyrite and pentlandite by millerite, with concurrent losses in Fe, S and Ni. Copper is lost throughout the alteration, and is most pronounced in the more advanced stages. The fluids responsible were most likely acidic and oxidised, with metals mobilised as chloride complexes. Using Rh as an immobile normalising element, the overall mass loss in the most altered samples is calculated to be up to 90%, consistent with textural relationships that indicate 40–90% volume loss from Styles 2–5, with sulfides replaced by secondary silicates, including phlogopite, quartz, chlorite, pyroxenes and minor amphiboles. Magnetite is not a significant alteration product and thus Fe is mobilised, or incorporated into silicates. Most trace elements present in the magmatic sulfide (the IPGE, Rh and Bi) remain in the sulfide phases, and are effectively transferred to pyrite during PMC alteration, except Pd, which remains in pentlandite, and is liberated from the sulfide assemblage when pentlandite disappears. Selenium tenors increase slightly with alteration, demonstrating that alteration decreases S/Se ratios. The significant mobilisation of Ni, Cu and Pd during PMC alteration produces fluids enriched in these elements that may represent a metal source for a number of enigmatic hydrothermal Ni deposits such as Avebury, Enterprise and Talvivaara, whose metal sources remain speculative. The PMC alteration of the GNPA Member may be specifically a source for the nearby Waterberg hydrothermal Pt deposit. Furthermore, this study has implications not only for magmatic ore deposits, but also for the general implications of sulfide transformation and metal transfer in ore systems in general.     

Dualistic distribution coefficients of elements in the system mineral-hydrothermal solution. I. Gold accumulation in pyrite

The use of trace elements (TE) as geochemical indicators is complicated by the dualism of their distribution coefficients D due to the additional (i.e., above the concentrations of an isomorphic component) incorporation of elements at structural defects of various nature (including the surface of the crystal). A pressing problem in this situation is to determine the true D values that pertain to the structural component of an admixture D ^str and evaluate effects of other modes of TE occurrence. Only upon distinguishing D ^str in the bulk coefficient D ^bulk it is possible to evaluate the ore potential of fluid in terms of certain TE from the composition of a mineral containing the TE. Pyrite synthesized in solutions of variable pH at 450°C and 1 kbar (100 MPa) at fluid portions sampled in a trap is utilized to demonstrate the role of a surface nonautonomous phase (NP) in the incorporation of gold in this mineral. The distribution coefficient of gold between pyrite and hydrothermal solution is 0.14 for “pure” pyrite and 0.05 for As-bearing pyrite (containing 0.02–0.05 wt % As), and these coefficients for NP are 310 and 170, respectively. This increases the D ^bulk for evenly distributed (“invisible”) gold by factors of four and nine. In contrast to the results of earlier studies conducted at room temperature and pressure or parameters close to them, our data demonstrate that the accumulation of “invisible” Au in pyrite is controlled not only by reducing adsorption with the development of Au(0) particles and films but also by Au incorporation in NP developing in the surface layer of the crystal approximately 500 nm thick as chemically bound Au [most likely as Au(I)]. The possible reason for the high absorption capacity of NP is the defect (pyrrhotite-like) structure, which is not saturated with bonds of excess S and sulfoxi onions.     

铜陵矿山酸性排水及固体废弃物中的重金属元素

在调查中国铜陵凤凰山铜矿和新桥硫铁矿两种不同类型矿山固体废弃物特征的基础上,研究了矿山尾矿和废石产生酸性排水的可能性及其差异以及矿山固体废弃物中重金属元素的赋存形式。结果表明,凤凰山铜矿的尾矿基本不产生矿山酸性排水,而新桥硫铁矿采矿废石产生矿山酸性排水,并且凤凰山铜矿的尾矿和新桥硫铁矿采矿废石中重金属元素的赋存形式也有差异,前者重金属Cu、Pb、Zn、Cd、As、Hg主要赋存于硅酸盐态中,而后者在还原态中有较高的含量,这反映了在地表条件下尾矿中大量重金属元素已经发生了迁移,而采矿废石已经开始氧化,且酸性排水的存在更有利于废石中重金属元素的迁移和扩散,进而导致矿区周围环境的污染。     

Partition of major and minor elements and equilibration in coexisting pyroxenes

The partition of Si, Al, Ti, Fe³⁺, Mg, Fe²⁺, Mn, Ca and Na between coexisting Ca-rich and Ca-poor pyroxenes from a wide variety of igneous and metamorphic rocks have been investigated systematically. Many of the distributions, and especially those for the partition of Ti, Mg, Fe²⁺, Mn and Na, indicate characteristic trends for pyroxenes from the various petrologic groups identified. The partition of Mg, Fe²⁺ and Mn correlate with inferred cooling rates, the partition co-efficients of pyroxenes from extruded and other quickly cooled rocks most nearly approaching unity. In contrast, the partition of Si and Ti and the absolute amounts of Al may be related to the physicochemical conditions prevailing during original crystallisation; Ti being particularly relatively enriched in Ca-rich pyroxenes of ultramafic associations. The trends of the compositions of the Ca-rich pyroxenes plotted in the pyroxene quadrilateral also correlate with cooling rates and comparison with the limited data available on the phase relations of coexisting pyroxenes suggests that sub-solidus chemical readjustments have occurred in both phases.     

PGE mineralization in marginal sulfide ores of the Chineisky layered intrusion, Russia

Summary We have undertaken a detailed study of platinum group element (PGE) mineralogy and geochemistry of disseminated sulfides associated with the marginal zone of the Chineisky layered mafic intrusion. Towards an intrusive contact the marginal zone reveals a gradual progression from gabbro-gabbronorites towards monzodiorite. Sulfides occur in all the rocks of the marginal zone including exocontact sandstone. They occur mainly as pyrrhotite, chalcopyrite, and pentlandite and show progressive enrichment in Cu towards the intrusive contact. In the same direction, PGE mineralogy reveals the following systematic changes: (1) size of PGE mineral grains decreases from 50 μm up to 1 μm; (2) the association of Pd minerals with Ni and Co arsenide and sulfarsenides becomes stronger; and (3) the composition of PGE minerals changes for palladium: Pd-Sn → Pd-As → Pd-Sb → Pd-Te → Pd-Bi; for platinum: Pt-Fe + PtAs₂ → PtS + PtAs₂ → PtAs_2. This zoning pattern is interpreted as the result of fractional crystallization of an immiscible sulfide melt, with the residual liquid, enriched in Cu, PGE, and volatile elements, being expelled towards the periphery of the intrusive body. PGE minerals also decompose in an oxidation zone. The most stable of them are paolovite and sperrylite, which both accumulated in placers derived from the massif. Pd is removed from the decomposed minerals, and then absorbed by brown iron and goethite in the oxidation zone. Author’s address: Nadezhda Tolstykh, Institute of Geology and Mineralogy SB RUS, pr. Ak. Koptyga 3, Novosibirsk 630090, Russia     

Platinum-group elements in rocks from the voikar-syninsky ophiolite complex,Polar Urals,U.S.S.R.

Analyses of platinum-group elements (PGE) in rocks collected from the Voikar-Syninsky ophiolite in the Polar Urals suggest that the distribution and geochemistry of PGE in this Paleozoic ophiolite are similar to those in Mesozoic ophiolites from elsewhere. Chondrite-normalized PGE patterns for chromitite, the tectonite unit, and ultramafic and mafic cumulate unit have negative slopes. These results are similar to those found for chromitites from other ophiolites; stratiform chromities show positive slopes. If the magmas that form both types of chromitite originate from similar mantle source material with respect to PGE content, the processes involved must be quite different. However, the distinct chondrite-normalized PGE patterns may reflect differing source materials.     

The distribution of divalent trace elements between sulfides,oxides, silicates and hydrothermal solutions: I. Thermodynamic basis

Experimental data for the standard Gibbs free energies of formation from the elements of a wide variety of metal sulfides and oxides, spinels, olivines and pyroxenes at 25°C and 1 bar define linear correlations, within about ±900 cal·mole^?1, with the corresponding conventional standard partial molal Gibbs free energies of formation of the aqueous M²⁺ cations of the form where a_MaZ and b_MaZ are empirically determined constants characteristic of the structure M_nZ. The only exceptions to correlations of this type are compounds of the heavy alkaline earths Ca, Sr and Ba, which appear to follow correlations with cation radius instead. The linear free energy correlations enable prediction of standard Gibbs free energies of formation of compositional end-members of a particular structure M_nZ provided that a_MaZ and b_MaZ are known accurately. When only the free energy of the Mg end-member is known, the standard Gibbs free energy of formation at 25°C and 1 bar of the Fe endmember, and hence a_MaZ and b_MaZ Can be predicted from the temperature independence of and estimated entropies and heat capacities for the Fe end-member. Using this approach, the free energies of ferrosilite, hedenbergite and annite at 25°C and 1 bar were predicted to within ±1000 cal·mole^?1 of the helgesonet al. (1978) values. Free energies of formation of talc (M₃Si₄O₁₀(OH)₂), clinchlore (M₅Al₂Si₃O₁₀(OH)₈), and tremolite (Ca₂M₅(Si₄O₁₁)₂(OH)₂)-type compounds where M is Mg, Mn, Zn, Fe, Co, or Ni were then predicted at 25°C and 1 bar.Calculation of the equilibrium distribution of Mg, Zn and Sr between galena and hydrothermal solution, and Zn, Mg, Fe and Mn between chlorite and hydrothermal solution demonstrates: (1) that the Sr contents of low temperature galenas (e.g. Mississippi Valley-type) should be negligible (reported analyses of Sr content and Sr isotopic composition of such galenas are probably attributable to fluid inclusions or carbonate inclusions); and (2), that the Zn contents of hydrothermal chlorites in a model of the midoceanic ridge hydrothermal systems are sensitive to temperature, to complexing in the aqueous phase, and to the overall Fe/Mg ratio of the chlorite.     

磁铁矿中微量元素和铂族元素的组成特征

文章分析了磁铁矿中铂族元素(PGE)含量的特征,发现磁铁矿中铂族元素富集为10-9级,主要为PPGE(即Pd,Pt,Rh)。富集PPGE的主要原因是其在热液活动的晚期阶段可以被轻微的再分配和富集,其含量的高低严格受岩浆结晶过程中氧逸度的控制。磁铁矿的结晶程度直接影响岩浆体系的氧逸度,控制了PGE的含量分布,进而影响成矿。     

GRV 13100顽火辉石球粒陨石中金属硫化物特征与成因

顽火辉石球粒陨石中的大量金属硫化物形成于早期极还原的太阳星云条件。GRV13100是一块发现于南极格罗夫山的顽火辉石球粒陨石,不透明矿物包括陨硫铁、陨硫铬铁矿、陨硫镁矿、陨硫钙矿、含硅铁纹石、陨磷铁矿、硅磷镍矿等金属硫化物和磷化物,总丰度达21%,经历了一定程度的热变质。通过对其岩石学和矿物化学特征研究,并和其它顽火辉球粒陨石进行对比分析,结果表明:(1)陨硫镁矿中FeS含量可以反映母体变质温度,GRV 13100中大部分陨硫镁矿变质温度为200℃～300℃,个别经历了400℃～800℃的高温,可能为外来吸入成因,或者代表了原始星云的凝聚或结晶温度;(2)陨硫镁矿形成于太阳星云的直接凝聚,并在橄榄石和顽火辉石冷凝结晶之后形成;(3)陨硫铁的成因分为原生和次生两种,原生的陨硫铁由太阳星云直接凝聚而成,次生的陨硫铁是在后期热变质过程中由铁镍金属经过硫化作用或者由陨硫镁矿分解而形成;(4)硅磷镍矿可能来自含硅铁纹石的出溶。本论文的研究工作为太阳系早期高度还原星云演化及其后期热变质提供了约束。     

The Merensky Cyclic Unit and its impact on footwall cumulates below Normal and Regional Pothole reef types in the Western Bushveld Complex

The Merensky Reef of the Bushveld Complex occurs in its highest stratigraphic position as a heterogeneous, pegmatitic, feldspathic melanorite bounded by two narrow chromitite stringers at the base of the Merensky Cyclic Unit (MCU). In the Swartklip Facies of the Rustenburg Layered Suite, the occurrence of widespread thermal and mechanical erosion termed “potholing” has led to the subdivision of the Merensky Reef into Normal Reef and Regional Pothole Reef sub-facies. The transition between the two sub-facies occurs where the MCU transgresses the lower chromitite stringer of the Normal Merensky Reef and cuts down into the underlying cumulate lithologies. In the Regional Pothole Reef at the Northam Platinum Mine, several economic reef types are identified, where the Merensky Reef becomes conformable to cumulate layering, in particular, to the footwall marker (NP2 reef type) and the upper pseudoReef (P2 reef type). The Normal Merensky Reef, as well as the P2 and NP2 Reefs, contains economic platinum group element (PGE) grades and includes the lower portion of the MCU melanorite and the Merensky Chromitite. Whole rock geochemistry indicates that this package is compositionally identical in Normal, P2, and NP2 Reefs, suggesting that the base of the MCU is a relatively homogeneous drape over both Normal and Regional Pothole Reef regions. However, the lower sections of the three Reefs are variables depending on the depth of transgression of the MCU. In the Normal and P2 reef types, transgression by the MCU was arrested within harzburgites, melanorites, and norites, resulting in coarse, pegmatitic textures in the immediate footwall units. For the NP2 Reef, transgression by the MCU was arrested within leucocratic rocks and resulted in the formation of troctolites below the Merensky Chromitite. These troctolites are characterised by a coupled relationship between olivine and sulphides and by changes in major element chemistry and PGE contents relative to equivalent units in the footwall of the Normal Reef. Along with micro-textural relationships, these features suggest that troctolization of leucocratic cumulates in the NP2 Reef beneath the Merensky chromitite was a result of a reactive infiltration of a chromite-saturated melt and an immiscible sulphide liquid from the overlying MCU, rather than a significant fluid flux from below. In all reef types, the concentration of S defines symmetrical peaks centred on the Merensky Chromitite (and chromitites from pre-existing cyclic units in Normal and P2 Reefs), whereas PGE concentrations define asymmetrical peaks with higher PGE contents in reconstituted footwall rocks relative to the MCU melanorite. This signature is attributable to a magmatic model of PGE collection followed by deposition towards the base of the MCU and within reconstituted footwall rocks. The continuity of the asymmetrical magmatic PGE signature between the Normal Reef and Regional Pothole Reef sub-facies indicates that PGE mineralization inherent to the Merensky magma occurred as a drape over a variably eroded and subsequent texturally and geochemically reworked or reconstituted footwall.