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1.
Deviations in the sulfur to selenium ratios (S/Se) from mantle values in magmatic Ni–Cu–Platinum Group Elements (PGE) sulfide deposits have been widely used to constrain the ore forming processes. Basically, S/Se ratios greater than mantle values are interpreted to be the result of contamination of the mantle derived magma by S-rich sedimentary rocks, whereas S/Se ratios lower than mantle values are thought to be the result of S loss during post-crystallization. However, there are many other processes involved in producing a deposit and it is possible that these may be also important in controlling S/Se ratios. In order to investigate the relative importance of these processes, we have compiled a data base of S, Se, δ34S and metal values from Ni–Cu–PGE sulfide deposits. This compilation shows that processes affecting S/Se ratios can be divided into two main classes: the magmatic processes and the late- to post-magmatic processes.
  • 1)Magmatic processes include the well-known addition of S from sedimentary rocks, variations in the sulfide to silicate liquid ratio (R-factor), depletion of the silicate magma in Se by early segregation of the sulfide liquid, and the moderate incompatibility of Se into the first sulfide minerals to crystallize from a sulfide liquid, the monosulfide-solid-solution (MSS). This incompatibility results in a change in S/Se ratio between the Fe-rich and Cu-rich zones of magmatic sulfide ores. The fractionation of Se during crystallization of sulfide liquids has not previously been appreciated.
  • 2)Late- to post-magmatic processes include: hydrothermal alteration, high-grade metamorphism, serpentinization and supergene weathering. Some metamorphosed Cu-deposits have low S/Se ratios suggesting S-loss by breakdown of sulfide minerals during a high-grade metamorphic event. However, the effectiveness of this process remains unclear and alternative models exist. The preferential remobilization of S relative to Se during hydrothermal alteration, serpentinization and supergene weathering leads to a moderate decrease of S/Se ratios values and can mask the initial S/Se ratio.
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2.
The configurational heat capacity, shear modulus and shear viscosity of a series of Na2O–Fe2O3–Al2O3–SiO2 melts have been determined as a function of composition. A change in composition dependence of each of the physical properties is observed as Na2O/(Na2O + Al2O3) is decreased, and the peralkaline melts become peraluminous and a new charge-balanced Al-structure appears in the melts. Of special interest are the frequency dependent (1 mHz–1 Hz) measurements of the shear modulus. These forced oscillation measurements determine the lifetimes of Si–O bonds and Na–O bonds in the melt. The lifetime of the Al–O bonds could not, however, be resolved from the mechanical spectrum. Therefore, it appears that the lifetime of Al–O bonds in these melts is similar to that of Si–O bonds with the Al–O relaxation peak being subsumed by the Si–O relaxation peak. The appearance of a new Al-structure in the peraluminous melts also cannot be resolved from the mechanical spectra, although a change in elastic shear modulus is determined as a function of composition. The structural shear-relaxation time of some of these melts is not that which is predicted by the Maxwell equation, but up to 1.5 orders of magnitude faster. Although the configurational heat capacity, density and shear modulus of the melts show a change in trend as a function of composition at the boundary between peralkaline and peraluminous, the deviation in relaxation time from the Maxwell equation occurs in the peralkaline regime. The measured relaxation times for both the very peralkaline melts and the peraluminous melts are identical with the calculated Maxwell relaxation time. As the Maxwell equation was created to describe the timescale of flow of a mono-structure material, a deviation from the prediction would indicate that the structure of the melt is too complex to be described by this simple flow equation. One possibility is that Al-rich channels form and then disappear with decreasing Si/Al, and that the flow is dominated by the lifetime of Si–O bonds in the Al-poor peralkaline melts, and by the lifetime of Al–O bonds in the relatively Si-poor peralkaline and peraluminous melts with a complex flow mechanism occurring in the mid-compositions. This anomalous deviation from the calculated relaxation time appears to be independent of the change in structure expected to occur at the peralkaline/peraluminous boundary due to the lack of charge-balancing cations for the Al-tetrahedra.  相似文献   

3.
Experimentally derived phase relations of arsenide in sulfide melt are presented to quantify the fractionation paths of As-bearing sulfide melts. When a natural sulfide melt reaches arsenide saturation, a separate Ni–PGE-rich arsenide melt exsolves. The arsenic saturation concentration in an Fe–Ni–Cu sulfide melt is between 0.5 and 1.5 wt%. The affinities of the chalcophile metals for an immiscible arsenide melt follow the order Pt > Pd > Ni ? Fe ≈ Cu. In natural systems, arsenide exsolution will be triggered by the activity of the nickel arsenide components dissolved in sulfide melt, Ni being the most common base metal with strong affinity to the Asn? anionic species. Arsenic may have a major effect on the fractionation paths of sulfide melts even if no separate arsenide phase forms. Arsenic, and probably many other chalcogens and metalloids in magmatic melts, may undergo associations with Pt and Pd well before discrete PGE minerals become stable phases.  相似文献   

4.
Liquid–liquid immiscibility has crucial influences on geological processes, such as magma degassing and formation of ore deposits. Sulfate, as an important component, associates with many kinds of deposits. Two types of immiscibility, including (i) fluid–melt immiscibility between an aqueous solution and a sulfate melt, and (ii) fluid–fluid immiscibility between two aqueous fluids with different sulfate concentrations, have been identified for sulfate–water systems. In this study, we investigated the immiscibility behaviors of a sulfate- and quartz-saturated Na2SO4–SiO2–H2O system at elevated temperature, to explore the phase relationships involving both types of immiscibility. The fluid–melt immiscibility appeared first when the Na2SO4–SiO2–H2O sample was heated to ~270°C, and then fluid–fluid immiscibility emerged while the sample was further heated to ~450°C. At this stage, the coexistence of one water-saturated sulfate melt and two aqueous fluids with distinct sulfate concentrations was observed. The three immiscible phases remain stable over a wide pressure–temperature range, and the appearance temperature of the fluid–fluid immiscibility increases with the increased pressure. Considering that sulfate components occur extensively in carbonatite-related deposits, the fluid–fluid immiscibility can result in significant sulfate fractionation and provides implications for understanding the formation of carbonatite-related rare earth deposits.  相似文献   

5.
6.
The Pb(II) and Ni(II) biosorption of a fungal biomass isolated from mine drainage of metal-processing industries in Balya (Bal?kesir province, Turkey) was optimized using a response surface methodology by altering parameters such as pH, initial metal concentration, contact time and biosorbent dosage. This strain was shown to be highly similar to Penicillium sp. Furthermore, zeta potential measurements and Fourier transform infrared spectroscopy were performed to understand the adsorption mechanism. A Box–Behnken design with 29 experiments was used to evaluate the interactions between independent variables. The results showed that the fungal biomass isolated from the metal mine drainage could have a significant environmental impact through the biosorption of Pb(II) and Ni(II) in waters polluted with heavy metals, particularly in the drainage from metal mines. The maximum removal values were 76 and 47 % at pH 4.5 for both Pb(II) and Ni(II), with 123 and 33 mg/L initial metal concentrations, 65 and 89 min contact times and 0.2 and 1.6 g/L biosorbent, respectively.  相似文献   

7.
Physical property measurements provide a critical link between geological observations and geophysical measurements and modelling. To enhance the reliability of gravity and magnetic modelling in the Yilgarn Craton's Agnew–Wiluna Greenstone Belt, mass and magnetic properties were analysed on 157 new rock samples and combined with an existing corporate database of field measurements. The new samples include sulfide ore, serpentinised and olivine-bearing ultramafic host-rocks, granitoid, and felsic and mafic volcanic and volcaniclastic country rock. Synthesis of the data provides a useful resource for future geophysical modelling in the region. Several rock types in the region have sufficiently distinct physical properties that a discriminant diagram is proposed to facilitate a basic classification of rock types based on physical properties. However, the accumulation of emplacement, metamorphic, hydrothermal and structural processes has complicated the physical properties of the rocks by imposing duplicate and sometimes opposing physical property trends. The data confirm that massive sulfide and ultramafic rocks have the most distinctive mass and magnetic properties but with variability imposed by their complex history. Sulfide content imposes the strongest control on densities, but can only be identified when comprising >10 vol% of the rock. The pyrrhotite-rich Ni-sulfide assemblages generally have similar magnetic properties to the host ultramafic rocks, but can have much lower susceptibilities where the thermal history of the rocks has favoured development of hexagonal pyrrhotite over monoclinic pyrrhotite. In ultramafic rocks that contain <10 vol% sulfides, density and susceptibility are primarily controlled by serpentinisation, with olivine breaking down to serpentine and magnetite in the presence of water. Serpentinisation dramatically lowered densities and increased susceptibilities, but had limited influence on the intensity of remanent magnetisation. All ultramafic rocks contain multidomain magnetite, and most contain low coercivity grains prone to overprinting by in situ viscous remanent magnetisation or drilling-induced isothermal remanent magnetisation during extraction. Despite the low coercivities, Koenigsberger ratios of 1–20 are observed indicating that viscous remanent magnetisation aligned parallel to the present Earth field must be considered in any magnetic modelling. It is also noted that coarser-grained intrusive varieties of all rock types (e.g. granite, gabbro) show remanent magnetisation intensities 1–2 orders of magnitude greater than their extrusive equivalents (felsic and basaltic volcanics).  相似文献   

8.
Experiments on water solubility in forsterite in the systems Mg2SiO4–K2Mg(CO3)2–H2O and Mg2SiO4–H2O–C were conducted at 7.5–14.0 GPa and 1200–1600 °C. The resulting crystals contain 448 to 1480 ppm water, which is 40–70% less than in the forsterite–water system under the same conditions. This can be attributed to lower water activity in the carbonate-bearing melt. The water content of forsterite was found to vary systematically with temperature and pressure. For instance, at 14 GPa in the system forsterite–carbonate–H2O the H2O content of forsterite drops from 1140 ppm at 1200 °C to 450 ppm at 1600 °C, and at 8 GPa it remains constant or increases from 550 to 870 ppm at 1300–1600 °C. Preliminary data for D-H-bearing forsterite are reported. Considerable differences were found between IR spectra of D-H- and H-bearing forsterite. The results suggest that CO2 can significantly affect the width of the olivine-wadsleyite transition, i.e., the 410-km seismic discontinuity, which is a function of the water content of olivine and wadsleyite.  相似文献   

9.
The thermal stability of sideronatrite, ideally Na2Fe3+(SO4)2(OH)·3(H2O), and its decomposition products were investigated by combining thermogravimetric and differential thermal analysis, in situ high-temperature X-ray powder diffraction (HT-XRPD) and Fourier transform infrared spectroscopy (HT-FTIR). The data show that for increasing temperature there are four main dehydration/transformation steps in sideronatrite: (a) between 30 and 40 °C sideronatrite transforms into metasideronatrite after the loss of two water molecules; both XRD and FTIR suggest that this transformation occurs via minor adjustments in the building block. (b) between 120 and 300 °C metasideronatrite transforms into metasideronatrite II, a still poorly characterized phase with possible orthorhombic symmetry, consequently to the loss of an additional water molecule; X-ray diffraction data suggest that metasideronatrite disappears from the assemblage above 175 °C. (c) between 315 and 415 °C metasideronatrite II transforms into the anhydrous Na3Fe(SO4)3 compound. This step occurs via the loss of hydroxyl groups that involves the breakdown of the [Fe3+(SO4)2(OH)] 2? chains and the formation of an intermediate transient amorphous phase precursor of Na3Fe(SO4)3. (d) for T > 500 °C, the Na3Fe(SO4)3 compound is replaced by the Na-sulfate thenardite, Na2SO4, plus Fe-oxides, according to the Na3Fe3+(SO4)3 → 3/2 Na2(SO4) + 1/2 Fe2O3 + SOx reaction products. The Na–Fe sulfate disappears around 540 °C. For higher temperatures, the Na-sulfates decomposes and only hematite survives in the final product. The understanding of the thermal behavior of minerals such as sideronatrite and related sulfates is important both from an environmental point of view, due to the presence of these phases in evaporitic deposits, soils and sediments including extraterrestrial occurrences, and from the technological point of view, due to the use of these materials in many industrial applications.  相似文献   

10.
The solubility of water in coexisting enstatite and forsterite was investigated by simultaneously synthesizing the two phases in a series of high pressure and temperature piston cylinder experiments. Experiments were performed at 1.0 and 2.0 GPa at temperatures between 1,100 and 1,420°C. Integrated OH absorbances were determined using polarized infrared spectroscopy on orientated single crystals of each phase. Phase water contents were estimated using the calibration of Libowitzky and Rossman (Am Mineral 82:1111–1115, 1997). Enstatite crystals, synthesized in equilibrium with forsterite and an aqueous phase at 1,350°C and 2.0 GPa, contain 114 ppm H2O. This is reduced to 59 ppm at 1,100°C, under otherwise identical conditions, suggesting a strong temperature dependence. At 1,350°C and 1.0 GPa water solubility in enstatite is 89 ppm, significantly lower than that at 2.0 GPa. In contrast water solubility in forsterite is essentially constant, being in the range 36–41 ppm for all conditions studied. These data give partition coefficients in the range 2.28–3.31 for all experiments at 1,350°C and 1.34 for one experiment at 1,100°C. The incorporation of Al2O3 in enstatite modifies the OH stretching spectrum in a systematic way, and slightly increases the water solubility.  相似文献   

11.
12.
Diamond crystallization has been studied in the SiO2–H2O–С, Mg2SiO4–H2O–С and H2O–С subsystems at 7.5 GPa and 1,600°C. We found that dissolution of initial graphite is followed by spontaneous nucleation of diamond and growth of diamond on seed crystals. In 15-h runs, the degree of graphite to diamond transformation [α = MDm/(MDm + MGr)100, where MDm is mass of obtained diamond and MGr mass of residual graphite] reached 100% in H2O-rich fluids but was only 35–50% in water-saturated silicate melts. In 40-h runs, an abrupt decrease of α has been established at the weight ratio H2O/(H2O + SiO2) ≤ 0.16 or H2O/(H2O + Mg2SiO4) ≤ 0.15. Our results indicate that α is a function of the concentration of water, which controls both the kinetics of diamond nucleation and the intensity of carbon mass transfer in the systems. The most favorable conditions for diamond crystallization in the mantle silicate environment at reliable PT-parameters occur in the fluid phase with low concentration of silicates solute. In H2O-poor silicate melts diamond formation is questionable.  相似文献   

13.
14.
According to the compositions of the underground gasfield brines in the west of Sichuan Basin,the phase equilibria in the ternary systems KBr-K2B4O7-H2O and KCl-K2B4O7-H2O at 373 K were studied using the isothermal dissolution equilibrium method.The solubilities of salts and the densities of saturated solutions in these ternary systems were determined.Using the experimental data,phase diagrams and density-composition diagrams were constructed.The two phase diagrams were simple co-saturation type,each having an invariant point,two univariant curves and two crystallization regions.The equilibrium solid phases in the ternary system KBr-K2B4O7-H2O are potassium bromide (KBr) and potassium tetraborate tetrahydrate (K2B4O7·4H2O),and those in the ternary system KCl-K2B4O7-H2O are potassium chloride (KCl) and potassium tetraborate tetrahydrate (K2B4O7·4H2O).Comparisons of the phase diagrams of the two systems at different temperatures show that there is no change in the crystallization phases,but there are changes in the size of the crystallization regions.As temperature increases,the solubility of K2B4O7·4H2O increases rapidly,so the crystallization field of K2B4O7·4H2O becomes smaller.  相似文献   

15.
Cobalt ( Co) and nickel (Ni) have similar geochemical behaviors and commonly co -vary in nature, but they may undergo decoupling in certain geological processes, especially in ore -forming processes, and the decoupling mechanism is not yet clear. This paper analyzes the distribution characteristics and migration behaviors of Co and Ni in major rock -forming minerals in different types of mafic-ultramafic rocks. The Ni (2500 x 10(-6) 3400 x 10(-6)) and Co (110 x 10(-6) 160 x 10(-6)) contents of mantle olivine are both higher than those of the primitive mantle. The Ni content shows no obvious correlation with the Fo value, while the Co content has a strong negative correlation with both the Fo value and the Ni/Co ratio. This indicates that partial melting does not cause significant changes in Ni content of olivine, but can control the Co content and the Ni/Co ratio, mainly due to the differences in compatibility between the two elements in olivine. Melt-rock reactions can cause significant Co-Ni decoupling between minerals and within minerals, but the mechanisms differ. In the process of reacting with basaltic magma, olivine mainly absorbs Co and loses Ni, while being affected by coexisting spinet minerals. When reacting with carbonatite melt, olivine loses Co, but Ni remains almost unchanged. As mantle derived basaltic magma intrudes into the lower crust, the migration of Co and Ni in pyroxenes is controlled by concentration gradients and sulfide crystallization. The local enrichment of Co provides an important material basis for the formation of Co -rich melts in deep crustal melting. During the differentiation and evolution of mafic-ultramafic magma, the chromite fractional crystallization and sulfide segregation can cause Co-Ni decoupling at both rock and/or mineral scales. Meanwhile, the enriched hydrous fluids released during chromite aggregation and sulfide melt solidification can significantly promote the efficiency of element exchange in sub-solidus state, especially strengthening the activity of Co, thus causing negative correlations between Co and Ni in olivine and even in chromite. Comparative studies show that the trends of Co and Ni content changes in mineral assemblages are evidently different, or even opposite, between mineralized and barren bodies and between ore -bearing and ore -free rocks, which provides a basis for identifying mineralization in rock bodies and guiding prospecting.  相似文献   

16.
17.
We define and calibrate a new model of molar volume as a function of pressure, temperature, ordering state, and composition for spinels in the supersystem (Mg, Fe2+)(Al, Cr, Fe3+)2O4 ? (Mg, Fe2+)2TiO4. We use 832 X-ray and neutron diffraction measurements performed on spinels at ambient and in situ high-P, T conditions to calibrate end-member equations of state and an excess volume model for this system. The effect on molar volume of cation ordering over the octahedral and tetrahedral sites is captured with linear dependence on Mg2+, Al3+, and Fe3+ site occupancy terms. We allow standard-state volumes and coefficients of thermal expansion of the end members to vary within their uncertainties during extraction of the mixing properties, in order to achieve the best fit. Published equations of state of the various spinel end members are analyzed to obtain optimal values of the bulk modulus and its pressure derivative, for each explicit end member. For any spinel composition in the supersystem, the model molar volume is obtained by adding excess volume and cation order-dependent terms to a linear combination of the five end-member volumes, estimated at pressure and temperature using the high-T Vinet equation of state. The preferred model has a total of 9 excess volume and order-dependent parameters and fits nearly all experiments to within 0.02 J/bar/mol, or better than 0.5 % in volume. The model is compared to the current MELTS spinel model with a demonstration of the impact of the model difference on the estimated spinel-garnet lherzolite transition pressure.  相似文献   

18.
The Outokumpu district within the North Karelia Schist Belt in eastern Finland hosts a number of Cu–Co–Zn–Ni–Ag–Au sulfide deposits that are associated with Palaeoproterozoic ophiolitic metaserpentinites derived from depleted mantle peridotites that were subsequently tectonically interleaved with allochthonous metaturbidites. The metaperidotites have been extensively metasomatized to quartz–carbonate–calc–silicate rocks of the Outokumpu assemblage. The Outokumpu area has been affected by a multiple-phase tectonic history comprising various phases of folding and shearing followed by several faulting events. Future exploration has to expand the search into deeper areas and requires knowledge of the subsurface geology. In order to unravel the complex structure 3D geologic models of different scales have been built using a variety of information including geological aeromagnetic and gravity maps, digital terrain models, and mine cross sections as well as data like drill core logs combined with observations from underground mine galleries, structural measurements, aeromagnetic data, and seismic surveys. For crustal structures, data from seismic surveys lines have been reprocessed for our purpose. Both deposit-scale and regional-scale models allow the reconstruction of a sequence of structural events. The mined ore has formed during remobilization of a proto-ore and is closely related to shear zones (thrusts) that truncate the Outokumpu assemblage. Later faults dismembered the ore explaining the variable depth of the different ore bodies along the Outokumpu ore zone. On larger scale at least four km-scale thrust sheets, separated by major listric shear zones can be identified in the ore belt, which are internally further imbricated by subordinate shear zones. These thrusts separate a number of lens-shape metaperidotite bodies that are probably surrounded by Outokumpu assemblage rocks. Thrust stacking was followed by at least three stages of faulting that divided the ore belt into fault-bounded blocks with heterogeneous displacements: (i) faulting along NW-dipping faults with unresolved kinematics, (ii) reverse faulting along c. 50°–60° SE-dipping faults, and (iii) SW–NE to SSW–NNE striking faults which may have formed at an earlier stage and have been reactivated.The specific Outokumpu alteration assemblage around metaperidotite bodies combined with shear zones acting as path ways for fluids are the main vectors to mineralization. Seismic reflection data do not provide a simple tool to directly detect the sites of Outokumpu assemblage bodies at depth but they identify strong reflector zones which are characteristic for though not exclusive to the assemblage, shear zones can be recognized as curved dislocations in the seismic lines. Our study shows that 3D modeling, when used in combination with surface geology and other geophysical data and good knowledge about the structural evolution clearly improves the interpretation of reflectors and enables the identification of strong reflector packages as Outokumpu assemblage that, due to absent geological control, have first been mapped as “unknown reflector”. It thus enhances the chances for locating potentially economic horizons at depth and to delineate target areas for detailed exploration.  相似文献   

19.
Perseverance is a world-class, komatiite-hosted nickel sulphide deposit situated in the well-endowed Leinster nickel camp of the Agnew–Wiluna greenstone belt, Western Australia. The mine stratigraphy at Perseverance trends north-northwest (NNW), dips steeply to the west, and is overturned. Stratigraphic footwall units lie along the western margin of the Perseverance Ultramafic Complex (PUC). The PUC comprises a basal nickel sulphide-bearing orthocumulate- to mesocumulate-textured komatiite that is overlain by a thicker, nickel sulphide-poor, dunite lens. Hanging wall rocks include rhyodacite that is texturally and compositionally similar to footwall volcanic rocks. These rocks separate the PUC from a second sequence of nickeliferous, E-facing, spinifex-textured komatiite units (i.e. the East Perseverance komatiite). Past workers argue for a conformable stratigraphic contact between the PUC and the East Perseverance komatiite and conclude that the PUC is extrusive. This study, however, clearly demonstrates that these komatiite sequences are discordant, implying that the PUC may have intruded rhyodacite country rock as a sill with subsequent structural juxtaposition against the East Perseverance komatiite. Early N–S shortening associated with the regional DI deformation event (corresponding to the local DP1 to DP3 events at Perseverance) resulted in the heterogeneous partitioning of strain along the margins of the competent dunite. A mylonite developed in the more ductile footwall rocks along the footwall margin of the PUC, while isoclinal F3 folds, such as the Hanging wall limb and Felsic Nose folds, formed in low-mean stress domains along the fringes of the elongated dunite lens. Strata-bound massive and disseminated nickel sulphides were passively fold thickened in hinge areas of isoclinal folds, whereas basal massive sulphides lubricated fold limbs and promoted thrust movement along shallowly dipping lithological contacts. Massive sulphides were physically remobilised up to 20 m from their primary footwall position into deposit-scale fold hinges to form the 1A and Felsic Nose orebodies. First-order controls on the geometry of the Perseverance deposit include the thermomechanical erosion of footwall rocks and the channelling of the mineralised komatiitic magma. Second- or third-order controls are several postvolcanic deformation events, which resulted in the progressive folding and shearing of the footwall contact, as well as the passive fold thickening of massive and disseminated sulphide orebodies. Massive sulphides were physically remobilised into multiple generations of fold hinges and shear zones. Important implications for near-mine exploration in the Leinster camp include identifying nickeliferous komatiite units, defining their three-dimensional geometry, and targeting fold hinge areas. Fold plunge directions and stretching lineations are indicators of potential plunge directions of massive sulphide orebodies.  相似文献   

20.
Geotechnical and Geological Engineering - In this paper, the possibility of using fine scrap tyre&nbsp;rubber to improve the mechanical properties of soil subjected to cyclic loading is...  相似文献   

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