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1.
We present a new formulation to describe the thermodynamics of liquids in the system O-S-Fe. The model is based on an associated regular solution formulation. According to this model, liquids in the O-S-Fe ternary are made up of an equilibrium solution of the six melt species S, Fe, FeO, FeO1.5, FeS and FeOS. The model presented here represents oxygen and sulfur fugacities as well as phase equilibria with stoichiometric solid phases better than models from the literature on O-Fe and S-Fe binaries. Furthermore, this model represents a substantial improvement on the model of Kress (1997), which is the only other thermodynamic model available in the ternary system. Asymmetric regular solution parameters are required along the FeO join in order to reproduce experimental data with the chosen list of species. Symmetric regular solution parameters are required along the Fe-S binary. Mixing between any of the species considered and FeOS close to ideal. The associated solution model presented here will serve as a more solid foundation for future models in O-S-Fe- Ni-Cu liquids. Efficient and robust strategies for calculating equilibrium speciation and estimating model parameters are presented. Received: 15 June 1999 / Accepted: 5 February 2000  相似文献   

2.
Ultrasonic longitudinal acoustic velocities in oxidized silicate liquids indicate that the pressure derivative of the partial-molar volume of Fe2O3 is the same in iron-rich alkali-, alkaline earth- and natural silicate melt compositions at 1 bar. The dV/dP for multicomponent silicate liquids can be expressed as a linear combination of partial-molar constants plus a positive excess term for Na2O−Al2O3 mixing. Partial-molar properties for FeO and Fe2O3 components allow extension of the empirical expression of Sack et al. (1980) to permit the calculation of Fe-redox equilibrium in a natural silicate liquid as a function of composition, temperature, fo2 and pressure; a more formal thermodynamic expression is presented in the Appendix. The predicted equilibrium fo2 of natural silicate melts, of fixed oxygen content, closely parallels that defined by the metastable assemblage fayalite+magnetite+β-quartz (FMQ), in pressure-temperature space. A silicate melt initially equilibrated at 3 GPa and FMQ, will remain within approximately 0.5 log10 units of FMQ during its closed-system ascent. Thus, for magmas closed to oxygen, iron-redox equilibrium in crystal-poor pristine glassy lavas represents an excellent probe of the relative oxidation state of their source regions.  相似文献   

3.
Experiments were performed in the system O–S–Fe–Ni designed to extend our understanding of the chemistry of sulfide liquids. Results indicate that adding nickel to Fe-rich sulfide liquids in equilibrium with silicate liquids extends their stability field to much higher oxygen fugacities and lower sulfur fugacities. Increasing Ni/Fe at a given temperature and sulfur and oxygen fugacity is accompanied by a significant decrease in the oxygen content of the sulfide liquid. Results of these experiments are combined with data from the literature to calibrate an associated regular solution model for O–S–Fe–Ni liquids. This model represents a complete refit of the associated regular solution model of Kress (Contrib Mineral Petrol 139:316–325, 2000). The resulting model is combined with the olivine solution model of Hirschmann (Am Mineral 76:1232–1248, 1991) to explore the effect of variations in oxygen and sulfur fugacities on the distribution of Fe and Ni between olivine and sulfide liquid. Predicted olivine–sulfide distribution trends parallel those observed by Gaetani and Grove (Geochim Cosmochim Acta 61:1829–1846, 1997), Gaetani and Grove (Earth Planet Sci Lett 169:147–163, 1999), Brenan and Caciagli (Geochim Cosmochim Acta 64:307–320, 2000) and Brenan (Geochim Cosmochim Acta 67:2663–2681, 2003), but are systematically offset toward lower predicted Ni in the sulfide. Nevertheless our results are consistent with the assertion that low K D os values in magmatic ore deposits such as the J-M Reef reflect high iron contents in the sulfides combined with relatively high oxygen fugacities.
Victor KressEmail:
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4.
The effect of Rayleigh distillation by outgassing of SO2 and H2S on the isotopic composition of sulfur remaining in silicate melts is quantitatively modelled.A threshold mole fraction of sulfur in sulfide component of the melts is reckoned to be of critical importance in shifting the δ^34S of the melts mith respect to the original magmas.The partial equilibrium fractionation in a magmatic system is evaluated by assuming that a non-equilibrium flux of sulfur occurs between magmatic volatiles and the melts,while an equilibrium fractionation is approached between sulfate and sulfide within the melts.The results show that under high fo2 conditions,the sulfate/sulfide ratio in a melt entds to increase,and the δ^34S value of sulfur in a solidified rock might then be shifted in the positive direction.This may either be due to Rayleigh outgassing in case the mole fraction of sulfide is less than the threshold,or due to a unidirectional increase in δ^34S value of the sulfate with decreaing temperature,Conversely,at low fo2,the sulfate/sulfide ratio tends to decrease and the δ^34S value of total sulfur could be driven in the negative direction,either because of the Rayleigh outgassing in case the mole fraction of sulfide is greater than the threshold,or because of a unidirectional decrease inδ^34S value of the sulfide.To establish isotopic equilibrium between sulfate and sulfide,the HM,QFM or WM buffers in the magmatic system are suggested to provide the redox couple that could simultaneously reduce the sulfate and oxidize the sulfide.CaO present in the silicatte Melts is also called upon to participate in the chemical equilibrium between sulfate and sulfide,Consequently,the δ^34S value of an igneous rock could considerably deviate from that of its original magma due to the influence of oxygen fugacity and temperature at the time of magma solidification.  相似文献   

5.
On the basis of experimental works in the FeS-FeO-SiO2(-Fe3O4 or -Na2O) system with synthetic ZnS or PbS, the partition of zinc and lead between silicate and sulfide liquids is shown to be affected by the oxygen content of the sulfide liquids. The partition coefficients K, metal wt. % in sulfide liquid / metal wt. % in silicate liquid, for zinc and lead go through a minimum at relatively low oxygen contents of the sulfide liquids. KZn and KPb for natural sulfide liquids in equilibrium with basic magmas near the earth's surface are estimated at 0.1–0.5 and greater than 10, respectively. Although KZn and KPb change appreciably with oxygen content of the sulfide liquids, they never become sufficiently high to concentrate zinc and lead in economic amounts in magmatic sulfide ores.  相似文献   

6.
 Interactions between several silicate and metallic phases are studied by applying a self consistent thermodynamic approach and using recent thermodynamic data. We compute proportions and compositions of oxidized silicates and of reduced metallic phase in equilibrium at various temperatures and oxygen fugacities. The empirically observed activity-composition relationships for ternary metallic alloys are used and their applications to a general thermodynamic expression for a non-regular ternary system is explicitly discussed. We show that the stability limits of olivines and pyroxenes with respect to precipitation of metallic phases under reducing conditions are directly related to the presence of nickel impurities. We precisely evaluate the modifications of the stability limits as a function of nickel content. For typical mantle olivines [Fe/(Fe+Mg) = 0.1] the stability limits are given for values of x Ni= Ni/(Ni+Fe+Mg) ranging from 10 ppm to 1% by: ln f O2=−39.83+ 7.86 ln x Ni, ln f O2=−14.68+6.21 ln x Ni, at 900 K and 1600 K, respectively. Received: 17 November 1999 / Accepted: 14 May 2000  相似文献   

7.
Summary Pyroclastites erupted from the Upper Pollara magma chamber (13 ka, Salina Island, Aeolian Archipelago) resulted from mingling and mixing of rhyolitic and andesitic magmas. An experimental study has been conducted on the rhyolitic end-member to constrain the pre-eruptive conditions of the magma. In order to check for the role of mixing on the equilibrium phase assemblage, three different starting compositions, corresponding to three different mixing degrees, have been used. The crystallization experiments were conducted at two different oxygen fugacities and at variable temperature and fluid contents. The results indicate that the natural mineralogical assemblage can only be reproduced from a composition showing a certain degree of mixing. Assuming a pressure of 200 MPa (generally accepted for the Aeolian Islands), the pre-eruptive temperature of the magmas is estimated between 755 and 800 °C and the water content of the melt was higher than 4–4.5 wt.%. The Upper Pollara magma crystallized at relatively high fO2 (ΔlogfO2 = Ni–NiO + 1 log unit), compared to rhyolitic magmas from Lipari and Vulcano. As this difference has not been observed for the most primitive magmas the difference in fO2 could be related to different degassing processes operating in Salina and Lipari – Vulcano magmas.  相似文献   

8.
We have performed experiments to constrain the effect of sulfur fugacity (fS2) and sulfide saturation on the fractionation and partitioning behavior of Pt, Pd and Au in a silicate melt–sulfide crystal/melt–oxide–supercritical aqueous fluid phase–Pt–Pd–Au system. Experiments were performed at 800 °C, 150 MPa, with oxygen fugacity (fO2) fixed at approximately the nickel–nickel oxide buffer (NNO). Sulfur fugacity in the experiments was varied five orders of magnitude from approximately log fS2 = 0 to log fS2 = −5 by using two different sulfide phase assemblages. Assemblage one consisted initially of chalcopyrite plus pyrrhotite and assemblage two was loaded with chalcopyrite plus bornite. At run conditions pyrrhotite transformed compositionally to monosulfide solid solution (mss), chalcopyrite to intermediate solid solution (iss), and in assemblage two chalcopyrite and bornite formed a sulfide melt. Run-product silicate glass (i.e., quenched silicate melt) and crystalline materials were analyzed by using both electron probe microanalysis and laser ablation inductively coupled plasma mass spectrometry. The measured concentrations of Pt, Pd and Au in quenched silicate melt in runs with log fS2 values ranging from approximately 0.0 to −5.0 do not exhibit any apparent dependence on fS2. The measured Pt, Pd and Au concentrations in mss do vary as a function of fS2. The measured Pt, Pd and Au concentrations in iss do not appear dependent on fS2. The data suggest that fS2, working in concert with fO2, via the determinant role that these variables play in controlling the magmatic sulfide phase assemblage and the solubility of Pt, Pd and Au as lattice bound components in magmatic sulfide phases, is a controlling factor on the budgets of Pt, Pd and Au during the evolution of magmatic systems.  相似文献   

9.
Differences between the δ18O values of Si- and Fe-rich immiscible liquids in the system Fe2SiO4-KAlSi2O6-SiO2 (Fa-Lc-Q) in isothermal experiments at 0.1 MPa have been determined experimentally to be 0.6 permil. The observed partition of 18O into the Si-rich liquid is consistent with previous experience with the preferential partition of 18O into Si-rich minerals in isothermal equilibrium with minerals of less polymerized structure. Crystallochemical principles affect the distribution of oxygen isotopes in coexisting isothermal liquids in the same way as they apply to isothermally coexisting crystals. The effects of Soret (thermal) diffusion on the distribution of oxygen isotopes in silicate liquids above the solvus in the system Fa-Lc-Q under conditions of an imposed temperature gradient of ca. 250 °C over 4 mm and at 2 GPa have also been investigated experimentally. Both the magnitude and the direction of separation of oxygen isotopes as a result of Soret diffusion are unexpected. For each of the silicate liquids, the cold end of the charge is enriched in 18O by up to 4.7 permil, and the highest δ18O values are associated with the most silica-poor compositions. The distribution of oxygen isotopes appears to be similar in each liquid, regardless of their chemical compositions, which is in contrast to the behaviour of cations whose distributions are compositionally dependent and characterized by strong crystallochemical effects wherein network-forming species such as Si and Al separate to the hot end and Mg, Fe and Ca are segregated preferentially to the cold end. Structural units in the melts are evidently less selective between oxygen isotopes than between cations, because oxygen redistribution over all possible sites in these units proceeds according to mass. Self-diffusion coefficients of oxygen in basaltic liquids estimated from the Soret experiments are in accord with those from other isotope tracer experiments, and comparable to those of Si. The possible effects of Soret diffusion on the oxygen isotopic composition of metasomatic veins in the mantle are examined in light of these data, and indicate that decay of the thermal gradients in the veins exceeds that of the diffusion of oxygen needed to produce variations in the δ18O values of mantle minerals. Variations in oxygen isotope ratios in most natural systems as a result of Soret effects are unlikely. Received: 6 January 1997 /  Accepted: 28 June 1998  相似文献   

10.
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  相似文献   

11.
To interpret the degassing of F-bearing felsic magmas, the solubilities of H2O, NaCl, and KCl in topaz rhyolite liquids have been investigated experimentally at 2000, 500, and ≈1 bar and 700° to 975 °C. Chloride solubility in these liquids increases with decreasing H2O activity, increasing pressure, increasing F content of the liquid from 0.2 to 1.2 wt% F, and increasing the molar ratio of ((Al + Na + Ca + Mg)/Si). Small quantities of Cl− exert a strong influence on the exsolution of magmatic volatile phases (MVPs) from F-bearing topaz rhyolite melts at shallow crustal pressures. Water- and chloride-bearing volatile phases, such as vapor, brine, or fluid, exsolve from F-enriched silicate liquids containing as little as 1 wt% H2O and 0.2 to 0.6 wt% Cl at 2000 bar compared with 5 to 6 wt% H2O required for volatile phase exsolution in chloride-free liquids. The maximum solubility of Cl− in H2O-poor silicate liquids at 500 and 2000 bar is not related to the maximum solubility of H2O in chloride-poor liquids by simple linear and negative relationships; there are strong positive deviations from ideality in the activities of each volatile in both the silicate liquid and the MVP(s). Plots of H2O versus Cl− in rhyolite liquids, for experiments conducted at 500 bar and 910°–930 °C, show a distinct 90° break-in-slope pattern that is indicative of coexisting vapor and brine under closed-system conditions. The presence of two MVPs buffers the H2O and Cl− concentrations of the silicate liquids. Comparison of these experimentally-determined volatile solubilities with the pre-eruptive H2O and Cl− concentrations of five North American topaz and tin rhyolite melts, determined from melt inclusion compositions, provides evidence for the exsolution of MVPs from felsic magmas. One of these, the Cerro el Lobo magma, appears to have exsolved alkali chloride-bearing vapor plus brine or a single supercritical fluid phase prior to entrapment of the melt inclusions and prior to eruption. Received: 6 November 1995 / Accepted: 29 January 1998  相似文献   

12.
The Portneuf–Mauricie Domain (PMD), located in the south-central part of the Grenville province, contains Mesoproterozoic Ni–Cu ± platinum-group element (PGE) prospects hosted in a variety of plutonic intrusions (layered, with simple structures, or zoned) and emplaced in a mature island arc setting. A two-stage model is envisaged to explain the formation of magmatic sulfides. An early loss of a small amount of sulfides in the conduits of primitive, hydrous mantle-derived melts under high fO2, resulted in depletion of the magmas in chalcophile and precious metals (Cu/Pd ratios vary from initial mantle values up to 1.6 × 106). Then, nearer the mineralized zones, the magmas interacted with sulfide-bearing country rocks, resulting in felsification of the magmas, assimilation of crustal sulfur (δ 34S values up to +5.5‰), and the formation of an immiscible sulfide liquid. Liquid-sulfide formation was followed by variable interactions between the silicate and sulfide magmas, which were responsible for the enrichment of sulfides in Ni, Cu, and, locally, PGE. Indeed, low R factors are found for prospects hosted in intrusions with a simple internal structure and in layered intrusions whereas high R factors are found for prospects hosted in zoned intrusions. Finally, sulfide melt may have been partly incorporated into later pulses of magma and injected into shallow magma chambers to form the PMD prospects. The PMD prospects share common characteristics with other well-known deposits (Aguablanca, Vammala, Stormyrplunen, and deposits in Alaskan/Ural-type intrusions), attesting to the Ni, Cu, and PGE potential of deposits associated with subduction-zone settings.  相似文献   

13.
The Janggun iron deposits, Republic of␣Korea, occur as lens-shaped magnesian skarn, magnetite and base-metal sulfide orebodies developed in the Cambrian Janggun Limestone Formation. Mineralization stage of the deposits can be divided into two separate events. The skarn stage (107 Ma) consists of magnetite, pyrrhotite, base-metal sulfides, carbonates and magnesian skarn minerals. The hydrothermal stage (70 Ma) consists of base-metal sulfides, native bismuth, bismuthinite, tetrahedrite, boulangerite, bournonite and stannite. Mineral assemblages, chemical compositions and thermodynamic considerations indicate that formation temperatures, −log fs2 and −log fo2 values of ore fluids from the skarn stage were 433 to 345 °C, 8.1 to 9.7 bar and 29.4 to 31.6 bar, and the hydrothermal stage was 245 to 315 °C, 10.4 to 13.2 bar and 33.6 to 35.4 bar, respectively. Thermochemical considerations indicate that the XCO2 during magnesian skarnization ranged from 0.06 to 0.09, and the activity of H+ presumably decreased when the fluids equilibrated with host dolomitic limestone which resulted in a pH change from about 6.1 to 7.8, and decreases in fo2 and fs2. The δ34S values of ore sulfides have a wide range from 3.2 to 11.6 ‰ (CDT). Calculated 34SH2 S values of ore fluids are 2.9 to 5.4 ‰ (skarn stage) and 8.7 to 13.5 ‰ (hydrothermal stage). These are interpreted to represent an initial deep-seated, igneous source of sulfur which gave way to influence of oxidized sedimentary sulfur to hydrothermal stage. The δ13C values of carbonates in ores range from −4.6 to −2.5 ‰ (PDB). It is likely that carbon in the ore fluids was a mixture of deep-seated magmatic carbon and dissolved carbon of dolomitic limestone. The δ18OH2 O and δD values (SMOW) of water in the ore fluids were 14.7 to 1.8 and −85 to −73 ‰ during the skarn stage and 11.1 to −0.2 and −87 to −80 ‰ in the hydrothermal stage. Received: 5 March 1997 / Accepted: 28 August 1997  相似文献   

14.
World-class Ni-Cu-PGE deposits: key factors in their genesis   总被引：55，自引：0，他引：55  
Magmatic Ni-Cu sulfide deposits form as the result of segregation and concentration of droplets of liquid sulfide from mafic or ultramafic magma, and the partitioning of chalcophile elements into these from the silicate melt. Sulfide saturation of a magma is not enough in itself to produce an ore deposit. The appropriate physical environment is required so that the sulfide liquid mixes with enough magma to become adequately enriched in chalcophile metals, and then is concentrated in a restricted locality so that the resulting concentration is of ore grade. The deposits of the Noril'sk region have developed within flat, elongate bodies (15 × 2 × 0.2 km) that intrude argillites, evaporites and coal measures, adjacent to a major, trans-crustal fault and immediately below the centre of a 3.5 km-thick volcanic basin. Studies of the overlying basalts have shown that lavas forming a 500 m-thick sequence within these have lost 75% of their Cu and Ni and more than 90% of their PGE. Overlying basalts show a gradual recovery in their chalcophile element concentrations to reach “normal” values 500 m above the top of the highly depleted zone. The ore-bearing Noril'sk-type intrusions correlate with those basalts above the depleted zone that contain “normal” levels of chalcophile elements. The high proportion of sulfide (2–10 wt.%) associated with the Noril'sk-type intrusions, the high PGE content of the ores, the extensive metamorphic aureole (100–400 m around the bodies), and the heavy sulfur isotopic composition of the ores (+8–+12 ∂34S) are explicable if the ore-bearing bodies are exit conduits from high level intrusions, along which magma has flowed en route to extrude at surface. The first magma to enter these intrusions reacted with much evaporitic sulfur, at a low “R” value and thus gave rise to sulfides with low metal tenors. Successive flow of magma through the system progressively enriched the sulfides in the conduits, losing progressively less of their chalcophile metals, and thus accounting for the upward increase in metals in successive lava flows above the highly depleted flows. The Voisey's Bay deposit lies partly within a 30–100 m-thick sheet of troctolite, interpreted as a feeder for the 1.334 Ga Voisey's Bay intrusion, and partly at the base of this intrusion, where the feeder adjoins it. Studies of olivine compositions indicate that an early pulse of magma through the feeder and into the intrusion was Ni depleted but that subsequent pulses were much less depleted. Trace element, Re-Os and S and O isotope data, and mineralogical studies indicate that the magma pulses interacted with country gneiss, probably principally in a deeper level intrusion, extracting SiO2, Na2O, K2O and possibly sulfur form the gneiss, which accounts for the magma becoming sulfide saturated. The Jinchuan deposit of north central China occurs within a 6 km-long dyke-like body of peridotite. The compositions of olivine within the dyke, the igneous rocks themselves, and the ore are all inconsistent with derivation of the body from ultramafic magma, as originally supposed, and indicate that the structure forms the keel of a much larger intrusion of magnesian basalt magma. Flow of magma into the intrusion has resulted in olivine and sulfide being retained where the keel was widening out into the intrusion. The West Australian komatiite-related deposits occur in thermal erosional troughs which have developed due to the channelisation of magma flow and the resulting thermal erosion of underlying sediments and basalt by the hot komatiite magma. The sediments are sulfide-rich, and may have contributed substantially to the sulfide of the ores. The mineralisation in the Duluth complex occurs in troctolitic intrusions along the western margin of the complex as a result of magma interacting with and extracting sulfur from the underlying graphite- and sulfide-bearing sediments. No magma flow channels have been identified so far, and the lack of magma flow subsequent to the development of sulfide immiscibility is regarded as the reason why these deposits are not of economic grade. When most major Ni-Cu sulfide deposits are compared, they prove to have a number of features in common; olivine-rich magma, proximity to a major crustal fault, sulfide-bearing country rocks, chalcophile element depletion in related intrusive or extrusive rocks, field and/or geochemical evidence of interaction between the magma and the country rocks, and the presence of or proximity to a magma conduit. The features are thought to explain the three key requirements (sulfide immiscibilty, adequate mixing between sulfides and magma, and localisation of the sulfides) discussed and have important implications with respect to exploration. Received: 9 January 1998 / Accepted: 21 September 1998  相似文献   

15.
Petrographic, electron microprobe, and bulk-rock geochemical analyses indicate that the distribution and composition of ferromagnesian silicates (biotite, garnet, and staurolite) in and adjacent to the metamorphosed Bleikvassli Zn–Pb–(Cu) volcanogenic massive sulfide deposit, Norway, are dependent upon the competing effects of f O2–f S2 and host-rock composition. The enrichment in magnesium content of these silicates within the orebody and at distances of as much as 5–10 m away is due to the increased f O2 and f S2 conditions imposed on the silicates in zones subject to minor hydrothermal alteration during regional metamorphism. Alternatively, within pelitic country rocks at distances >5–10 m from ore, the host-rock chemistry controls the composition of metamorphic silicate minerals. Also, country rocks within a few meters of ore are distinguished by the common presence of zinc-bearing staurolite (up to 9 wt% ZnO) coexisting with biotite ± garnet. Rocks in the Bleikvassli deposit were hydrothermally enriched in zinc and fluorine prior to metamorphism. The fluorine resides mainly in biotite, which is an additional contributing factor to the magnesium enrichment of that mineral due to Fe2+–F avoidance. Our inference that the sulfidation–oxidation halo around the Bleikvassli ore deposit is only meters in width contrasts with the view of Maiga (1983), who proposed the effects of sulfidation could be identified at distances >159 m from ore. It is evident that the delineation of a sulfidation–oxidation halo bordering a metamorphosed massive sulfide deposit must be done carefully in order to discriminate between the effects due to variations in primary rock composition versus those resulting from a sulfur and oxygen fugacity gradient between the massive sulfides and the sulfur-poor country rocks. Received: 1 March 1998 / Accepted: 3 May 2000  相似文献   

16.
Gossan Hill is an Archean (∼3.0 Ga) Cu–Zn–magnetite-rich volcanic-hosted massive sulfide (VHMS) deposit in the Yilgarn Craton of Western Australia. Massive sulfide and magnetite occur within a layered succession of tuffaceous, felsic volcaniclastic rocks of the Golden Grove Formation. The Gossan Hill deposit consists of two stratigraphically separate ore zones that are stratabound and interconnected by sulfide veins. Thickly developed massive sulfide and stockwork zones in the north of the deposit are interpreted to represent a feeder zone. The deposit is broadly zoned from a Cu–Fe-rich lower ore zone, upwards through Cu–Zn to Zn–Ag–Au–Pb enrichment in the upper ore zone. New sulfur isotope studies at the Gossan Hill deposit indicate that the variation is wider than previously reported, with sulfide δ34S values varying between −1.6 and 7.8‰ with an average of 2.1 ± 1.4‰ (1σ error). Sulfur isotope values have a broad systematic stratigraphic increase of approximately 1.2‰ from the base to the top of the deposit. This variation in sulfur isotope values is significant in view of typical narrow ranges for Archean VHMS deposits. Copper-rich sulfides in the lower ore zone have a narrower range (δ34S values of −1.6 to 3.4‰, average ∼1.6 ± 0.9‰) than sulfides in the upper ore zone. The lower ore zone is interpreted to have formed from a relatively uniform reduced sulfur source dominated by leached igneous rock sulfur and minor magmatic sulfur. Towards the upper Zn-rich ore zone, an overall increase in δ34S values is accompanied by a wider range of δ34S values, with the greatest variation occurring in massive pyrite at the southern margin of the upper ore zone (−1.0 to 7.8‰). The higher average δ34S values (2.8 ± 2.1‰) and their wider range are explained by mixing of hydrothermal fluids containing leached igneous rock sulfur with Archean seawater (δ34S values of 2 to 3‰) near the paleoseafloor. The widest range of δ34S values at the southern margin of the deposit occurs away from the feeder zone and is attributed to greater seawater mixing away from the central upflow zone. Received: 10 June 1999 / Accepted: 28 December 1999  相似文献   

17.
Equilibrium volumes and expansivities of three liquids in the system anorthite (CaAl2Si2O8)–diopside (CaMgSi2O6) have been derived from dilatometric measurements of the equilibrium length of samples in the glass transition range. The typical temperature range of 40 K for the measurements is limited at low temperature by the very long times necessary to reach structural equilibrium and at high temperature by the penetration of the rod used to measure sample dilatation. Despite such narrow intervals, the expansivities are determined to better than 3% thanks to the high precision with which length changes are measured. The coefficient of volume thermal expansion (1/V dV/dT) of the fully relaxed liquid just above the glass transition is found to decrease linearly from diopside composition (139 ± 4 × 10−6 K−1) to anorthite composition (59 ± 2 × 10−6 K−1). These values are greater than those determined for the same liquids at superliquidus temperatures, demonstrating that expansivities of silicate melts may decrease markedly with increasing temperature. A predictive model based upon partial molar volumes which vary as a linear function of the logarithm of temperature is proposed. Received: 25 February 2000 / Accepted: 29 May 2000  相似文献   

18.
The Voisey's Bay nickel–copper deposit and the Pants Lake sulfide occurrences are the most important mineral systems discovered to date within the Nain Plutonic Suite in northern Labrador. There are many intriguing similarities at both locations. Both are hosted by relatively small troctolite/gabbro bodies that intrude the sulfide-bearing paragneiss of the Churchill Province, and these intrusions contain inclusions of the paragneiss. Similar chemical reactions of the gneissic inclusions with the host magmas are observed at both locations. The reactions resulted in the addition of SiO2, K2O, Na2O and sulfur to the magmas, and are responsible for sulfide-saturation and resultant segregation of immiscible sulfide liquids from the magmas. The initial sulfide liquids in both cases were relatively poor in metals, containing <2.5 wt% Ni and 2 wt% Cu. The sulfides at Pants Lake remained poor in metals because of a lack of subsequent interaction with new, chalcophile-undepleted magma. At Voisey's Bay, the initial sulfides segregated in a dynamic conduit, and were subsequently upgraded in metals to ∼6 wt% Ni and 3 wt% Cu by a new surge of undepleted magma using the same conduit. These sulfides were then concentrated to form large sulfide bodies in the wider parts of the conduit and its entry to an upper chamber in response to a sudden change of liquid velocity in these environments. This study confirms three of the most important factors for the formation of magmatic sulfide deposits in an evolved magma system: (1) contamination of magma with sulfide-bearing country rock to achieve sulfide saturation; (2) a dynamic magmatic system such as a magma conduit to transport large volume of sulfide liquid and to concentrate them in limited localities, and (3) upgrading of metals in the sulfide by new, chalcophile-undepleted magma. Received: 20 February 2000 / Accepted: 14 September 2000  相似文献   

19.
Garnet + liquid equilibrium   总被引：1，自引：0，他引：1  
New experiments were performed to determine saturation conditions for garnet and silicate liquid. Starting compositions were natural basalt powders ranging from komatiite to nephelinite, which were partially melted at pressures between 25 and 100 kbar. Rounded grains of natural pyrope or grossular were added to some experiments to induce garnet saturation, and to aid the segregation of liquid pools for microprobe analysis. Simple expressions describing K eq as a function of P, T and liquid composition were calibrated by linear least squares analysis of the data from this, and other, studies. Since garnets do not often occur as phenocrysts, equations were designed to predict garnet compositions when P, T and a silicate liquid composition are given. The regression data have a pressure range of 20–270 kbar, and compositions as diverse as nephelinite and komatiite. These models should thus apply to a broad range of geological problems. The majorite component in garnet was found to increase with increasing P, but compositional effects are also important. A garnet saturation surface applied to liquids with chondritic compositions shows that such liquids crystallize garnet with Mj contents of 0.27–0.42 at 200 kbar. Models of Earth differentiation thus need to account not only for fractionation of majorite, but also for Fe-, Ca-, Na- and Ti-bearing garnet components, which occur in non-trivial quantities at high pressure. Since many models of igneous petrogenesis rely on mineral-melt partition coefficients for the minor elements Na, Ti, and Cr, partition coefficients for these elements were also examined. The K d gar/liq for Na was found to be P-sensitive; Na contents of basalts may thus potentially yield information regarding depths of partial melting. Received : 28 May 1997 / 25 November 1997  相似文献   

20.
Zusammenfassung Ausgeprägte Wechselbeziehungen existieren zwischen zahlreichen Erzen und den sie umhüllenden Gesteinen. Zum Beispiel sind sulfidische Eisen-Nickel-Kupfeterze fast ausschließlich an basische Gesteine gebunden, wie Norite, während Molybdänsulfidlagerstätten, oder auch Blei-Zink-Vererzungen, in sauren Gesteinen, etwa Graniten und Monzoniten, anzutreffen sind. Experimentelle Untersuchungen an entsprechenden silikatisch-sulfidischen Stoff-systemen zeigen in augenfälliger Weise eine weitgehende Unmischbarkeit im Schmelzfluß. Die Löslichkeit von Sulfiden in Silikatschmelzen ist gering selbst bei niedriger Sauerstoffugazität und nimmt mit steigender f02 noch weiter ab. Zufuhr von Schwefel zu einer homogenen Schmelze noritischer Zusammensetzung, mit kleinen Nickel- und Kupfergehalten, führt zur Bildung einer sulfidisch-oxidischen Schmelze, die mit der Silikatschmelze koexistiert. Die Silikatschmelze puffert die Zusammensetzung der sulfidisch-oxidischen Schmelze, welche bei der Abkühlung zu einem Gemisch aus Magnetit und monosulfidischen Mischkristallen, (Fe, Ni, Cu) 1–x S, kristallisiert. Bei weiterer Temperaturerniedrigung zerfällt die Mischkristallphase zu Pyrrhotin, Kupferkies und Pentlandit, gemäß der charakteristischen Erzparagenese vom Typus Sudbury. Bereiche von miteinander unmischbaren Schmelzen existieren auch in Systemen, welche granitische oder monzonitische und auch sulfidische Komponenten beinhalten. Reaktionen zwischen Schwefeldampf und silikatischen Mineralien führen zur Bildung von Sulfiden und Oxiden, welche gewöhnlich in metamorphen Gesteinen zu beobachten sind.
Pronounced correlations exist between many ores and the rock types in which they occur. For instance, iron-nickel-copper sulfide ores are almost exclusively located in mafic rocks, such as norites and molybdenum sulfide deposits and vein-type lead-zinc sulfide deposits occur in silicic rocks, such as granites and monzonites. Experimental investigations of pertinent systems containing sulfide as well as silicate components have demonstrated the presence of wide fields of liquid immiscibility. The solubilities of sulfides in liquid silicates are low (<1000 ppm) even at low oxygen fugacities and diminish further with increase in f02. Addition of sulfur to homogeneous noritic-type liquid which contains small amounts of nickel and copper produces a sulfide-oxide liquid which coexists with the silicate liquid. The silicate liquid buffers the composition of the sulfide-oxide liquid. The latter crystallizes on cooling to a mixture of magnetite and a (Fe, Ni, Cu)1–x S solid solution wich in turn decomposes to the pyrrhotite, chalcopyrite, pentlandite assemblages characteristic of Sudbury-type deposits. Liquid immiscibility fields containing coexisting silicate and sulfide-oxide liquids exist also in systems containing granitic or monzonitic as well as the sulfide components. Reactions between sulfur vapor and silicate minerals produce sulfides and oxides commonly observed in metamorphosed rocks.
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