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1.
In order to model the processes of formation of the highly alkaline (potassic) melts during the partial melting of the eclogite nodules in kimberlites, experiments on the melting of the model and natural eclogites in presence of the H2O-CO2 and H2O-CO2-KCl fluids at 5 GPa and 1200 and 1300°C are performed. A comparative analysis of the phase relations in the systems with H2O-CO2 and H2O-CO2-KCl demonstrate that KCl in the fluid equilibrated with eclogites intensifies their melting. It is related to both high Cl concentration in the forming silicate melt (2.0–5.5 wt %) and its enrichment in K2O owing to the K-Na exchange reactions with the immiscible chloride melt. Because of these reactions, the K2O/Cl ratio in the melts increases with the KCl content in the system and reaches 2.5–3.5 in the silicate melts coexisting with the immiscible chloride liquid. However, the ratio KCl/(H2O + CO2 + KCl) in the fluid does not influence on the ratio K2O/Cl in the melts. Thus, the solubility KCl in the melts, apparently, does not depend on presence of the H2O-CO2 fluid, at least, within the concentration range used in the experiments (up to 20 wt %). The experiments show that the deliberated chloride liquid is necessary to form the potassium-rich chlorine-bearing silicate melts during the eclogite melting. It corresponds to the KCl content in the system above 5 wt %.  相似文献   

2.
Melting relations at 5 and 20 kbar on the composition join sanidine-potassium carbonate are dominated by a two-liquid region that covers over 60% of the join at 1,300 ° C. At this temperature, the silicate melt contains approximately 19 wt% carbonate component at 5 kbar and 32 wt% carbonate component at 20 kbar. The conjugate carbonate melt contains less than 5 wt% silicate component, and it varies less as a function of temperature than does the silicate melt.Partition coefficients for Ce, Sm, and Tm between the immiscible carbonate and silicate melts at 1,200 ° and 1,300 ° C at 5 and 20 kbar are in favor of the carbonate melt by a factor of 2–3 for light REE and 5–8 for heavy REE. The effect of pressure on partitioning cannot be evaluated independently because of complementary changes in melt compositions.Minimum REE partition coefficients for CO2 vapor/carbonate melt and CO2 vapor/silicate melt can be calculated from the carbonate melt/silicate melt partition coefficients, the known proportions of melt, and maximum estimates of the proportion of CO2 vapor. The vapor phase is enriched in light REE relative to both melts at 20 kbar and enriched in all REE, especially the light elements, at 5 kbar. The enrichment of REE in CO2 vapor relative to both melts is 3–4 orders of magnitude in excess of that in water vapor (Mysen, 1979) at 5 kbar and is approximately the same as that in water vapor at 20 kbar.Mantle metasomatism by a CO2-rich vapor enriched in light REE, occurring as a precursor to magma genesis, may explain the enhanced REE contents and light REE enrichment of carbonatites, alkali-rich silicate melts, and kimberlites. Light REE enrichment in fenites and the granular suite of nodules from kimberlites attests to the mobility of REE in CO2-rich fluids under both mantle and crustal conditions.  相似文献   

3.
The nucleation of H2O bubbles in magmas has been proposed as a trigger for volcanic eruptions. To determine how bubbles nucleate heterogeneously in silicate melts, experiments were carried out in which high-silica rhyolitic melts were hydrated at 740-800°C and 50-175 MPa, decompressed by 20-70 MPa, and held at the lower pressures for ≥10 s before being quenched. The hydration conditions were subliquidus, and all samples contain blocky magnetite + needle-shaped hematite ± plagioclase. Magnetite is abundant at 800°C and high pressures, whereas hematite becomes more abundant at lower temperatures and pressures. Bubbles nucleated in a single event in all samples, with the number density (NT) of bubbles varying between 2 × 107 and 1 × 109 cm−3. At low degrees of supersaturation, one to a few bubbles nucleate on faces of magnetite, but at medium to high degrees of supersaturation, multiple bubbles nucleate on single magnetite grains. On hematite, one to a few bubbles nucleated at the ends of the needle-shaped crystals at medium supersaturations, but formed along their entire lengths at high supersaturations. NT increases as water diffusivity decreases, indicating that the number of bubbles nucleated is influenced by their growth, which depletes the melt with respect to H2O and lowers supersaturation. If volcanic eruptions are triggered by bubble formation in magmas stored in shallow-level magma chambers, then the supersaturations needed for heterogeneous nucleation suggest that only small amounts of crystallization are needed, whereas homogeneous nucleation is unlikely to trigger eruptions.  相似文献   

4.
We report results of experiments constraining oxygen isotope fractionations between CO2 vapor and Na-rich melilitic melt at 1 bar and 1250 and 1400°C. The fractionation factor constrained by bracketed experiments, 1000.lnαCO2-Na melilitic melt, is 2.65±0.25 ‰ (±2σ; n=92) at 1250°C and 2.16±0.16 ‰ (2σ; n=16) at 1400°C. These values are independent of Na content over the range investigated (7.5 to 13.0 wt. % Na2O). We combine these data with the known reduced partition function ratio of CO2 to obtain an equation describing the reduced partition function ratio of Na-rich melilite melt as a function of temperature. We also fit previously measured CO2-melt or -glass fractionations to obtain temperature-dependent reduced partition function ratios for all experimentally studied melts and glasses (including silica, rhyolite, albite, anorthite, Na-rich melilite, and basalt). The systematics of these data suggest that reduced partition function ratios of silicate melts can be approximated either by using the Garlick index (a measure of the polymerization of the melt) or by describing melts as mixtures of normative minerals or equivalent melt compositions. These systematics suggest oxygen isotope fractionation between basalt and olivine at 1300°C of approximately 0.4 to 0.5‰, consistent with most (but not all) basalt glass-olivine fractionations measured in terrestrial and lunar basalts.  相似文献   

5.
Syngenetic garnet of eclogitic/pyroxenitic composition included in a polycrystalline diamond aggregate from the Venetia kimberlite, Limpopo Belt, South Africa shows multiple inclusions of spherules consisting of 61±5 vol% Fe3C (cohenite), 30±2 vol% Fe-Ni and 9±3 vol% FeS (troilite). Troilite forms shells around the native iron-cohenite assemblage, implying that both compositions were immiscible melts and were trapped rapidly by the silicate. It is proposed that this polycrystalline diamond-silicate-metallic spherule assemblage formed in very local pressure and fO2 conditions in cracks at the base of the subcratonic lithosphere from a C-H-O fluid that reacted with surrounding silicate at about 1,300–1,400 °C. In a mantle fluid consisting of CH4>H2O>H2 near fO2=IW, the H2 activity increases rapidly when carbon from the fluid is consumed by diamond precipitation, driving the oxygen fugacity of the system to lower values along the diamond saturation curve. Water from the fluid induces melting of surrounding silicate material, and hydrogen reduces metals in the silicate melt, reflected by an unusually low Ni content of the garnet. The carbon isotopic composition of 13C=–13.69 (PDB) and the lack of nitrogen as an impurity is consistent with formation of the diamond from non-biogenic methane, whereas 18O=7.4 (SMOW) of the garnet implies derivation of the silicate from subduction-related material. Hence, very localized and transient reducing conditions within the subcratonic lithosphere can be created by this process and do not necessarily call for involvement of fluids derived from subducted material of biogenic origin.Editorial responsibility: J. Hoefs  相似文献   

6.
This experimental study examines the mineral/melt partitioning of Na, Ti, La, Sm, Ho, and Lu among high-Ca clinopyroxene, plagioclase, and silicate melts analogous to varying degrees of peridotite partial melting. Experiments performed at a pressure of 1.5 GPa and temperatures of 1,285 to 1,345 °C produced silicate melts saturated with high-Ca clinopyroxene, plagioclase and/or spinel, and, in one case, orthopyroxene and garnet. Partition coefficients measured in experiments in which clinopyroxene coexists with basaltic melt containing ~18 to 19 wt% Al2O3 and up to ~3 wt% Na2O are consistent with those determined experimentally in a majority of the previous studies, with values of ~0.05 for the light rare earths and of ~0.70 for the heavy rare earths. The magnitudes of clinopyroxene/melt partition coefficients for the rare earth elements correlate with pyroxene composition in these experiments, and relative compatibilities are consistent with the effects of lattice strain energy. Clinopyroxene/melt partition coefficients measured in experiments in which the melt contains ~20 wt% Al2O3 and ~4 to 8 wt% Na2O are unusually large (e.g., values for Lu of up to 1.33±0.05) and are not consistent with the dependence on pyroxene composition found in previous studies. The magnitudes of the partition coefficients measured in these experiments correlate with the degree of polymerization of the melt, rather than with crystal composition, indicating a significant melt structural influence on trace element partitioning. The ratio of non-bridging oxygens to tetrahedrally coordinated cations (NBO/T) in the melt provides a measure of this effect; melt structure has a significant influence on trace element compatibility only for values of NBO/T less than ~0.49. This result suggests that when ascending peridotite intersects the solidus at relatively low pressures (~1.5 GPa or less), the compatibility of trace elements in the residual solid varies significantly during the initial stages of partial melting in response to the changing liquid composition. It is unlikely that this effect is important at higher pressures due to the increased compatibility of SiO2, Na2O, and Al2O3 in the residual peridotite, and correspondingly larger values of NBO/T for small degree partial melts.Editorial responsibility: T.L. Grove  相似文献   

7.
Phase relations have been determined for a Paricutin Volcano andesite at pressures to 10 kilobars and for H2O contents in the melt of 2 to 10 weight percent. Runs were made under H2O-saturated and undersaturated conditions. In undersaturated runs a H2O-CO2 fluid phase was always present. Fugacity of H2O in melt, which is directly related to H2O content in the melt, was calculated from thermodynamic data. Plagioclase was found to be the liquidus phase when H2O contents in melt were less than about two percent. With more H2O, orthopyroxene, in some cases joined by olivine, assumes the liquidus. Clinopyroxene crystallizes near the liquidus only for H2O contents greater than five percent. The upper temperature stability limit of hornblende is about 950° C, well below the other silicate liquidi except at H2O-saturated conditions above 5 kb.The geometry of undersaturated liquidi and experimental phase compositions may be compared to the mode and phase compositions of the natural rock. From this comparison, megaphenocrysts of the natural rock are interpreted to have crystallized from a lava which had a water content of 2.2±0.5 percent and a temperature of 1110±40°C. Mass-balance calculations on experimental and natural phase assemblages show that the Paricutin series could not have formed by fractionation at pressures less than 10 kb; rather, it was probably derived by partial melting of subducted basaltic oceanic floor.  相似文献   

8.
The viscosity of a silicate melt of composition NaAlSi2O6 was measured at pressures from 1.6 to 5.5 GPa and at temperatures from 1,350 to 1,880°C. We employed in situ falling sphere viscometry using X-ray radiography. We found that the viscosity of the NaAlSi2O6 melt decreased with increasing pressure up to 2 GPa. The pressure dependence of viscosity is diminished above 2 GPa. By using the relationship between the logarithm of viscosity and the reciprocal temperature, the activation energies for viscous flow were calculated to be 3.7 ± 0.4 × 102 and 3.7 ± 0.5 × 102 kJ/mol at 2.2 and 2.9 GPa, respectively.  相似文献   

9.
Solubility mechanisms of water in depolymerized silicate melts quenched from high temperature (1000°-1300°C) at high pressure (0.8-2.0 GPa) have been examined in peralkaline melts in the system Na2O-SiO2-H2O with Raman and NMR spectroscopy. The Na/Si ratio of the melts ranged from 0.25 to 1. Water contents were varied from ∼3 mol% and ∼40 mol% (based on O = 1). Solution of water results in melt depolymerization where the rate of depolymerization with water content, ∂(NBO/Si)/∂XH2O, decreases with increasing total water content. At low water contents, the influence of H2O on the melt structure resembles that of adding alkali oxide. In water-rich melts, alkali oxides are more efficient melt depolymerizers than water. In highly polymerized melts, Si-OH bonds are formed by water reacting with bridging oxygen in Q4-species to form Q3 and Q2 species. In less polymerized melts, Si-OH bonds are formed when bridging oxygen in Q3-species react with water to form Q2-species. In addition, the presence of Na-OH complexes is inferred. Their importance appears to increase with Na/Si. This apparent increase in importance of Na-OH complexes with increasing Na/Si (which causes increasing degree of depolymerization of the anhydrous silicate melt) suggests that water is a less efficient depolymerizer of silicate melts, the more depolymerized the melt. This conclusion is consistent with recently published 1H and 29Si MAS NMR and 1H-29Si cross polarization NMR data.  相似文献   

10.
The stability and partial melting of synthetic pargasite in the presence of enstatitic orthopyroxene (opx), forsterite, diopsidic clinopyroxene (cpx), plagioclase (An50), and water has been studied in the range of 0.4–6.0 kb and 750–1000°C in the system Na2O-CaO-MgO-Al2O3-SiO2-H2O with a fixed bulk composition of pargasite+5 opx. The addition of orthopyroxene effectively reduces the stability field of pargasite by approximately 200°C at 1 kb. The invariant point involving pargasite coexisting with water-saturated liquid and anhydrous phase shifts from about 0.85 kb and 1025°C to 2.5±0.5 kb and 925±25°C with the addition of opx. Based on the solidus mineral assemblage and direct chemical analysis of quenched glass, the vapor-saturated liquid has a composition close to that of intermediate plagioclase. A layered silicate, interpreted to be Na-phlogopite, has an upper-thermal stability that nearly equals that of pargasite in the field of partial melting and coexists with liquid, pargasite, cpx, and forsterite at 6 kb, 1000°C. These results support the hypothesis that mantle metasomatism could involve formation of pargasitic amphibole from a silicate melt at depths as shallow as 8–10 km.  相似文献   

11.
High-pressure liquids in the MgO-SiO2-H2O (MSH) system have been investigated at 11 and 13.5 GPa and between 1000 and 1350 °C. A bulk composition more magnesian than the tie-line forsterite-H2O was employed for the study. Rocking multi-anvil experiments were combined with a diamond trap set-up. After termination of the experiments, the liquid trapped in the diamond layer was analysed by laser ablation ICP-MS using the ‘freezing’ technique. At 11 GPa, liquids coexist with one or two of phase A, clinohumite, chondrodite, and forsterite. A marked discontinuity in the evolution of liquid compositions near 1100 °C is observed at 11 GPa. A step of ∼13 wt% H2O and 13 wt% MgO is interpreted to result from overstepping the fluid-saturated solidus reaction mass balanced to 1.00(18) phase A + 1.07(4) fluid = 0.63(15) chondrodite + 1.44(2) melt. At 13.5 GPa liquids coexist with one or two of hydrous wadsleyite, clinohumite, superhydrous B, phase B, and forsterite. The discontinuity in liquid composition is no longer present, indicating that the second critical endpoint of the solidus has been overstepped. Thus, hydrous melts in the Mg-rich part of the MSH system (molar bulk Mg/Si > 2) are chemically distinct from aqueous fluids at pressure up to 11 GPa. Convergence of fluid and melt compositions along the solidus resulting in a supercritical liquid occurs between 11 and 13.5 GPa, at which pressure the entire MSH system becomes supercritical.  相似文献   

12.
We determined total CO2 solubilities in andesite melts with a range of compositions. Melts were equilibrated with excess C-O(-H) fluid at 1 GPa and 1300°C then quenched to glasses. Samples were analyzed using an electron microprobe for major elements, ion microprobe for C-O-H volatiles, and Fourier transform infrared spectroscopy for molecular H2O, OH−, molecular CO2, and CO32−. CO2 solubility was determined in hydrous andesite glasses and we found that H2O content has a strong influence on C-O speciation and total CO2 solubility. In anhydrous andesite melts with ∼60 wt.% SiO2, total CO2 solubility is ∼0.3 wt.% at 1300°C and 1 GPa and total CO2 solubility increases by about 0.06 wt.% per wt.% of total H2O. As total H2O increases from ∼0 to ∼3.4 wt.%, molecular CO2 decreases (from 0.07 ± 0.01 wt.% to ∼0.01 wt.%) and CO32− increases (from 0.24 ± 0.04 wt.% to 0.57 ± 0.09 wt.%). Molecular CO2 increases as the calculated mole fraction of CO2 in the fluid increases, showing Henrian behavior. In contrast, CO32− decreases as the calculated mole fraction of CO2 in the fluid increases, indicating that CO32− solubility is strongly dependent on the availability of reactive oxygens in the melt. These findings have implications for CO2 degassing. If substantial H2O is present, total CO2 solubility is higher and CO2 will degas at relatively shallow levels compared to a drier melt. Total CO2 solubility was also examined in andesitic glasses with additional Ca, K, or Mg and low H2O contents (<1 wt.%). We found that total CO2 solubility is negatively correlated with (Si + Al) cation mole fraction and positively correlated with cations with large Gibbs free energy of decarbonation or high charge-to-radius ratios (e.g., Ca). Combining our andesite data with data from the literature, we find that molecular CO2 is more abundant in highly polymerized melts with high ionic porosities (>∼48.3%), and low nonbridging oxygen/tetrahedral oxygen (<∼0.3). Carbonate dominates most silicate melts and is most abundant in depolymerized melts with low ionic porosities, high nonbridging oxygen/tetrahedral oxygen (>∼0.3), and abundant cations with large Gibbs free energy of decarbonation or high charge-to-radius ratio. In natural silicate melt, the oxygens in the carbonate are likely associated with tetrahedral and network-modifying cations (including Ca, H, or H-bonds) or a combinations of those cations.  相似文献   

13.
This experimental study examines the mineral/melt partitioning of incompatible trace elements among high-Ca clinopyroxene, garnet, and hydrous silicate melt at upper mantle pressure and temperature conditions. Experiments were performed at pressures of 1.2 and 1.6 GPa and temperatures of 1,185 to 1,370 °C. Experimentally produced silicate melts contain up to 6.3 wt% dissolved H 2O, and are saturated with an upper mantle peridotite mineral assemblage of olivine+orthopyroxene+clinopyroxene+spinel or garnet. Clinopyroxene/melt and garnet/melt partition coefficients were measured for Li, B, K, Sr, Y, Zr, Nb, and select rare earth elements by secondary ion mass spectrometry. A comparison of our experimental results for trivalent cations (REEs and Y) with the results from calculations carried out using the Wood-Blundy partitioning model indicates that H 2O dissolved in the silicate melt has a discernible effect on trace element partitioning. Experiments carried out at 1.2 GPa, 1,315 °C and 1.6 GPa, 1,370 °C produced clinopyroxene containing 15.0 and 13.9 wt% CaO, respectively, coexisting with silicate melts containing ~1–2 wt% H 2O. Partition coefficients measured in these experiments are consistent with the Wood-Blundy model. However, partition coefficients determined in an experiment carried out at 1.2 GPa and 1,185 °C, which produced clinopyroxene containing 19.3 wt% CaO coexisting with a high-H 2O (6.26±0.10 wt%) silicate melt, are significantly smaller than predicted by the Wood-Blundy model. Accounting for the depolymerized structure of the H 2O-rich melt eliminates the mismatch between experimental result and model prediction. Therefore, the increased Ca 2+ content of clinopyroxene at low-temperature, hydrous conditions does not enhance compatibility to the extent indicated by results from anhydrous experiments, and models used to predict mineral/melt partition coefficients during hydrous peridotite partial melting in the sub-arc mantle must take into account the effects of H 2O on the structure of silicate melts.  相似文献   

14.
《Applied Geochemistry》1996,11(3):481-487
Geological studies demonstrate that liquid immiscibility in felsic magma closely associates with the ore forming process. In order to obtain experimental evidence demonstrating the relationship between the ore forming process and liquid immiscibility in felsic magma, we carried out a series of experiments at high temperature and atmospheric pressure. The experimental results show that the granite ∼ KBF4∼Na2MoO4 system is a homogeneous melt at high temperature. With decrease in temperature, however, the melt decomposes into two immiscible melts: silicate melt and ore-forming melt. The ore-forming melt exists as globules in the silicate phase. Molybdenm, Ca, Na, Mg, P, Mn, F, B, and OH are concentrated in these globules. The ore forming melt is characterized with very low SiO2 and Al2O3 concentrations but the concentration of MoO3 and CaO is very high. In contrast, the silicate melts are significantly enriched in SiO2 and Al2O3, and depleted in MoO3 and CaO. In the silicate melt the concentrations of network modifying elements (e.g. Mo, Ca, Na, P, Mg) and volatiles (F, OH) are very low. The differences between the two immiscible melts exist not only in chemical composition but also in structure. The ore-forming melt structurally consists of [MoO4], [MoOF4], [B(OH)4], and OH, while the silicate melt is [Si04]. Because of the difference in composition and structure the two immiscible melts possess different physical properties. Compared to silicate melt, the ore-forming melt has a lower density and viscosity, which permits the globules to behave as bubbles in granite magma and to move and concentrate in the upper part of magma chamber. This process is probably responsible for the concentration of ore-forming elements in the upper part of granite bodies and their immediate aureoles. The present experimental results suggest that liquation in felsic magma can be the first step in the ore-forming process during granitoid evolution.  相似文献   

15.
Partitioning of F between H2O and CO2 fluids and topaz rhyolite melt   总被引：2，自引：0，他引：2  
Fluid/melt distribution coefficients for F have been determined in experiments conducted with peraluminous topaz rhyolite melts and fluids consisting of H2O and H2O+CO2 at pressures of 0.5 to 5 kbar, temperatures of 775°–1000°C, and concentrations of F in the melt ranging from 0.5 to 6.9 wt%. The major element, F, and Cl concentrations of the starting material and run product glasses were determined by electron microprobe, and the concentration of F in the fluid was calculated by mass balance. The H2O concentrations of some run product glasses were determined by ion microprobe (SIMS). The solubility of melt in the fluid phase increases with increasing F in the system; the solubility of H2O in the melt is independent of the F concentration of the system with up to 6.3 wt% F in the melt. No evidence of immiscible silica- and fluoriderich liquids was detected in the hydrous but water-undersaturated starting material glasses (8.5 wt% F in melt) or in the water-saturated run product glasses. F concentrates in topaz rhyolite melts relative to coexisting fluids at most conditions studied; however, DF (wt% F in fluid/wt% F in melt) increases strongly with increasing F in the system. Maximum values of DF in this study are significantly larger than those previously reported in the literature. Linear extrapolation of the data suggests that DF is greater than one for water-saturated, peraluminous granitic melts containing 8 wt% F at 800° C and 2 kbar. DF increases as temperature and as (H2O/H2O+CO2) of the fluid increase. For topaz rhyolite melts containing 1 wt% F and with H2O-rich fluids, DF is independent of changes in pressure from 2 to 5 kbar at 800° C; for melts containing 1 wt% F and in equilibrium with CO2-bearing fluids the concentrations of F in fluid increases with increasing pressure. F-and lithophile element-enriched granites may evolve to compositions containing extreme concentrations of F during the final stages of crystallization. If F in the melt exceeds 8 wt%, DF is greater than one and the associated magmatic-hydrothermal fluid contains >4 molal F. Such F-enriched fluids may be important in the mass transport of ore constituents, i.e., F, Mo, W, Sn, Li, Be, Rb, Cs, U, Th, Nb, Ta, and B, from the magma.  相似文献   

16.
Fluid activity ratios calculated between millimeter- to centimeter-scale layers in banded mafic eclogites from the Tauern Window, Austria, indicate that variations in a H 2 O existed between layers during equilibration at P approximately equal to 2GPa and T approximately equal to 625°C, whereas a CO 2 was nearly constant between the same layers. Model calculations in the system H2O–CO2–NaCl show that these results are consistent with the existence of different saturated saline brines, carbonic fluids, or immiscible pairs of both in different layers. The data cannot be explained by the exisience of water-rich fluids in all layers. The model fluid compositions agree with fluid inclusion compositions from eclogite-stage veins and segregations that contain (1) saline brines (up to 39 equivalent wt. % NaCl) with up to six silicate, oxide, and carbonate daughter phases, and (2) carbonic fluids. The formation of crystalline segregations from fluid-filled pockets or hydrofractures indicates high fluid pressures at 2 GPa; the record of fluid variability in the banded eclogite host rocks, however, implies that fluid transport was limited to local flow along individual layers and that there was no large-scale mixing of fluids during devolatilization at depths of 60–70 km. The lack of evidence for fluid mixing may, in part, reflect variations in wetting behavior of fluids of different composition; nonwetting fluids (water-rich or carbonic) would be confined to intergranular pore spaces and would be essentially immobile, whereas wetting fluids (saline brines) could migrate more easily along an interconnected fluid network. The heterogeneous distribution of chemically distinct fluids may influence chemical transport processes during subduction by affecting mineral-fluid element partitioning and by altering the migration properties of the fluid phase(s) in the downgoing slab.  相似文献   

17.
The structure of silicate melts in the system Na2O·4SiO2 saturated with reduced C-O-H volatile components and of coexisting silicate-saturated C-O-H solutions has been determined in a hydrothermal diamond anvil cell (HDAC) by using confocal microRaman and FTIR spectroscopy as structural probes. The experiments were conducted in-situ with the melt and fluid at high temperature (up to 800 °C) and pressure (up to 1435 MPa). Redox conditions in the HDAC were controlled with the reaction, Mo + H2O = MoO2 + H2, which is slightly more reducing than the Fe + H2O = FeO + H2 buffer at 800 °C and less.The dominant species in the fluid are CH4 + H2O together with minor amounts of molecular H2 and an undersaturated hydrocarbon species. In coexisting melt, CH3 - groups linked to the silicate melt structure via Si-O-CH3 bonding may dominate and possibly coexists with molecular CH4. The abundance ratio of CH3 - groups in melts relative to CH4 in fluids increases from 0.01 to 0.07 between 500 and 800 °C. Carbon-bearing species in melts were not detected at temperatures and pressures below 400 °C and 730 MPa, respectively. A schematic solution mechanism is, Si-O-Si + CH4?Si-O-CH3+H-O-Si. This mechanism causes depolymerization of silicate melts. Solution of reduced (C-O-H) components will, therefore, affect melt properties in a manner resembling dissolved H2O.  相似文献   

18.
Experiments in the systems diopside-albite (Di-Ab) and diopside-albite-dolomite (Di-Ab-Dmt), doped with a wide range of trace elements, have been used to characterise the difference between clinopyroxene-silicate melt and clinopyroxene-carbonate melt partitioning. Experiments in Di-Ab-Dmt yielded clinopyroxene and olivine in equilibrium with CO2-saturated dolomitic carbonate melt at 3 GPa, 1375 °C. The experiments in Di-Ab were designed to bracket those conditions (3 GPa, 1640 °C and 0.8 GPa, 1375 °C), and so minimise the contribution of differential temperature and pressure to partitioning. Partition coefficients, determined by SIMS analysis of run products, differ markedly for some elements between Di-Ab and Di-Ab-Dmt systems. Notably, in the carbonate system clinopyroxene-melt partition coefficients for Si, Al, Ga, heavy REE, Ti and Zr are higher by factors of 5 to 200 than in the silicate system. Conversely, partition coefficients for Nb, light REE, alkali metals and alkaline earths show much less fractionation (<3). The observed differences compare quantitatively with experimental data on partitioning between immiscible carbonate and silicate melts, indicating that changes in melt chemistry provide the dominant control on variation in partition coefficients in this case. The importance of melt chemistry in controlling several aspects of element partitioning is discussed in light of the energetics of the partitioning process. The compositions of clinopyroxene and carbonate melt in our experiments closely match those of near-solidus melts and crystals in CMAS-CO2 at 3 GPa, suggesting that our partition coefficients have direct relevance to melting of carbonated mantle lherzolite. Melts so produced will be characterised by elevated incompatible trace element concentrations, due to the low degrees of melting involved, but marked depletions of Ti and Zr, and fractionated REE patterns. These are common features of natural carbonatites. The different behaviour of trace elements in carbonate and silicate systems will lead to contrasted styles of trace element metasomatism in the mantle. Received: 15 July 1999 / Accepted: 18 February 2000  相似文献   

19.
The NaCl-H_2O binary system is a major component of solutions coexisting with ores. Observation ofsaturated solutions of NaCl-H_2O by using the method of hydrothermal diamond anvil cell (HDAC) is a new approach tothe study of ore-forming fluids. The salinities of NaCl-H_2O solutions in experimental observation are in a range of 32-55%. The observed temperature range is 25℃-850℃, and the pressure range 1 atm-10 kb. In this temperature-pressure range, the supercritical single phase, two phases (L,V) close to the critical state and two-phased (L+V) immis-cible region were observed. And for the salinity of 35% the two phase L+V immiscible region of NaCl-H_2O solutionwas observed in a range of 253-720℃. Another temperature range, 400-817℃, was observed for the immiscible two-phased region of 50% salinity solution. In the high-temperature part of the two-phased immiscible region, the phase na-ture is very unstable. A "critical phenomenon" was observed when the heating path was very close to the critical state.It is possible to observe a 'critical phenomenon': an "explosion" occurred almost constantly at the interface between theliquid and vapour and the interface is rather obscure. A continuous transition between phases L and V could be foundin the immiscible L+V phase while heating continuously. Moreover, as the NaCl-H_2O solution was separated into liq-uid and vapour phases, static charges surrounding each vapour bubble could be seen, and these bubbles were attractedtogether by the static charges to form a special solution structure. Besides, critical states of different salinities of NaCl-H_2O were observed in order to study the properties of the fluids occurring in the rocks in the earth interior, the origin ofore-bearing fluids and the significance of supercritical fluid with respect to the ore formation. The comparison of the sa-linity data of the fluid inclusions in the minerals of ore deposits with observations of NaCl-H_2O under HDAC in theconditions of high temperatures and pressures, combined with further thermodynamic analysis of ore-formation condi-tions would explain in depth the factors determining the ore formation.  相似文献   

20.
The solubility behavior of H2O in melts in the system Na2O-SiO2-H2O was determined by locating the univariant phase boundary, melt = melt + vapor in the 0.8-2 GPa and 1000°-1300°C pressure and temperature range, respectively. The NBO/Si-range of the melts (0.25-1) was chosen to cover that of most natural magmatic liquids. The H2O solubility in melts in the system Na2O-SiO2-H2O (XH2O) ranges between 18 and 45 mol% (O = 1) with (∂XH2O/∂P)T∼14-18 mol% H2O/GPa. The (∂XH2O/∂P)T is negatively correlated with NBO/Si (= Na/Si) of the melt. The (∂XH2O/∂T)P is in the −0.03 to +0.05 mol% H2O/°C range, and is negatively correlated with NBO/Si. The [∂XH2O/∂(NBO/Si)]P,T is in the −3 to −8 mol% H2O/(NBO/Si) range. Melts with NBO/Si similar to basaltic liquids (∼0.6-∼1.0) show (∂XH2O/∂T)P<0, whereas more polymerized melts exhibit (∂XH2O/∂T)P>0. Complete miscibility between hydrous melt and aqueous fluid occurs in the 0.8-2 GPa pressure range for melts with NBO/Si ≤0.5 at T >1100°C. Miscibility occurs at lower pressure the more polymerized the melt.  相似文献   

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