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1.
Experiments at 750 °C, 200 MPa(H2O), a (H2O)=1, and fO2∼Ni-NiO established that the equilibrium among tourmaline, biotite, cordierite, and melt (± spinel, aluminosilicate, or corundum) occurs with ∼2 wt% B2O3 in strongly peraluminous melt with an aluminosity, measured by the parameter ASI, of >1.2. The experiments demonstrate the relationship of tourmaline stability to the activity product of the tourmaline components boron and aluminum, which are inversely related to one another. Tourmaline is unstable in metaluminous to mildly peraluminous melts (ASI <1.2) at 750 °C regardless of their boron content. For a given aluminosity, addition of components such as F requires a greater boron content of melt at this equilibrium. The stability of tourmaline increases with decreasing temperatures below 750 °C. At the inception of melting, tourmaline breaks down incongruently to assemblages containing crystalline AFM silicates (biotite, cordierite, garnet, sillimanite), aluminates (spinel, corundum), and B-enriched but Fe-Mg-poor melt. Granitic melts are likely to be undersaturated in tourmaline from the start of their crystallization, and their initial boron contents will be limited by the abundance of tourmaline in their source rocks. Quartzofeldspathic (gneissic, metapelitic) rocks that reached conditions of the granulite facies and still contain (prograde) tourmaline are rare, and probably have never yielded a partial melt. Most leucogranitic magmas will initially crystallize biotite, cordierite, or garnet, but not tourmaline. With crystallization, the Fe-Mg content of melt decreases, and the B2O3 content increases until the tourmaline-biotite and/or tourmaline-cordierite (or garnet) equilibria are attained. The B2O3 content of melt is buffered as long as these equilibria continue to operate, but low initial Fe-Mg contents of the magmas limit the quantity of boron that can be consumed by these reactions to <1 wt% B2O3. Normally, leucogranitic magmas contain insufficient Fe and Mg to conserve all boron as tourmaline and thus lose a large fraction of magmatic boron to wallrocks. Leucogranites and pegmatites with tourmaline as an early and only AFM silicate mineral probably contained >2 wt% B2O3 in their bulk magmas. Received: 6 August 1996 / Accepted: 21 July 1997  相似文献   

2.
Dynamics of Na in sodium aluminosilicate glasses and liquids   总被引：1，自引：0，他引：1  
23Na NMR measurements on Na2Si3O7, Na3AlSi6O15, and NaAlSi3O8 glasses from room temperature to 1200°C show that the dynamics and local structure of sodium in silicate/aluminosilicate glasses and melts vary with composition and temperature.The peak positions decrease in frequency between room temperature and 200°C indicating that the Na sees a larger average site as temperature is increased. Between 200°–300° and 700°C, line widths, nutation frequencies and peak positions are consistent with motional averaging of quadrupolar satellites. Above 700°C there is little or no change in the peak positions with temperature. Chemical shifts of the materials at 1000°C (Na2Si3O7: 3.6; Na3AlSi6O15:-1.3; NaAlSi3O8:-6.4 ppm) indicate a slight change in the average Na coordination number from 6–7 for the silicate to 7–8 for the aluminosilicates.  相似文献   

3.
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   

4.
The carbon isotopic fractionation between CO2 vapour and sodamelilite (NaCaAlSi2O7) melt over a range of pressures and temperatures has been investigated using solid-media piston-cylinder high pressure apparatus. Ag2C2O4 was the source of CO2 and experimental oxygen fugacity was buffered at hematite-magnetite by the double capsule technique. The abundance and isotopic composition of carbon dissolved in sodamelilite (SM) glass were determined by stepped heating and the 13C of coexisting vapour was determined directly by capsule piercing. CO2 solubility in SM displays a complex behavior with temperature. At pressures up to 10 kbars CO2 dissolves in SM to form carbonate ion complexes and the solubility data suggest slight negative temperature dependence. Above 20 kbars CO2 reacts with SM to form immiscible Na-rich silicate and Ca-rich carbonate melts and CO2 solubility in Na-enriched silicate melt rises with increasing temperature above the liquidus. Measured values for carbon isotopic fractionation between CO2 vapour and carbonate ions dissoived in sodamelilite melt at 1200°–1400° C and 5–30 kbars average 2.4±0.2, favouring13C enrichment in CO2 vapour. The results are maxima and are independent of pressure and temperature. Similar values of 2 are obtained for the carbon isotopic fractionation between CO2 vapour and carbonate melts at 1300°–1400° C and 20–30 kbars.  相似文献   

5.
The critical role of iron on crystal-silicate liquid relationships and melt differentiation is mainly controlled by the redox conditions prevailing in magmas, but the presently available database merely constrains the thermodynamic properties of iron-bearing components in strongly reduced and anhydrous molten silicate where iron is in the ferrous form. This paper provides new standard states for pure ferrous (FeOliq) and ferric (Fe2O3liq) molten iron oxides and extends the experimental database towards oxidizing and water-bearing domains. Iron-iridium, iron-platinum alloys, magnetite or hematite were equilibrated with synthetic silicic liquids at high temperature and high pressure under controlled oxygen fugacity (fO2) to determine activity-composition relationships for FeOliq and Fe2O3liq. Between 1000 and 1300°C, the fO2 ranges from that in air to 3-log units below that of the nickel-nickel oxide buffer (NNO). Experiments were performed on both anhydrous and hydrous melts containing up to 6-wt.% water. Incorporation of water under reducing conditions increases the activity coefficient of FeOliq but has an opposite effect on Fe2O3liq. As calcium is added to system, the effect of water becomes weaker and is inverted for Fe2O3liq. Under oxidizing conditions, water has a negligible effect on both activities of FeOliq and Fe2O3liq. In contrast, changes in redox conditions dominate the activity coefficients of both FeOliq and Fe2O3liq, which increase significantly with increasing fO2. The present results combined with the previous work provide a specific database on the energetics of iron in silicate melts that cover most of the condition prevailing in natural magmas.  相似文献   

6.
We have determined the stability of rutile and karrooite on the liquidus of pseudobinary silicate melts of anorthite–diopside eutectic composition with, in addition, of up to 32 wt% TiO2 at one atm total pressure and at wide range of oxygen fugacities. At 1,300°C and at an fO2 below 10–11.2 atm rutile (TiO2) is replaced as liquidus phase by the pseudobrookite-type MgTi2O5–Ti3O5 solid solution with some Al in the crystal structure. The composition of karrooite was found to be strongly dependent on oxygen fugacity. Crystalline phases were identified by transmission electron microscopy (TEM). The results obtained in this study are relevant for understanding the chemistry of lunar armalcolites. Using excess rutile solubility at reducing conditions, we estimated the Ti4+ /Ti3+ ratio in silicate melts at 1,300°C as function of fO2.  相似文献   

7.
The speciation of water in silicate melts   总被引：1，自引：0，他引：1  
Previous models of water solubility in silicate melts generally assume essentially complete reaction of water molecules to hydroxyl groups. In this paper a new model is proposed that is based on the hypothesis that the observed concentrations of molecular water and hydroxyl groups in hydrous silicate glasses reflect those of the melts from which they were quenched. The new model relates the proportions of molecular water and hydroxyl groups in melts via the following reaction describing the homogeneous equilibrium between melt species: H2Omolecular (melt) + oxygen (melt) = 2OH (melt). An equilibrium constant has been formulated for this reaction and species are assumed to mix ideally. Given an equilibrium constant for this reaction of 0.1–0.3, the proposed model can account for variations in the concentrations of molecular water and hydroxyl groups in melts as functions of the total dissolved water content that are similar to those observed in glasses. The solubility of molecular water in melt is described by the following reaction: H2O (vapor) = H2Omolecular (melt).These reactions describing the homogeneous and heterogeneous equilibria of hydrous silicate melts can account for the following observations: the linearity between fH2O and the square of the mole fraction of dissolved water at low total water contents and deviations from linearity at high total water contents; the difference between the partial molar volume of water in melts at low total water contents and at high total water contents; the similarity between water contents of vapor-saturated melts of significantly different compositions at high pressures versus the dependence on melt composition of water solubility in silicate melts at low pressures; and the variations of viscosity, electrical conductivity, the diffusivity of “water,” the diffusivity of cesium, and phase relationships with the total dissolved water contents of melts.This model is thus consistent with available observations on hydrous melt systems and available data on the species concentrations of hydrous glasses and is easily tested, since measurements of the concentrations of molecular water and hydroxyl groups in silicate glasses quenched from melts equilibrated over a range of conditions and total dissolved water contents are readily obtainable.  相似文献   

8.
The effects of F, B2O3 and P2O5 on the H2O solubility in a haplogranite liquid (36 wt. % SiO2, 39 wt. % NaAlSi3O8, 25 wt. % KAlSi3O8) have been determined at 0.5, 1, 2, and 3 kb and 800, 850, and 900°C. The H2O solubility increases with increasing F and B content of the melt. The H2O solubility increase in more important at high pressure (2 and 3 kb) than at low pressure (0.5 kb). At 2 kb and 800°C, the H2O solubility increases from 5.94 to 8.22 wt. % H2O with increasing F content in the melt from 0 to 4.55 wt. %, corresponding to a linear H2O solubility increase of 0.53 mol H2O/mol F. With addition of 4.35 wt. % B2O3, the H2O solubility increases up to 6.86 wt. % H2O at 2 kb and 800°C, corresponding to a linear increase of 1.05 mol H2O/mol B2O3. The results allow to define the individual effects of fluorine and boron on H2O solubility in haplogranitic melts with compositions close to that of H2O-saturated thermal minima (at 0.5–3 kb). Although P has a dramatic effect on the phase relations in the haplogranite system, its effect on the H2O solubility was found to be negligible in natural melt compositions. The concominant increase in H2O solubility and F can not be interpreted on the basis of the available spectroscopic data (existence of hydrated aluminofluoride complexes or not). In contrast, hydrated borates or more probably boroxol complexes have been demonstrated in B-bearing hydrous melts.  相似文献   

9.
We experimentally determined the boron partitioning and boron isotope fractionation between coexisting liquid and vapor in the system H2O−NaCl−B2O3. Experiments were performed along the 400 and 450°C isotherms. Pressure conditions ranged from 23 to 28 MPa at 400°C and from 38 to 42 MPa at 450°C. Boron partitions preferentially into the liquid. Its overall liquid-vapor fractionation is, however, weak: Calculated boron distribution coefficients DBliquid-vapor are < 2.5 at all run conditions. With decreasing pressure (i.e. increasing opening of the solvus) DBliquid-vapor increases along the individual isotherms. Extrapolation to salt saturated conditions yields maximum boron liquid-vapor fractionations of DBliquid-vapor = 1.8 at 450°C and DBliquid-vapor = 2.7 at 400°C. 11B preferentially fractionates into the vapor. Calculated Δ11Bvapor-liquid = {[(11B/10B)vapor - (11B/10B)liquid]/(11B/10B)NBS 951}*1000 are small and range from 0.2 (± 0.7) to 0.9 (± 0.5) ‰ at 450°C and from 0.1 (± 0.6) to 0.7 (± 0.6) ‰ at 400°C. The data indicate increasing isotopic fractionation with decreasing pressure (i.e. increasing opening of the solvus). Extrapolation to salt saturated conditions yields maximum boron isotope liquid-vapor fractionations of Δ11Bvapor-liquid = 1.5 (± 0.7) ‰ at 450°C and Δ11Bvapor-liquid = 1.3 (± 0.6) ‰ at 400°C. The weak boron isotope fractionation suggests similar trigonal speciation in liquid and vapor. Although the boron and boron isotope fractionation between liquid and vapor is only weak, mass balance calculations indicate that for high degrees of fractionation liquid-vapor phase separation in an open system can significantly alter the boron and boron isotope signature of low-salinity hydrous fluids in hydrothermal systems. Comparing the model calculations with natural oceanic hydrothermal fluids, however, indicate that other processes than fluid phase separation dominate the boron geochemistry in oceanic hydrothermal fluids.  相似文献   

10.
Structural interaction between dissolved fluorine and silicate glass (25°C) and melt (to 1400°C) has been examined with 19F and 29Si MAS NMR and with Raman spectroscopy in the system Na2O-Al2O3-SiO2 as a function of Al2O3 content. Approximately 3 mol.% F calculated as NaF dissolved in these glasses and melts. From 19F NMR spectroscopy, four different fluoride complexes were identified. These are (1) Na-F complexes (NF), (2) Na-Al-F complexes with Al in 4-fold coordination (NAF), (3) Na-Al-F complexes with Al in 6-fold coordination with F (CF), and (4) Al-F complexes with Al in 6-fold, and possibly also 4-fold coordination (TF). The latter three types of complexes may be linked to the aluminosilicate network via Al-O-Si bridges.The abundance of sodium fluoride complexes (NF) decreases with increasing Al/(Al + Si) of the glasses and melts. The NF complexes were not detected in meta-aluminosilicate glasses and melts. The NAF, CF, and TF complexes coexist in peralkaline and meta-aluminosilicate glasses and melts.From 29Si-NMR spectra of glasses and Raman spectra of glasses and melts, the silicate structure of Al-free and Al-poor compositions becomes polymerized by dissolution of F because NF complexes scavenge network-modifying Na from the silicate. Solution of F in Al-rich peralkaline and meta-aluminous glasses and melts results in Al-F bonding and aluminosilicate depolymerization.Temperature (above that of the glass transition) affects the Qn-speciation reaction in the melts, 2Q3 ⇔ Q4 + Q2, in a manner similar to other alkali silicate and alkali aluminosilicate melts. Dissolved F at the concentration level used in this study does not affect the temperature-dependence of this speciation reaction.  相似文献   

11.
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   

12.
In situ X-ray diffraction study on KAlSi3O8 has been performed using the cubic type high pressure apparatus, MAX90, combined with synchrotron radiation. We determined the phase relations of sanidine, the wadeite-type K2Si4O9+kyanite (Al2SiO5)+coesite (SiO2) assemblage, and hollandite-type KAlSi3O8, including melting temperatures of potassic phases, up to 11 GPa. Our data on subsolidus phase boundaries are close to the recent data of Yagi and Akaogi (1991). Melting relations of sanidine are consistent with the low pressure data of Lindsley (1966). The breakdown of sanidine into three phases reduces melting temperature, and wadeite-type K2Si4O9 melts first around 1500° C in three phase coexisting region. Melting point of hollandite-type KAlSi3O8 is between 1700° C and 1800° C at 11 GPa. If these potassic phases host potassium in the earth's mantle, the true mantle solidus temperature will be much lower than the reported dry solidus temperature of peridotite.  相似文献   

13.
The structure of H2O-saturated silicate melts and of silicate-saturated aqueous solutions, as well as that of supercritical silicate-rich aqueous liquids, has been characterized in-situ while the sample was at high temperature (to 800 °C) and pressure (up to 796 MPa). Structural information was obtained with confocal microRaman and with FTIR spectroscopy. Two Al-bearing glasses compositionally along the join Na2O•4SiO2-Na2O•4(NaAl)O2-H2O (5 and 10 mol% Al2O3, denoted NA5 and NA10) were used as starting materials. Fluids and melts were examined along pressure-temperature trajectories of isochores of H2O at nominal densities (from PVT properties of pure H2O) of 0.85 g/cm3 (NA10 experiments) and 0.86 g/cm3 (NA5 experiments) with the aluminosilicate + H2O sample contained in an externally-heated, Ir-gasketed hydrothermal diamond anvil cell.Molecular H2O (H2O°) and OH groups that form bonds with cations exist in all three phases. The OH/H2O° ratio is positively correlated with temperature and pressure (and, therefore, fugacity of H2O, fH2O) with (OH/H2O°)melt > (OH/H2O°)fluid at all pressures and temperatures. Structural units of Q3, Q2, Q1, and Q0 type occur together in fluids, in melts, and, when outside the two-phase melt + fluid boundary, in single-phase liquids. The abundance of Q0 and Q1 increases and Q2 and Q3 decrease with fH2O. Therefore, the NBO/T (nonbridging oxygen per tetrahedrally coordination cations), of melt is a positive function of fH2O. The NBO/T of silicate in coexisting aqueous fluid, although greater than in melt, is less sensitive to fH2O.The melt structural data are used to describe relationships between activity of H2O and melting phase relations of silicate systems at high pressure and temperature. The data were also combined with available partial molar configurational heat capacity of Qn-species in melts to illustrate how these quantities can be employed to estimate relationships between heat capacity of melts and their H2O content.  相似文献   

14.
The investigation of hydrous boro(alumino)silicate melts and glasses with near infrared (NIR) spectroscopy revealed an important effect of boron on the water speciation. In the NIR spectra of B-bearing glasses new hydroxyl-related bands develop at the high frequency side of the 4500 cm−1 peak. In NaAlSi3O8 + B2O3 glasses this new peak is present as a shoulder at 4650 cm−1, and in NaAlSi3O8-NaBSi3O8 (Ab-Rd) glasses it appears as a resolved peak at 4710 cm−1. These bands increase with increasing boron concentration, suggesting that they are due to B-OH complexes. Furthermore, the variations in the NIR spectra indicate that with increasing B-content, but constant total water concentration, the amount of structurally bonded hydroxyl groups increases at the expense of molecular H2O. For example, at a total water concentration of 4 wt.%, pure Rd-glass contains ∼50% more water as hydroxyl groups than pure Ab-glass.In-situ NIR spectroscopy at high P and T using a hydrothermal diamond-anvil cell was used to gain information about the temperature dependence of the water speciation in NaBSi3O8 melts. The data demonstrate the conversion of molecular H2O to hydroxyl groups with increasing temperature. However, a fully quantitative evaluation of the high T spectra was hampered by problems with defining the correct baseline in the spectra. As an alternative approach annealing experiments on a Rd-glass containing 2.8 wt.% water were performed. The results confirm the conversion of H2O to OH groups with increasing T, but also suggest that the OH groups represented by the 4710 cm−1 peak (B-OH) participate much less in the conversion reaction compared to X-OH, represented by the 4500 cm−1 peak.  相似文献   

15.
Reactions between hornblende-plagioclase amphibolite and acidic and alkaline B-bearing aqueous fluids have been investigated by experiments at 475°–600° C and 200 MPa. At 600° C, hornblende+calcic plagioclase react to form tourmaline+danburite+clinopyroxene+quartz in acidic fluids containing 0.5–1.0 wt% B2O3.Tourmaline is precipitated directly from acidic fluids, and the reaction is driven by neutralization of fluids by Na±Ca derived from the breakdown of reactant solids. The concentration of B2O3 in fluids needed to stabilize tourmaline increases as pH increases (above approximately 6.0), and tourmaline is unstable in alkaline fluids (pH > approximately 6.5–7.0) regardless of B concentration. In addition to acid-base relations, tourmaline stability is favored by comparatively higher activity coefficients for Al species in acidic fluids. The concentrations of Al and Si in fluid increase with alkalinity, with the eventual production of felsic borosilicate melts through partial melting of the plagioclase component of the amphibolite. In seeded experiments, tourmaline also contributes components to melt. Partial melting is evident in the range 500°–525° C at 200 MPa in experiments with 8wt% B2O3 in fluid as Na2B4O7. The experimental results are applied primarily to metasomatic reactions between mafic rocks and borate fluids derived from granitic magmas, but tourmaline stability and partial melting in mafic regional metamorphic systems are also discussed briefly.  相似文献   

16.
Viscosity experiments were conducted with two flux-rich pegmatitic melts PEG0 and PEG2. The Li2O, F, B2O3 and P2O5 contents of these melts were 1.04, 4.06, 2.30 and 1.68 and 1.68, 5.46, 2.75 and 2.46 wt%, respectively. The water contents varied from dry to 9.04 wt% H2O. The viscosity was determined in internally heated gas pressure vessels using the falling sphere method in the temperature range 873–1,373 K at 200 and 320 MPa pressure. At 1,073 K, the viscosity of water-rich (~9 wt% H2O) melts is in the range of 3–60 Pa s, depending on the melt composition. Extrapolations to lower temperature assuming an Arrhenian behavior indicate that highly fluxed pegmatite melts may reach viscosities of ~30 Pa s at 773 K. However, this value is a minimum estimation considering the strongly non-Arrhenian behavior of hydrous silicate melts. The experimentally determined melt viscosities are lower than the prediction of current models taking compositional parameters into account. Thus, these models need to be improved to predict accurately the viscosity of flux-rich water bearing melts. The data also indicate that Li influences significantly the melt viscosity. Decreasing the molar Al/(Na + K + Li) ratio results in a strong viscosity decrease, and highly fluxed melts with low Al/(Na + K + Li) ratios (~0.8) have a rheological behavior which is very close to that of supercritical fluids.  相似文献   

17.
The role of the oxygen fugacity on the incorporation of nitrogen in basaltic magmas has been investigated using one atmosphere high temperature equilibration of tholeiitic-like compositions under controlled nitrogen and oxygen partial pressures in the [C-N-O] system. Nitrogen was extracted with a CO2 laser under high vacuum and analyzed by static mass spectrometry. Over a redox range of 18 oxygen fugacity log units, this study shows that the incorporation of nitrogen in silicate melts follows two different behaviors. For log fO2 values between −0.7 and −10.7 (the latter corresponding to IW − 1.3), nitrogen dissolves as a N2 molecule into cavities of the silicate network (physical solubility). Nitrogen presents a constant solubility (Henry’s) coefficient of 2.21 ± 0.53 × 10−9 mol g−1 atm−1 at 1425°C, identical within uncertainties to the solubility of argon. Further decrease in the oxygen fugacity (log fO2 between −10.7 and −18 corresponding to the range from IW − 1.3 to IW − 8.3) results in a drastic increase of the solubility of nitrogen by up to 5 orders of magnitude as nitrogen becomes chemically bounded with atoms of the silicate melt network (chemical solubility). The present results strongly suggest that under reducing conditions nitrogen dissolves in silicate melts as N3− species rather than as CN− cyanide radicals. The nitrogen content of a tholeiitic magma equilibrated with N2 is computed from thermochemical processing of our data set as
  相似文献   

18.
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   

19.
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   

20.
Detailed analyses of melt and fluid inclusions combined with an electron-microprobe survey of boron-bearing minerals reveal the evolution of boron in a highly evolved peraluminous granite-pegmatite complex and the associated high- and medium-temperature ore-forming hydrothermal fluids (Ehrenfriedersdorf, Erzgebirge, Germany). Melt inclusions in granite represent embryonic pegmatite-forming melts containing about 10 wt% H2O and 1.8 wt% B2O3. These melts are also enriched in F, P, and other incompatible elements such as Be, Sn, Rb, and Cs. Ongoing differentiation and volatile enrichment drove the system into a solvus, where two pegmatite-forming melts coexisted. The critical point is at about 712 °C, 100 MPa, 20 wt% H2O and 4.1 wt% B2O3. Cooling and concomitant fractional crystallisation from 700 to 500 °C induced development of two conjugate melts, an H2O-poor (A-melt) and an H2O-rich melt (B-melt) along the opening solvus. Boron is a major element in both melts and is preferentially partitioned into the H2O-rich melt. Temperature-dependent distribution coefficients DboronB - melt/A - melt D_{{\rm{boron}}}^{{\rm{B - melt/A - melt}}} are 1.3 at 650 °C, 1.5 at 600 °C, and 1.8 at 500 °C. In both melts, boron concentrations decreased during cooling because of exsolution of a boron-rich hypersaline brine throughout the pegmatitic stage. Boromuscovite containing up to 8.5 wt% was another sink for boron at this stage. The end of the melt-dominated pegmatitic stage was attained at a solidus temperature of around 490 °C. Fluid inclusions of the hydrothermal stage reveal trapping temperatures of 480 to 370 °C, along with varying densities and highly variable B2O3 contents ranging from 0.20 to 2.94 wt%. A boiling system evolved, indicating a complex interplay between closed- and open-system behaviour. Pressure switched from lithostatic to hydrostatic and back, generating hydrothermal convection cells where meteoric waters were introduced and mixed with magmatic fluids. Boron-rich solutions originated from magmatic fluids, whereas boron-depleted fluids were mainly of meteoric origin. This highlights the potential of boron for discriminating fluids of different origin. Tin is continuously enriched during the evolution because tin and boron are cross-linked by formation of boron-, fluorine- and tin-fluorine-bearing complexes and is finally deposited within quartz-cassiterite veins during the transition from closed- to open-system behaviour. Boron does not only trace the complex evolution of the Ehrenfriedersdorf complex but exerts, together with H2O, F and P, an important control on the physical and chemical properties of pegmatite-forming melts, and particularly on the formation of a two-melt solvus at low pressure. We discuss this with respect to experimental results on H2O solubility and the critical behaviour of the haplogranite-water system which contained variable concentrations of volatiles.  相似文献   

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