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1.
Infrared spectroscopy was used to determine the concentrations of molecular water and hydroxyl groups in hydrous rhyolitic, orthoclasic, jadeitic, and Ca–Al-silicate glasses synthesized by quenching of melts from elevated presure and temperature. The rhyolitic glasses and some of the Ca–Al-silicate glasses were quenched from water-vapor-saturated melts and used to determine the solubility of water in melts of these compositions. For all compositions studied, hydroxyl groups are the dominant hydrous species at low total water contents, whereas molecular water dominates at elevated water contents. Although the trends in species concentrations in all these compositions are similar, the proportions of the two hydrous species are influenced by silicate chemistry: increasing silica content and K relative to Na both favor molecular water over hydroxyl. Results on rhyolitic glass demonstrate that molecular water is also favored by decreasing temperature at T<850°C. For rhyolitic glasses quenched from vapor-saturated melts, the mole fraction of molecular water is proportional to water fugacity for P(H2O)1500 bars, demonstrating that the behavior of molecular water is approximately Henrian at total water contents up to at least several weight percent. Data on water solubility for albitic, orthoclasic, and Ca–Al-silicate melts to higher pressures can also be fit by assuming Henrian behavior for molecular water and can be used to set constraints on the partial molar volume of water in these melts. The demonstration of Henry's law for molecular water in these liquids provides a link between spectroscopic measurements of microscopic species concentrations and macroscopic thermodynamic properties.  相似文献   

2.
Water in silicate glasses: An infrared spectroscopic study   总被引：11，自引：2，他引：11  
Infrared and near-infrared transmission spectra have been taken on 19 volcanic and synthetic silicate glasses with known H2O contents (0.06–6.9 wt. %). Absorption peaks were observed at wavelengths of 1.41 m, 1.91 m, 2.22 m, 2.53 m, and 2.8 m. These peaks have been attributed to the first overtone of the OH stretching vibration, the combination stretching+bending mode of H2O molecules, the combination stretching+bending mode of X-OH groups, a combination mode of the fundamental OH stretch+a low energy lattice vibration, and the fundamental OH stretching mode, respectively. Molar absorptivities of the peaks have been determined to be 0.2, 1.8, 1.0, 0.9, and 67 l/mol-cm. These values apply over the full range of glass compositions studied (albite, rhyolite, basalt).Quantitative determinations of total H2O contents and of the concentrations of molecular water and hydroxyl groups in silicate glasses are possible using these molar absorptivities, although they are limited in their accuracy by the accuracy of the reported water contents of the glasses used to calibrate these molar absorptivities. The most important uses of this technique may stem from its applicability to microsamples (100 m) and to the determination of the concentrations of hydroxyl groups and molecular water in quenched silicate melts.Hydroxyl groups are the dominant hydrogen-bearing species in water-bearing glasses at low total water contents, but molecular H2O was detected in all samples with 0.5 weight percent total water. The concentration of hydroxyl groups increases rapidly with total water content at low total water contents, but more slowly at higher (>3 wt. %) total water contents; it may level off or even decrease at high total water contents. The concentration of molecular water increases slowly at low total water contents and more rapidly at high total water contents. More water is dissolved as molecular water than as hydroxyl groups at total water contents greater than 4 wt. %. Molecular water in these glasses is probably structurally bound rather than present as fluid inclusions as a separate phase, since ice bands were not observed in spectra taken at 78K and since samples were free of visible bubbles.It is proposed that the speciation of water in silicate glass formed by rapid quenching from melt equilibrated at high temperatures reflects that of the melt. According to this hypothesis, neither high water contents nor high pressures are needed to stabilize substantial quantities of molecular water in melts. This hypothesis, that water dissolves in silicate melts as both molecular water and hydroxyl groups in proportions similar to those measured in waterbearing glasses, can explain the variations in viscosity, electrical conductivity, diffusivity of water, diffusivity of cesium, and phase relationships that are observed in melts as functions of total water content. It also explains the observation that at vapor-saturation at high pressures, where most of the dissolved water is expected to be present as molecular water, water solubilities are similar for all melts but that at low pressures and water contents, where most dissolved water is present in dissociated form as hydroxyl groups, vapor-saturated water solubilities differ for different melt compositions. The linear relationship between water fugacity and the square of the mole fraction of total dissolved water observed for silicate melts at low water contents and the observed deviations from this linear relationship at high total water contents can be accounted for by this hypothesis.  相似文献   

3.
Water in Albitic Glasses   总被引：2，自引：1，他引：2  
Infrared spectroscopy has been calibrated to provide a preciseand accurate method for determining the concentrations of molecularwater and hydroxyl groups in hydrous albitic glasses. At totalwater contents less than 4 wt.%, most of the water is dissolvedas hydroxyl groups; at higher total water contents, molecularwater becomes the dominant species. For total water contentsabove 4 wt.%, the amount of water dissolved as hydroxyl groupsis nearly constant at about 2 wt.% and additional water is incorporatedas molecular water. These trends in the concentrations of theH-bearing species are similar to those observed in other silicateglasses using infrared and NMR spectroscopies. The ratio ofmolecular water to hydroxyl groups at a given total water contentis independent of the pressure and only weakly dependent onthe temperature of equilibration. Molecular water and hydroxyl group concentrations in glassesprovide constraints on the dissolution mechanisms of water insilicate liquids. Several mixing models involving homogeneousequilibria of the form H2O+O2– = 2OH– among meltspecies in albitic melts have been developed. These models canaccount for the measured species concentrations if the effectsof non-ideal behavior or mixing of polymerized units are included,or by allowing for several different anhydrous species. We used two thermodynamic models of hydrous albitic melts tocalculate phase equilibria. The first assumes that Henry's lawholds for molecular water in albitic liquids; i.e. that theactivity of molecular water in the melt is proportional to itsmole fraction as determined by infrared spectroscopy. The seconddescribes the speciation and thermodynamics of hydrous albiticmelts using the formalism of a strictly regular solution. Thesemodels can account reasonably well for the position of the vapor-saturatedsolidus of high albite and the pressure and temperature dependenceof the solubility of water in albitic melts. To the extent thatthese models are successful, our approach provides a directlink between measured species concentrations in hydrous albiticglasses and the macroscopic thermodyn amic properties of theNaAlSi3O8-H2O system.  相似文献   

4.
Quantification of water content in silicate glasses is of vital significance in understanding magma evolution and metamorphic anataxis. Here we provide a method for the determination of total dissolved water content and water speciation in silicate melts by confocal laser Raman spectrometry based on a set of hydrous rhyolitic glasses. A series of alumino-silicate glasses with water contents from 0.33 to 9.05% m/m were synthesised in a piston cylinder apparatus. Synchrotron-FTIR mapping shows that these glasses have relatively homogeneous distributions of dissolved water. Total water contents of the glasses were precisely measured by TC/EA-MS and FTIR. Both external and internal calibration were established for the quantitative analysis of water content and water speciation in the silicate glasses based on excellent linear correlation between total dissolved water content and integrated area of the water Raman band. Furthermore, by decomposing the total water Raman bands into four Gaussians components, the relative concentration of water speciation (OH groups and molecules H2Om) dissolved in the glasses was determined with a similar trend to water speciation data derived from FTIR. We suggest that the relative concentration of water speciation can be estimated in rhyolitic glasses with 4–8% m/m H2O. Our work provides an accurate method to determine total water content and a potential tool to limit the relative concentration of water speciation dissolved in silicic glasses.  相似文献   

5.
Water speciation in rhyolitic melts with dissolved water ranging from 0.8 to 4 wt% under high pressure was investigated. Samples were heated in a piston-cylinder apparatus at 624-1027 K and 0.94-2.83 GPa for sufficient time to equilibrate hydrous species (molecular H2O and hydroxyl group, H2Om + O ? 2OH) in the melts and then quenched roughly isobarically. The concentrations of both hydrous species in the quenched glasses were measured with Fourier transform infrared (FTIR) spectroscopy. For the samples with total water content less than 2.7 wt%, the equilibrium constant (K) is independent of total H2O concentration. Incorporating samples with higher water contents, the equilibrium constant depends on total H2O content, and a regular solution model is used to describe the dependence. K changes with pressure nonmonotonically for samples with a given water content at a given temperature. The equilibrium constant does not change much from ambient pressure to 1 GPa, but it increases significantly from 1 to 3 GPa. In other words, more molecular H2O reacts to form hydroxyl groups as pressure increases from 1 GPa, which is consistent with breakage of tetrahedral aluminosilicate units due to compression of the melt induced by high pressure. The effect of 1.9 GPa (from 0.94 to 2.83 GPa) on the equilibrium constant at 873 K is equivalent to a temperature effect of 49 K (from 873 K to 922 K) at 0.94 GPa. The results can be used to evaluate the role of speciation in water diffusion, to estimate the apparent equilibrium temperature, and to infer viscosity of hydrous rhyolitic melts under high pressure.  相似文献   

6.
The solubility of CO2 in dacitic melts equilibrated with H2O-CO2 fluids was experimentally investigated at 1250°C and 100 to 500 MPa. CO2 is dissolved in dacitic glasses as molecular CO2 and carbonate. The quantification of total CO2 in the glasses by mid-infrared (MIR) spectroscopy is difficult because the weak carbonate bands at 1430 and 1530 cm−1 can not be reliably separated from background features in the spectra. Furthermore, the ratio of CO2,mol/carbonate in the quenched glasses strongly decreases with increasing water content. Due to the difficulties in quantifying CO2 species concentrations from the MIR spectra we have measured total CO2 contents of dacitic glasses by secondary ion mass spectrometry (SIMS).At all pressures, the dependence of CO2 solubility in dacitic melts on xfluidCO2,total shows a strong positive deviation from linearity with almost constant CO2 solubility at xCO2fluid > 0.8 (maximum CO2 solubility of 795 ± 41, 1376 ± 73 and 2949 ± 166 ppm at 100, 200 and 500 MPa, respectively), indicating that dissolved water strongly enhances the solubility of CO2. A similar nonlinear variation of CO2 solubility with xCO2fluid has been observed for rhyolitic melts in which carbon dioxide is incorporated exclusively as molecular CO2 (Tamic et al., 2001). We infer that water species in the melt do not only stabilize carbonate groups as has been suggested earlier but also CO2 molecules.A thermodynamic model describing the dependence of the CO2 solubility in hydrous rhyolitic and dacitic melts on T, P, fCO2 and the mol fraction of water in the melt (xwater) has been developed. An exponential variation of the equilibrium constant K1 with xwater is proposed to account for the nonlinear dependence of xCO2,totalmelt on xCO2fluid. The model reproduces the CO2 solubility data for dacitic melts within ±14% relative and the data for rhyolitic melts within 10% relative in the pressure range 100-500 MPa (except for six outliers at low xCO2fluid). Data obtained for rhyolitic melts at 75 MPa and 850°C show a stronger deviation from the model, suggesting a change in the solubility behavior of CO2 at low pressures (a Henrian behavior of the CO2 solubility is observed at low pressure and low H2O concentrations in the melt). We recommend to use our model only in the pressure range 100-500 MPa and in the xCO2fluid range 0.1-0.95. The thermodynamic modeling indicates that the partial molar volume of total CO2 is much lower in rhyolitic melts (31.7 cm3/mol) than in dacitic melts (46.6 cm3/mol). The dissolution enthalpy for CO2 in hydrous rhyolitic melts was found to be negligible. This result suggests that temperature is of minor importance for CO2 solubility in silicic melts.  相似文献   

7.
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   

8.
Haplobasaltic melts with a 101 kPa dry eutectic composition (An42Di58) and varying water contents were equilibrated with their platinum capsule at 1523 K and 200 MPa in an internally heated pressure vessel (IHPV) equipped with a rapid quench device. Experimental products were inclusion-free glasses representative of the Pt-saturated silicate melts at the experimental conditions. Platinum concentrations were determined using an isotope dilution multicollector inductively coupled plasma mass spectrometer and water contents and distribution by Karl Fischer titration and Fourier transform infrared spectroscopy, respectively.The water content of the melt has no intrinsic effect on platinum solubility, for concentrations between 0.9 wt.% and 4.4 wt.% H2O (saturation). Platinum solubility increases with increasing water content, but this effect is an indirect effect because increasing water content at fixed fH2 (imposed by the IHPV) increases the oxygen fugacity of the experiment.The positive oxygen fugacity dependence of Pt solubility in a hydrous silicate melt at 200 MPa is identical to that in anhydrous melts of the same composition determined in previous studies at 101 kPa. This study extends the range of platinum solubilities to oxygen fugacities lower than was previously possible. Combining the data of this and previous studies, Pt solubility is related to oxygen fugacity (in bar) at 1523 K by the equation:
[Pt]total(ppb)=1389×fO2+7531×(fO2)1/2  相似文献   

9.
Dissolution of water in magmas significantly affects phase relations and physical properties. To shed new light on the this issue, we have applied 1H and 29Si nuclear magnetic resonance (NMR) spectroscopic techniques to hydrous silicate glasses (quenched melts) in the CaO-MgO-SiO2 (CMS), Na2O-SiO2, Na2O-CaO-SiO2 and Li2O-SiO2 systems. We have also carried out ab initio molecular orbital calculations on representative clusters to gain insight into the experimental results.The most prominent result is the identification of a major peak at ∼1.1 to 1.7 ppm in the 1H MAS NMR spectra for all the hydrous CMS glasses. On the basis of experimental NMR data for crystalline phases and ab initio calculation results, this peak can be unambiguously attributed to (Ca,Mg)OH groups. Such OH groups, like free oxygens, are only linked to metal cations, but not part of the silicate network, and are thus referred to as free hydroxyls in the paper. This represents the first direct evidence for a substantial proportion (∼13∼29%) of the dissolved water as free hydroxyl groups in quenched hydrous silicate melts. We have found that free hydroxyls are favored by (1) more depolymerized melts and (2) network-modifying cations of higher field strength (Z/R2: Z: charge, R: cation-oxygen bond length) in the order Mg > Ca > Na. Their formation is expected to cause an increase in the melt polymerization, contrary to the effect of SiOH formation. The 29Si MAS NMR results are consistent with such an interpretation. This water dissolution mechanism could be particularly important for ultramafic and mafic magmas.The 1H MAS NMR spectra for glasses of all the studied compositions contain peaks in the 4 to 17 ppm region, attributable to SiOH of a range of strength of hydrogen bonding and molecular H2O. The relative population of SiOH with strong hydrogen bonding grows with decreasing field strength of the network-modifying cations. Ab initio calculations confirmed that this trend largely reflects hydrogen bonding with nonbridging oxygens.  相似文献   

10.
Carbon dioxide solubilities in H2O-free hydrous silicate melts of natural andesite (CA), tholeiite (K 1921), and olivine nephelinite (OM1) compositions have been determined employing carbon-14 beta-track mapping techniques. The CO2 solubility increases with increasing pressure, temperature, and degree of silica-undersaturation of the silicate melt. At 1650° C, CO2 solubility in CA increases from 1.48±0.05 wt % at 15 kbar to 1.95±0.03 wt % at 30 kbar. The respective solubilities in OM1 are 3.41±0.08 wt % and 7.11±0.10 wt %. The CO2 solubility in K1921 is intermediate between those of CA and OM1 compositions. At lower temperatures, the CO2 contents of these silicate melts are lower, and the pressure dependence of the solubility is less pronounced. The presence of H2O also affects the CO2 solubility (20–30% more CO2 dissolves in hydrous than in H2O-free silicate melts); the solubility curves pass through an isothermal, isobaric maximum at an intermediate CO2/(CO2+H2O) composition of the volatile phase. Under conditions within the upper mantle where carbonate minerals are not stable and CO2 and H2O are present a vapor phase must exist. Because the solubility of CO2 in silicate melts is lower than that of H2O, volatiles must fractionate between the melt and vapor during partial melting of peridotite. Initial low-temperature melts will be more H2O-rich than later high-temperature melts, provided vapor is present during the melting. Published phase equilibrium data indicate that the compositional sequence of melts from peridotite +H2O+CO2 parent will be andesite-tholeiite-nephelinite with increasing temperature at a pressure of about 20 kbar. Examples of this sequence may be found in the Lesser Antilles and in the Indonesian Island Arcs.  相似文献   

11.
Water solubility and speciation have been studied in melts from the system albite-nepheline. Water solubility was determined at PH2O = 200 MPa and T = 1200ºC using Karl Fischer titration (KFT) and weight loss methods. It increases from 5.8?±?0.1 wt. % in the albite melt to 7.25?±?0.25 % in the nepheline melt. The solubility dependence has a sigmoidal shape with a steep increase in the Ab40–Ab60 compositional range. The densities of the hydrous glasses have been measured using the thermal-gradient method. Infrared (IR) combination bands of molecular H2O and hydroxyl groups in these glasses demonstrate a systematic shift to lower frequencies with increasing alkalinity. The data are consistent with the appearance of aluminate species (Al-O-Al fragments) appearing at 40–60 wt.% nepheline (Ab60–Ab40).  相似文献   

12.
Diffusion of water was experimentally investigated for melts of albitic (Ab) and quartz-orthoclasic (Qz29Or71, in wt %) compositions with water contents in the range of 0 to 8.5 wt % at temperatures of 1100 to 1200 °C and at pressures of 1.0 and 5.0 kbar. Apparent chemical diffusion coefficients of water (D water) were determined from concentration-distance profiles measured by FTIR microspectroscopy. Under the same P-T condition and water content the diffusivity of water in albitic, quartz-orthoclasic and haplogranitic (Qz28Ab38 Or34, Nowak and Behrens, this issue) melts is identical within experimental error. Comparison to data published in literature indicates that anhydrous composition only has little influence on the mobility of water in polymerized melts but that the degree of polymerization has a large effect. For instance, Dwater is almost identical for haplogranitic and rhyolitic melts with 0.5–3.5 wt % water at 850 °C but it is two orders of magnitude higher in basaltic than in haplogranitic melts with 0.2–0.5 wt % water at 1300 °C. Based on the new water diffusivity data, recently published in situ near-infrared spectroscopic data (Nowak 1995; Nowak and Behrens 1995), and viscosity data (Schulze et al. 1996) for hydrous haplogranitic melts current models for water diffusion in silicate melts are critically reviewed. The NIR spectroscopy has indicated isolated OH groups, pairs of OH groups and H2O molecules as hydrous species in polymerized silicate melts. A significant contribution of isolated OH groups to the transport of water is excluded for water contents above 10 ppm by comparison of viscosity and water diffusion data and by inspection of concentration profiles from trace water diffusion. Spectroscopic measurements have indicated that the interconversion of H2O molecules and OH pairs is relatively fast in silicate glasses and melts even at low temperature and it is inferred that this reaction is an active step for migration of water. However, direct jumps of H2O molecules from one cavity within the silicate network to another one can not be excluded. Thus, we favour a model in which water migrates by the interconversion reaction and, possibly, small sequences of direct jumps of H2O molecules. In this model, immobilization of water results from dissociation of the OH pairs. Assuming that the frequency of the interconversion reaction is faster than that of diffusive jumps, OH pairs and water molecules can be treated as a single diffusing species having an effective diffusion coefficient . The shape of curves of Dwater versus water content implies that increases with water content. The change from linear to exponential dependence of Dwater between 2 and 3 wt % water is attributed to the influence of the dissociation reaction at low water content and to the modification of the melt structure by incorporation of OH groups. Received: 26 March 1996 / Accepted: 23 August 1996  相似文献   

13.
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   

14.
The influence of water on melting of mantle peridotite   总被引：47，自引：8，他引：39  
This experimental study examines the effects of variable concentrations of dissolved H2O on the compositions of silicate melts and their coexisting mineral assemblage of olivine + orthopyroxene ± clinopyroxene ± spinel ± garnet. Experiments were performed at pressures of 1.2 to 2.0 GPa and temperatures of 1100 to 1345 °C, with up to ∼12 wt% H2O dissolved in the liquid. The effects of increasing the concentration of dissolved H2O on the major element compositions of melts in equilibrium with a spinel lherzolite mineral assemblage are to decrease the concentrations of SiO2, FeO, MgO, and CaO. The concentration of Al2O3 is unaffected. The lower SiO2 contents of the hydrous melts result from an increase in the activity coefficient for SiO2 with increasing dissolved H2O. The lower concentrations of FeO and MgO result from the lower temperatures at which H2O-bearing melts coexist with mantle minerals as compared to anhydrous melts. These compositional changes produce an elevated SiO2/(MgO + FeO) ratio in hydrous peridotite partial melts, making them relatively SiO2 rich when compared to anhydrous melts on a volatile-free basis. Hydrous peridotite melting reactions are affected primarily by the lowered mantle solidus. Temperature-induced compositional variations in coexisting pyroxenes lower the proportion of clinopyroxene entering the melt relative to orthopyroxene. Isobaric batch melting calculations indicate that fluid-undersaturated peridotite melting is characterized by significantly lower melt productivity than anhydrous peridotite melting, and that the peridotite melting process in subduction zones is strongly influenced by the composition of the H2O-rich component introduced into the mantle wedge from the subducted slab. Received: 7 April 1997 / Accepted: 9 January 1998  相似文献   

15.
The H2O and H2 solubilities in an albite melt at 1200° C and 2 kbar over the entire range of gas phase composition, from pure hydrogen to pure water were studied in gas-media pressure vessels. The water solubility initially increases with increasing hydrogen content until a maximum of 9.19 wt% H2O atXH 2 v =0.1 is reached, withXH 2 v >0.1 the water solubility decreases. The hydrogen solubility curve has a maximum atXH 2 v =0.42 where the concentration reaches 0.206 wt% H2O. Over the entire compositional range1H NMR (nuclear magnetic resonance) spectra show distinct absorption lines due to protons bound to OH groups and to isolated firmly bound water molecules. In NMR and Raman spectra there were no bands attributable to the H–H vibrations of molecular hydrogen. The X-ray photo-electronic spectra of hydrogen-bearing glasses show the Si2p (99 eV) band which corresponds to the zero-valency silicon. The formation of OH groups and molecular water during interaction between hydrogen-bearing fluids and melts under reducing conditions has a qualitative effect, the same as for water dissolution. Another point of interest is that hydrogen-bearing melts undergo more depolymerization than do hydrous melts.  相似文献   

16.
A symmetrical, strictly regular solution model is used to estimate H2O solubilities in silicate melts. The standard state chemical potential of dissolved H2O and the adjustable parameter in the activity coefficient are determined by least squares analyses of data on H2O solubility in silicate melts. The adjustable parameter in the expression for the activity coefficient (In) is a function only of the anhydrous melt composition and eleven values are provided for melts ranging in composition from picrite to rhyolite. At the 95% confidence level, the model should estimate H2O contents to within 4.8% of the amount present if the amount present is less than 10 wt.%. This compares to the reproducibility of 2.25% of the amount present for experimental determinations. To apply the model to rocks and magmas estimates ofT, P, and the fugacity of H2O are required.Variation of the H2O content of the melt changes the activity of other components. Knowledge of this variation removes the requirement that the fugacity of H2O be estimated. Application of the properties of exact differentials to the Gibbs function for the hydrous melt provides an expression relating the chemical potential of a feldspar component to the H2O content of the melt. This expression contains a second adjustable parameter which depends on the anhydrous melt composition. Using this second expression, the H2O content can be estimated ifT, P, and feldspar composition are known. Data are too meagre to evaluate the quantitative success of the second method.  相似文献   

17.
Solubility of Au in Cl- and S-bearing hydrous silicate melts   总被引：2，自引：0，他引：2  
The solubility of Au in Cl- and S-bearing hydrous rhyodacitic and andesitic melts has been experimentally investigated at 1050 °C, 200 MPa and log fO2 close to the Ni/NiO solid oxygen buffer (NNO). The concentrations of Au in the experimental glasses have been determined using Laser Ablation ICP-MS (LA) with special efforts to avoid incorporation of Au micronuggets in the analysis. It is concluded that metal micronuggets are an experimental artefact and produced by Au partitioning into the fluids during heating with consequent precipitation on fluid dissolution in the melting glass powder. Hence, the micronuggets do not represent quench phases and must be excluded from the analysis. The micro-analytical data obtained by LA show that Au concentrations vary from ∼0.2 to ∼2.5 ppm by weight, generally consistent with the literature data for other melt compositions. The measured Au concentrations increase with increasing amounts of Cl and S dissolved in the silicate melt and show a correlation with the apparent activities of Cl and S in the system. The apparent activities of Cl and S are defined by the simplified linear relationship between volatile concentrations in the melt and activity of volatiles. The maximum activity (a∗ = 1) is assumed to be reached at the saturation of the systems in respect of Cl-rich brine or FeS liquid for Cl and S, respectively. The dependence of Au solubility on the concentrations/activities of Cl and S at the fixed redox conditions shows that Au may form not only oxide- but also Cl- and S-bearing complexes in silicate melts. Furthermore, it indicates that exsolution of S and Cl from the melt by degassing/segregation/crystallization processes may lead to mobilization and extraction of Au into the fluid, liquid and/or mineral phase(s).  相似文献   

18.
The diffusion of water in dacitic and andesitic melts was investigated at temperatures of 1458 to 1858 K and pressures between 0.5 and 1.5 GPa using the diffusion couple technique. Pairs of nominally dry glasses and hydrous glasses containing between 1.5 and 6.3 wt.% dissolved H2O were heated for 60 to 480 s in a piston cylinder apparatus. Concentration profiles of hydrous species (OH groups and H2O molecules) and total water (CH2Ot = sum of OH and H2O) were measured along the cylindrical axis of the diffusion sample using IR microspectroscopy. Electron microprobe traverses show no significant change in relative proportions of anhydrous components along H2O profiles, indicating that our data can be treated as effective binary interdiffusion between H2O and the rest of the silicate melt. Bulk water diffusivity (DH2Ot) was derived from profiles of total water using a modified Boltzmann-Matano method as well as using fittings assuming a functional relationship between DH2Ot and CH2Ot. In dacitic melts DH2Ot is proportional to CH2Ot up to 6 wt.%. In andesitic melts the dependence of DH2Ot on CH2Ot is less pronounced. A pressure effect on water diffusivity could not be resolved for either dacitic or andesitic melt in the range 0.5 to 1.5 GPa. Combining our results with previous studies on water diffusion in rhyolite and basalt show that for a given water content DH2Ot increases monotonically with increasing melt depolymerization at temperatures >1500 K. Assuming an Arrhenian behavior in the whole compositional range, the following formulation was derived to estimate DH2Ot (m2/s) at 1 wt.% H2Ot in melts with rhyolitic to andesitic composition as a function of T (K), P (MPa) and S (wt.% SiO2):
  相似文献   

19.
A suite of six hydrous (7 wt.% H2O) sodium silicate glasses spanning sodium octasilicate to sodium disilicate in composition were analyzed using 29Si single pulse (SP) magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy, 1H-29Si cross polarization (CP) MAS NMR, and fast MAS 1H-NMR. From the 29Si SPMAS data it is observed that at low sodium compositions dissolved water significantly depolymerizes the silicate network. At higher sodium contents, however, dissolved H2O does not affect a significant increase in depolymerization over that predicted based on the Na/Si ratio alone. The fast MAS 1H-NMR data reveal considerable complexity in proton environments in each of the glasses studied. The fast MAS 1H-NMR spectra of the highest sodium concentration glasses do not exhibit evidence of signficantly greater fractions of dissolved water as molecular H2O than the lower sodium concentration glasses requiring that the decrease in polymerization at high sodium contents involves a change in sodium solution mechanism. Variable contact time 1H-29Si cross polarization (CP) MAS NMR data reveal an increase in the rotating frame spin lattice relaxation rate constant (T1ρ*) for various Qn species with increasing sodium content that correlates with a reduction in the average 1H-29Si coupling strength. At the highest sodium concentration, however, T1ρ* drops significantly, consistent with a change in the Na2O solution mechanism.  相似文献   

20.
We have measured the water solubility between 1 atmosphere and 5 kilobars for a calcium aluminosilicate melt of molar composition CaO 0.28, Al2O3 0.06, SiO2 0.66 (An9Wo38Qz53). The water contents were measured via thermogravimetric analysis of isobarically quenched glasses, and range from 0.121 wt% H2O near 1 aim to 9.25 wt% H2O at 5 kilobars. The molar water solubility lies between those of SiO2 and albite melts below around three kilobars, and crosses the albite solubility curve above this pressure. The present results are compared with data in the literature on related calcium aluminosilicate melts. There seems to be little variation of water solubility with composition for calcium aluminosilicate melts, unlike analogous alkali aluminosilicate compositions. Examination of the data suggests that there may be a maximum in molar water solubility along the albite-anorthite join.  相似文献   

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