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1.
Near-infrared (NIR) absorption bands related to total water (4000 and 7050 cm−1), OH groups (4500 cm−1) and molecular H2O (5200 cm−1) were studied in two polymerised glasses, a synthetic albitic composition and a natural obsidian. The water contents of the glasses were determined using Karl Fischer titration. Molar absorption coefficients were calculated for each of the bands using albitic glasses containing between 0.54 and 9.16 wt.% H2O and rhyolitic glasses containing between 0.97 and 9.20 wt.% H2O. Different combinations of baseline type and intensity measure (peak height/area) for the combination bands at 4500 and 5200 cm−1 were used to investigate the effect of evaluation procedure on calculated hydrous species concentrations. Total water contents calculated using each of the baseline/molar absorption coefficient combinations agree to within 5.8% relative for rhyolitic and 6.5% relative for albitic glasses (maximum absolute differences of 0.08 and 0.15 wt.% H2O, respectively). In glasses with water contents >1 wt.%, calculated hydrous species concentrations vary by up to 17% relative for OH and 11% relative for H2O (maximum absolute differences of 0.33 and 0.43 wt.% H2O, respectively). This variation in calculated species concentrations is typically greater in rhyolitic glasses than albitic. In situ, micro-FTIR analysis at 300 and 100 K was used to investigate the effect of varying temperature on the NIR spectra of the glasses. The linear and integral molar absorption coefficients for each of the bands were recalculated from the 100 K spectra, and were found to vary systematically from the 300 K values. Linear molar absorption coefficients for the 4000 and 7050 cm−1 bands decrease by 16–20% and integral molar absorption coefficients by up to 30%. Depending on glass composition and baseline type, the integral molar absorption coefficients for the absorption bands related to OH groups and molecular H2O change by up to −5.8 and +7.4%, respectively, while linear molar absorption coefficients show less variation, with a maximum change of ∼4%. Using the new molar absorption coefficients for the combination bands to calculate species concentrations at 100 K, the maximum change in species concentration is 0.08 wt.% H2O, compared with 0.39 wt.% which would be calculated if constant values were assumed for the combination band molar absorption coefficients. Almost all the changes in the spectra can therefore be interpreted in terms of changing molar absorption coefficient, rather than interconversion between hydrous species. Received: 17 December 1998 / Revised, accepted 8 July 1999  相似文献   

2.
To interpret the degassing of F-bearing felsic magmas, the solubilities of H2O, NaCl, and KCl in topaz rhyolite liquids have been investigated experimentally at 2000, 500, and ≈1 bar and 700° to 975 °C. Chloride solubility in these liquids increases with decreasing H2O activity, increasing pressure, increasing F content of the liquid from 0.2 to 1.2 wt% F, and increasing the molar ratio of ((Al + Na + Ca + Mg)/Si). Small quantities of Cl− exert a strong influence on the exsolution of magmatic volatile phases (MVPs) from F-bearing topaz rhyolite melts at shallow crustal pressures. Water- and chloride-bearing volatile phases, such as vapor, brine, or fluid, exsolve from F-enriched silicate liquids containing as little as 1 wt% H2O and 0.2 to 0.6 wt% Cl at 2000 bar compared with 5 to 6 wt% H2O required for volatile phase exsolution in chloride-free liquids. The maximum solubility of Cl− in H2O-poor silicate liquids at 500 and 2000 bar is not related to the maximum solubility of H2O in chloride-poor liquids by simple linear and negative relationships; there are strong positive deviations from ideality in the activities of each volatile in both the silicate liquid and the MVP(s). Plots of H2O versus Cl− in rhyolite liquids, for experiments conducted at 500 bar and 910°–930 °C, show a distinct 90° break-in-slope pattern that is indicative of coexisting vapor and brine under closed-system conditions. The presence of two MVPs buffers the H2O and Cl− concentrations of the silicate liquids. Comparison of these experimentally-determined volatile solubilities with the pre-eruptive H2O and Cl− concentrations of five North American topaz and tin rhyolite melts, determined from melt inclusion compositions, provides evidence for the exsolution of MVPs from felsic magmas. One of these, the Cerro el Lobo magma, appears to have exsolved alkali chloride-bearing vapor plus brine or a single supercritical fluid phase prior to entrapment of the melt inclusions and prior to eruption. Received: 6 November 1995 / Accepted: 29 January 1998  相似文献   

3.
 The speciation of water dissolved in glasses along the join NaAlSi3O8-KAlSi3O8 has been investigated using infrared spectroscopy. Hydrous melts have been hydrothermally synthesized by chemical equilibration of cylinders of bubble-free anhydrous start glasses with water at 1040° C and 2 kbar. These melts have been isobarically and rapidly (200° C/s) “drop”-quenched to room temperature and then subsequently depressurized. The speciation of water in the quenched glasses reflects the state of water speciation at a temperature (the so-called fictive temperature) where the quenched-in structure of the glasses closely corresponds to the melt structure at equilibrium. This fictive temperature is detectable as the macroscopically measureable glass transition temperature of these melt compositions. A separate set of experiments using vesicular samples of the same chemistry has precisely defined the glass transition temperature of these melts (±5° C) on the basis of homogenization temperatures for water-filled fluid inclusions (Romano et al. 1994). The spectroscopic data on the speciation of water in these quenched glasses has been quantified using experimentally determined absorptivities for OH and H2O for each individual melt composition. The knowledge of glass transition temperatures, together with quantitative speciation data permits an analysis of the temperature dependence of the water speciation over the 113° C range of fictive temperatures obtained for these water-saturated melts. The variation of water speciation, cast as the equilibrium constant K where K = [H2O] [O m ]/[OH]2 is plotted versus the fictive temperature of the melt to obtain the temperature dependence of speciation. Such a plot describes a single linear trend of the logarithm of the equilibrium constant versus reciprocal temperature, implying that the exchange of K for Na has little influence on melt speciation of water. The enthalpy derived from temperature dependence is 36.5(±5) kJ/mol. The results indicate a large variation in speciation with temperature and an insensitivity of the speciation to the K–Na exchange. Received: 8 March 1995/Accepted: 6 June 1995  相似文献   

4.
The modeling of the solubility of water and carbon dioxide in silicate liquids (flash problem) is performed by assuming mechanical, thermal, and chemical equilibrium between the liquid magma and the gas phase. The liquid phase is treated as a mixture of ten silicate components + H2O or CO2, and the gas phase as a pure H2O or CO2. A general model for the solubility of a volatile component in a liquid is adopted. This requires the definition of a mixing equation for the excess Gibbs free energy of the liquid phase and an appropriate reference state for the dissolved volatile. To constrain the model parameters and identify the most appropriate form of the solubility equations for each dissolved volatile, a large number of experimental solubility determinations (640 for H2O and 263 for CO2) have been used. These determinations cover a large region of the P-T-composition space of interest. The resultant water and carbon dioxide solubility models differ in that the water model is regular and isometric, and the carbon dioxide model is regular and non-isometric. This difference is consistent with the different speciation modalities of the two volatiles in the silicate liquids, producing a composition-independent partial molar volume of dissolved water and a composition-dependent partial molar volume of dissolved carbon dioxide. The H2O solubility model may be applied to natural magmas of virtually any composition in the P-T range 0.1 MPa–1 GPa and > 1000 K, whereas the CO2 solubility model may be applied to several GPa pressures. The general consistency of the water solubility data and their relatively large number as compared to the calibrated model parameters (11) contrast with the large inconsistencies of the carbon dioxide solubility determinations and their low number with respect to the CO2 model parameters (22). As a result, most of the solubility data in the database are reproduced within 10% of approximation in the case of water, and 30% in the case of carbon dioxide. When compared with the experimental data, the H2O and CO2 solubility models correctly predict many features of the saturation surface in the P-T-composition space, including the change from retrograde to prograde H2O solubility in albitic liquids with increasing pressure, the so-called alkali effect, the increasing CO2 solubility with increasing degree of silica undersaturation, the Henrian behavior of CO2 in most silicate liquids up to about 30–50 MPa, and the proportionality between the fugacity in the gas phase, or the saturation activity in the liquid phase, and the square of the mole fraction of the dissolved volatile found in some unrelated silicate liquid compositions. Received: 21 August 1995 / Accepted: 8 July 1996  相似文献   

5.
The Beer–Lambert law is traditionally used to determine water and carbon concentrations in glasses from their infrared (IR) spectra. In practice, this method requires estimation of the thickness and density of the glass as well as the calibration of the molecular absorptivities of the species concerned. All of these parameters can be sources of practical difficulties and analytical uncertainty. These weaknesses in the application of the Beer–Lambert law have been overcome by an empirical analysis of the infrared spectra. Using a set of 292 spectra obtained on 113 natural and experimental tholeiitic glasses (SiO2 48.5–51 wt%; water contents 0–4000 ppm H2O), it can be shown that the thickness–density (ρ d) product of a glass sample can be directly and reliably inferred from its IR spectrum. This allows the Beer–Lambert law to be rewritten. The new form no longer requires thickness or density estimations to determine volatile contents. Moreover, if needed, the thickness of the glass slab can also be accurately determined from the IR spectra. This new method is developed for quantitative determination of water concentrations in MORB glasses but can also be applied to any minor species (carbon, sulfur, etc.) provided it is active in the IR domain and that a suitable independent frequency of IR absorption can be identified. Precision is about 60 ppm H2O on O–H− contents. This method, tested on natural and experimental MORB-type glasses, can be applied to any chemical composition provided a set of reference spectra is available. Received: 16 September 1999 / Accepted: 18 February 2000  相似文献   

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

7.
Fluorine-, boron- and phosphorus-rich pegmatites of the Variscan Ehrenfriedersdorf complex crystallized over a temperature range from about 700 to 500 °C at a pressure of about 1 kbar. Pegmatite quartz crystals continuously trapped two different types of melt inclusions during cooling and growth: a silicate-rich H2O-poor melt and a silicate-poor H2O-rich melt. Both melts were simultaneously trapped on the solvus boundaries of the silicate (+ fluorine + boron + phosphorus) − water system. The partially crystallized melt inclusions were rehomogenized at 1 kbar between 500 and 712 °C in steps of 50 °C by conventional rapid-quench hydrothermal experiments. Glasses of completely rehomogenized inclusions were analyzed for H2O by Raman spectroscopy, and for major and some trace elements by EMP (electron microprobe). Both types of melt inclusions define a solvus boundary in an XH2O–T pseudobinary system. At 500 °C, the silicate-rich melt contains about 2.5 wt% H2O, and the conjugate water-rich melt about 47 wt% H2O. The solvus closes rapidly with increasing temperature. At 650 °C, the water contents are about 10 and 32 wt%, respectively. Complete miscibility is attained at the critical point: 712 °C and 21.5 wt% H2O. Many pegmatites show high concentrations of F, B, and P, this is particularly true for those pegmatites associated with highly evolved peraluminous granites. The presence of these elements dramatically reduces the critical pressure for fluid–melt systems. At shallow intrusion levels, at T ≥ 720 °C, water is infinitely soluble in a F-, B-, and P-rich melt. Simple cooling induces a separation into two coexisting melts, accompanied with strong element fractionation. On the water-rich side of the solvus, very volatile-rich melts are produced that have vastly different physical properties as compared to “normal” silicate melts. The density, viscosity, diffusivity, and mobility of such hyper-aqueous melts under these conditions are more comparable to an aqueous fluid. Received: 15 September 1999 / Accepted: 10 December 1999  相似文献   

8.
Activities of CoO in (Co,Mn)O solid solutions in contact with metallic Co have been determined on ten compositions ranging from 0.12 to 0.84 XCoO in order to calibrate the divariant equilibrium between (Co,Mn)O oxide solutions and Co metal as an oxygen fugacity sensor for application in experimental petrology. Experiments were conducted over the temperature range 900–1300 K at 1 bar, using an electrochemical technique with oxygen-specific calcia-stabilized zirconia (CSZ) electrolytes. Co + CoO or Fe + FeO was used as the reference electrode. Compositions of the (Co,Mn)O solid solutions were measured after each run by electron microprobe, and these were checked for internal consistency by measuring the lattice parameter by X-ray diffraction. Activity–composition relations were fitted to the Redlich–Kister formalism. (Co,Mn)O solid solutions exhibit slight positive deviations from ideality, which are symmetrical (corresponding to a regular solution mixing model) across the entire composition range with A0 G = 3690(±47) Jmol−1. Excess entropies and enthalpies were also derived from the emf data and gave Sex=0.77(±0.08) JK−1 mol−1 and Hex=4558(±90) Jmol−1 respectively. The experimental data from this study have been used to formulate the (Co,Mn)O/Co oxygen fugacity sensor to give an expression: where μO2 CoCoO=−492,186 + 509.322 T − 53.284 T lnT + 0.02518 T2, taken from O'Neill and Pownceby (1993). Received: 10 September 1999 / Accepted: 4 April 2000  相似文献   

9.
The system KAlO2–MgO–SiO2–H2O–CO2 has long been used as a model for the processes of granulite-facies metamorphism and the development of orthopyroxene-bearing mineral assemblages through the breakdown of biotite-bearing assemblages. There has been considerable controversy regarding the role of carbon dioxide in metamorphism and partial melting. We performed new experiments in this system (at pressures of 342 to 1500 MPa with T between 710 and 1045 °C and X Fl H2O between 0.05 and 1.00), accurately locating most of the dehydration and melting equilibria in P-T-X Fl H2O space. The most important primary result is that the univariant reaction Phl + Qtz + Fl = En + Sa + melt must be almost coincident with the fluid-absent reaction (Phl + Qtz = En + Sa + melt) in the CO2-free subsystem. In conjunction with the results of previous measurements of CO2 solubility in silicate melts and phase equilibrium experiments, our theoretical analysis and experiments suggest that CO2 cannot act as a flux for partial melting. Crustal melting in the presence of H2O–CO2 mixed fluids will always occur at temperatures higher than with pure H2O fluid present. Magmas produced by such melting will be granitic (s.l.) in composition, with relatively high SiO2 and low MgO contents, irrespective of the H2O–CO2 ratio in any coexisting fluid phase. We find no evidence that lamprophyric magmas could be generated by partial fusion of quartz-saturated crustal rocks. The granitic melts formed will not contain appreciable dissolved CO2. The channelled passage of hot CO2-rich fluids can cause local dehydration of the rocks through which they pass. In rock-dominated (as opposed to fluid-dominated) systems, minor partial melting can also occur in veins initially filled with CO2-rich fluid, as dehydration and local disequilibrium drive the fluid towards H2O-rich compositions. However, CO2 is unlikely to be a significant agent in promoting regional granulite-grade metamorphism, melting, magma generation, metasomatism or long-range silicate mass transfer in Earth's crust. The most viable model for the development of granulite-facies rocks involves the processes of fluid-absent partial melting and withdrawal of the melt phase to higher crustal levels. Received: 28 November 1996 / Accepted: 25 June 1997  相似文献   

10.
To assist in the assignment and interpretation of 23Na NMR spectra in silicate and aluminosilicate minerals and glasses we have calculated the 23Na NMR shieldings and the electric field gradients (EFG) at the Na for a number of Na-containing species. Included are Na(OH2) n +, n = 1, 2, 4, 5, 6 and 8, and Na+ complexes with SiH3OH, SiH3ONa and O(SiH3)2. We have also evaluated shieldings and EFGs for Na-centered clusters extracted from crystalline Na2SiO3 and anhydrous sodalite, Na6[AlSiO4]6. Using 6-31G* SCF optimized geometries and the GIAO method with a 6-31G* basis set [and 6-311(2d,p) bases for the smaller clusters] we find a calculated increase in shielding with coordination number (CN) for the Na(OH2) n +, n = 4, 6, 8 series that agrees reasonably well with experimental trends. Calculated changes in the Na shielding as water is replaced by bridging or nonbridging silicate O atoms are also consistent with experimental observations. The deshielding of Na (with respect to gas-phase Na+) which is produced by an O-containing ligand is a strongly decreasing function of the R(Na–O) and a weakly decreasing function of the underbonding or free valence of the O. Deshielding contributions to the isotropic shielding from different ligands are additive to good approximation for low CN species, so that the total deshielding can be calculated accurately by summing the contributions from the individual ligands. However for the larger CN species the directly calculated deshieldings are substantially smaller than those obtained using such an additivity approximation. We further test this approximation by calculating the deshieldings for Na in 12 different sites in silicate and aluminosilicate minerals which have recently been studied experimentally, using our calculated deshielding contributions for individual O-containing ligands and experimental values for the Na–O distances. Correlation coefficients between the experimental shifts and the calculated deshieldings are around 0.9 and the slope of the correlation is almost 1.0 . Calculations on large Na-centered clusters extracted from the crystal structures of Na2SiO3 and anhydrous sodalite reproduce the experimental values for both NMR shieldings and electric field gradients but at considerable computational cost. Comparison with recent 23Na NMR studies on hydrous albite glasses indicates that coordination of either H2O or OH− to the Na could give the magnitude of deshielding observed, depending upon the detailed Na–O distances within the hydrous glass. Received: 31 December 1998 / Revised, accepted: 11 May 1999  相似文献   

11.
 The lattice constants of paragonite-2M1, NaAl2(AlSi3)O10(OH)2, were determined to 800 °C by the single-crystal diffraction method. Mean thermal expansion coefficients, in the range 25–600 °C, were: αa = 1.51(8) × 10−5, αb = 1.94(6) × 10−5, αc = 2.15(7) ×  10−5 °C−1, and αV = 5.9(2) × 10−5 °C−1. At T higher than 600 °C, cell parameters showed a change in expansion rate due to a dehydroxylation process. The structural refinements of natural paragonite, carried out at 25, 210, 450 and 600 °C, before dehydroxylation, showed that the larger thermal expansion along the c parameter was mainly due to interlayer thickness dilatation. In the 25–600 °C range, Si,Al tetrahedra remained quite unchanged, whereas the other polyhedra expanded linearly with expansion rate proportional to their volume. The polyhedron around the interlayer cation Na became more regular with temperature. Tetrahedral rotation angle α changed from 16.2 to 12.9°. The structure of the new phase, nominally NaAl2 (AlSi3)O11, obtained as a consequence of dehydroxylation, had a cell volume 4.2% larger than that of paragonite. It was refined at room temperature and its expansion coefficients determined in the range 25–800 °C. The most significant structural difference from paragonite was the presence of Al in fivefold coordination, according to a distorted trigonal bipyramid. Results confirm the structural effects of the dehydration mechanism of micas and dioctahedral 2:1 layer silicates. By combining thermal expansion and compressibility data, the following approximate equation of state in the PTV space was obtained for paragonite: V/V 0 = 1 + 5.9(2) × 10−5 T(°C) − 0.00153(4) P(kbar). Received: 12 July 1999 / Revised, accepted: 7 December 1999  相似文献   

12.
In the Mazowe area some 40 km NW of Harare in Zimbabwe, gold mineralization is hosted in a variety of lithologies of the Archean Harare-Bindura-Shamva greenstone belt, in structures related to the late Archean regional D2/3 event. Conspicuous mineralzogical differences exist between the mines; the mainly granodiorite-hosted workings at Mazowe mine are on pyrite-rich reefs, mines of the Bernheim group have metabasalt host rocks and are characterized by arsenopyrite-rich ores, and Stori's Golden Shaft and Alice mine, both in metabasalts, work sulfide-poor quartz veins. In contrast to the mineralogical diversity, near-identical fluid inventories were found at the different mines. Both H2O-CO2-CH4 fluids of low salinity, and highly saline fluids are present and are regarded to indicate fluid mixing during the formation of the deposits. Notably, these fluid compositions in the Mazowe gold field markedly contrast to ore fluids “typical” of Archean mesothermal gold deposits on other cratons. Stable isotope compositions of quartz from the various deposits (δ18O=10.8 to 13.2‰ SMOW), calcite (δ18O=9.5 to 11.9‰ SMOW and δ13C=−3.2 to −8.0‰ PDB), inclusion water (δD=−28 to −40‰ SMOW) and sulfides (δ34S=1.3 to 3.2‰ CDT) are uniform within the range typical for Archean lode gold deposits worldwide. The fluid and stable isotope compositions support the statement that the mineralization in the Mazowe gold field formed from relatively reduced fluids with a “metamorphic” signature during a single event of gold mineralization. Microthermometric data further indicate that the deposits formed in the PT range of 1.65–2.3 kbar and 250–380 °C. Ages obtained by using the Sm/Nd and Rb/Sr isotope systems on scheelites are 2604 ± 84 Ma for the mineralization at Stori's Golden Shaft mine, and 2.40 ± 0.20 Ga for Mazowe mine. The Archean age at Stori's is regarded as close to the true age of gold mineralization in the area, whereas the Proterozoic age at Mazowe mine probably reflects later resetting. Received: 30 September 1998 / Accepted: 17 August 1999  相似文献   

13.
2 study area was assessed with respect to its heavy-metal load on the basis of the current guideline values. The heavy-metal loads of the soils in the study area have ranges of <0.2–200 mg kg−1 for Cd, <10–30,000 mg kg−1 for Pb, 7–10,000 mg kg−1 for Cu and 50–55,000 mg kg−1 for Zn. Mobility of the heavy metals was determined by extraction at different pH values. The acid neutralisation capacity (ANCx) at these pH values was also determined to estimate the probability that the pH can drop to pH=x. The ANC values in the study area ranged from 6 to 3000 mmol H+ kg−1, from −33 to 800 mmol H+ kg−1 and from −74 to 160 mmol H+ kg−1 for ANC3.5, ANC5.0 and ANC6.2, respectively. Together with pedological data, the extraction experiments permit differentiation between soil units that have been placed in the same environmental hazard class on the basis of total heavy-metal loads. Received: 10 August 1998 · Accepted: 14 August 1999  相似文献   

14.
The solubility behavior of phosphorus in glasses and melts in the system Na2O-Al2O3-SiO2-P2O5 has been examined as a function of temperature and Al2O3 content with microRaman spectroscopy. The Al2O3 was added (2, 4, 5, 6, and 8 mol% Al2O3) to melts with 80 mol% SiO2 and ∼2 mol% P2O5. The compositions range from peralkaline, via meta-aluminous to peraluminous. Raman spectra were obtained of both the phosphorus-free and phosphorous-bearing glasses and melts between 25 and 1218 °C. The Raman spectrum of Al-free, P-bearing glass exhibits a characteristic strong band near 940 cm−1 assigned to P=O stretching in orthophosphate complexes together with a weaker band near 1000 cm−1 assigned P2O7 complexes. With increasing Al content, the proportion of P2O7 initially increases relative to PO4 and is joined by AlPO4 complexes which exhibit a characteristic P-O stretch mode slightly above 1100 cm−1. The latter complex appears to dominate in meta-aluminosilicate glass and is the only phosphate complex in peraluminous glasses. When P-bearing peralkaline silicate and aluminosilicate glasses are transformed to supercooled melts, there is a rapid decrease in PO4/P2O7 so that in the molten state, PO4 units are barely discernible. The P2O7/AlPO4 abundance ratio in peralkaline compositions increases with increasing temperature. This decrease in PO4/P2O7 with increasing temperature results in depolymerization of the silicate melts. Dissolved P2O5 in peraluminous glass and melts forms AlPO4 complexes only. This solution mechanism has no discernible influence on the aluminosilicate melt structure. There is no effect of temperature on this solution mechanism. Received: 7 October 1997 / Accepted: 11 May 1998  相似文献   

15.
  The diffusivity of water has been investigated for a haplogranitic melt of anhydrous composition Qz28Ab38Or34 (in wt %) at temperatures of 800–1200°C and at pressures of 0.5–5.0 kbar using the diffusion couple technique. Water contents of the starting glass pairs varied between 0 and 9 wt %. Concentration-distance profiles for the different water species (molecular water and hydroxyl groups) were determined by near-infrared microspectroscopy. Because the water speciation of the melt is not quenchable (Nowak 1995; Nowak and Behrens 1995; Shen and Keppler 1995), the diffusivities of the individual species can not be evaluated directly from these profiles. Therefore, apparent chemical diffusion coefficients of water (D water) were determined from the total water profiles using a modified Boltzmann-Matano analysis. The diffusivity of water increases linearly with water content <3 wt % but exponentially at higher water contents. The activation energy decreases from 64 ± 10 kJ/mole for 0.5 wt % water to 46 ± 5 kJ/mole for 4 wt % water but remains constant at higher water contents. A small but systematic decrease of D water with pressure indicates an average activation volume of about 9 cm3/mole. The diffusivity (in cm2/s) can be calculated for given water content (in wt %), T (in K) and P (in kbar) by
in the ranges 1073 K ≤ T ≤ 1473 K; 0.5 kbar ≤ P≤ 5␣kbar; 0.5 wt % ≤ C water ≤ 6 wt %. The absence of alkali concentration gradients in the glasses after the experiments shows that interdiffusion of alkali and H+ or H3O+ gives no contribution to the transport of water in aluminosilicate melts. The H/D interdiffusion coefficients obtained at 800°C and 5 kbar using glass pieces with almost the same molar content of either water or deuterium oxide are almost identical to the chemical diffusivities of water. This indicates that protons are transported by the neutral component H2O under these conditions. Received: 26 March 1996 / Accepted: 23 August 1996  相似文献   

16.
 The polarized single-crystal Raman spectra of synthetic H2O-containing alkali-free beryl were recorded at room and low temperatures, and the polarized single-crystal IR spectra at room temperature. The H2O molecule in the channel cavities is characterized by a Raman-active symmetric stretching vibration (ν1) at 3607 cm−1 and an IR-active asymmetric stretch (ν3) at 3700 cm−1 at room temperature. At low temperatures this ν3 mode is observed in the Raman. Weak ν1 and ν3 modes of a second type of H2O are also observed in the Raman spectra but only at 5 K. The H⋯&middot;H vector of the most abundant type of H2O is parallel to the channel axis of beryl along [0 0 0 1]. The components of the polarizability tensor of the ν1 mode of H2O are similar to, but not exactly the same as, those of a free H2O molecule. The Raman measurements indicate that the H2O molecule is rotationally disordered around [0 0 0 1]. External translation and librational modes of H2O could be observed as overtones with the internal H2O-stretching modes. In the case of the librational motions, normal modes could also be observed directly in the Raman spectra at ∼200 cm−1. The energies of the translational modes can be determined from an analysis of the overtones and are about 9 cm−1 in energy (i.e., Tz). The energies of the librational modes are about 210 cm−1 for Rx and 190 cm−1 for Ry. Received: 8 April 1999 / Accepted: 5 April 2000  相似文献   

17.
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18.
We have experimentally investigated the kinetics of melting of an aplitic leucogranite (quartz+sodic plagioclase of ≈Ab90+K-feldspar+traces of biotite) at 690, 740, and 800°C, all at 200 MPa H2O. Leucogranite cylinders, 3.5 mm in diameter and 7 mm in length, were run in the presence of excess H2O using cold-seal pressure vessels for 11–2,925 h. At 690 and 740°C and any experimental time, and 800°C and short run times, silicate glass (melt at run conditions) occurs as interconnected films along most of the mineral boundaries and in fractures, with the predominant volume occurring along quartz/feldspars boundaries and quartz/plagioclase/K-feldspar triple junctions. Glass film thickness is roughly constant throughout a given experimental charge and increases with experimental temperature and run duration. The results indicate that H2O-saturated partial melting of a quartzo-feldspathic protolith will produce an interconnected melt phase even at very low degrees (<5 vol%) of partial melting. Crystal grain boundaries are therefore completely occluded with melt films even at the lowest degrees of partial melting, resulting in a change in the mechanism of mass transport through the rock from advection of aqueous vapor to diffusion through silicate melt. At 690 and 740°C the compositions of glasses are homogeneous and (at both temperatures) close to, but not on, the H2O-saturated 200 MPa haplogranite eutectic; glass compositions do not change with run duration. At 800°C glasses are heterogeneous and plot away from the minimum, although their molar ratios ASI (=mol Al2O3/CaO+Na2O+K2O) and Al/Na are constant throughout the entire charge at any experimental time. Glass compositions within individual 800°C experiments form linear trends in (wt%) normative quartz–albite–orthoclase space. The linear trends are oriented perpendicular to the 200 MPa H2O haplogranite cotectic line, reflecting nearly constant albite/orthoclase ratio versus variable quartz/feldspar ratio, and have endpoints between the 800°C isotherms on the quartz and feldspar liquidus surfaces. With increasing experimental duration the trends migrate from the potassic side of the minimum toward the bulk rock composition located on the sodic side, due to more rapid (and complete) dissolution of K-feldspar relative to plagioclase. The results indicate that partial melting at or slightly above the solidus (690–740°C) is interface reaction-controlled, and produces disequilibrium melts of near-minimum composition that persist metastably for up to at least 3 months. Relict feldspars show no change in composition or texture, and equilibration between melt and feldspars might take from a few to tens of millions of years. Partial melting at temperatures well above the solidus (800°C) produces heterogeneous, disequilibrium liquids whose compositions are determined by the diffusive transport properties of the melt and local equilibrium with neighboring mineral phases. Feldspars recrystallize and change composition rapidly. Partial melting and equilibration between liquids and feldspars might take from a few to tens of years (H2O-saturated conditions) at these temperatures well above the solidus.  相似文献   

19.
A new approach was developed to measure the water content of silicate glasses using Raman spectroscopy, which is independent of the glass matrix composition and structure. Contrary to previous studies, the compositional range of our studied silicate glasses was not restricted to rhyolites, but included andesitic, basaltic and phonolitic glasses. We used 21 glasses with known water contents for calibration. To reduce the uncertainties caused by the baseline removal and correct for the influence of the glass composition on the spectra, we developed the following strategy: (1) application of a frequency-dependent intensity correction of the Raman spectra; (2) normalization of the water peak using the broad T–O and T–O–T vibration band at 850–1250 cm−1 wavenumbers (instead of the low wavenumber T–O–T broad band, which appeared to be highly sensitive to the FeO content and the degree of polymerization of the melt); (3) normalization of the integrated Si-O band area by the total number of tetrahedral cations and the position of the band maximum. The calibration line shows a ±0.4 wt% uncertainty at one relative standard deviation in the range of 0.8–9.5 wt% water and a wide range of natural melt compositions. This method provides a simple, quick, broadly available and cost-effective way for a quantitative determination of the water content of silicate glasses. Application to silicate melt inclusions yielded data in good agreement with SIMS data.  相似文献   

20.
Raman spectroscopy was used to analyze quantitatively water in silicate glasses and melt inclusions and to monitor H2O–OH speciation. Calibration is based on synthetic glasses with various water contents (0.02–7.67% H2O); water determination and OH–H2O differentiation on the area of the Si–O broad band at 468 cm–1 and the asymmetric O–H band at 3,550 cm–1. Each Raman spectrum has been decomposed into four Gaussian + Lorentzian components centered at 3,330, 3,458, 3,560, and 3,626 cm–1 using the Levenberg–Marquardt algorithm. These components are interpreted to be two different types of H2O molecule sites. The influence of the temperature on the loss of water is more important for molecular water than for the hydroxyl groups. The H2O–OH partition confirms the typical evolution of water speciation in rhyolitic glasses as a function of the bulk water content. Method limitations have been studied for the application to natural melt inclusions.Editorial responsibility: T.L Grove  相似文献   

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